WO2012035061A1

WO2012035061A1 - Process for the preparation of 1,2-diamines by intermolecular transfer of two nitrogen groups onto alkenes and intermediates thereof

Info

Publication number: WO2012035061A1
Application number: PCT/EP2011/065929
Authority: WO
Inventors: Kilian MUÑIZ
Original assignee: Institut Catala dInvestigacio Quimica ICIQ
Current assignee: Institut Catala dInvestigacio Quimica ICIQ
Priority date: 2010-09-15
Filing date: 2011-09-14
Publication date: 2012-03-22
Anticipated expiration: 2013-03-15

Abstract

A new process for the diamination of alkenes is provided, as well as the new compounds prepared thereof. A process for the preparation of the primary amines obtained from the diaminated alkenes of the provided preparation process is also provided.

Description

Process for the preparation of 1 ,2-diamines by intermolecular transfer of two nitrogen groups onto alkenes and intermediates thereof.

The present invention relates to processes for the intermolecular transfer of nitrogen groups onto alkenes, the products thereof and their use as intermediates to produce 1 ,2-diamines.

BACKGROUND ART 1 ,2-Diamines represent an important functional group in organic chemistry, that are present in a large variety of natural products, molecules of general pharmaceutical and biological interest, functional metal complexes and catalysts. Accordingly, 1 ,2-diamines constitute an important class of compounds as a result of their useful biological activities and their utility as chiral auxiliaries and ligands in asymmetric synthesis.

The synthesis of these compounds has been mainly developed in the state of the art through a combination of several synthetic steps. Although the direct diamination of alkenes, i.e. by their direct oxidative transformation, is an especially efficient method for the synthesis of such compounds, said methods are rare. In fact, the direct diamination of alkenes has been developed in an intramolecular reaction, where one or two of the two nitrogen atoms to be transferred are contained within a radical substituent connected to the alkene (Sibbald et al., 2009; Hovelmann et al., 2008). Alternatively, it has been developed for alkenes functionalized or activated by the presence of an additional neighbouring double bond, e.g. conjugated dienes, a process known also as diamination of butadienes hence, limited to the synthesis of alkenyl diamines (Bar et al., 2005; Du et al. 2007). Reactions of amino-amides with respect to N to N' acyl migration and formation of cyclic lactams have been disclosed. In particular, it has been found that the direction and speed of migration of N-benzoylethylenediamines is determined by the relative nucleophilicities of the two nitrogen atoms concerned (C.J.M. Stirling 1958).

In summary, current methods for diamination of alkenes are limited to intramolecular processes and to the reactions of functionalized or activated alkenes and/or suffer from limited substrate scope.

There is, accordingly, a need for new processes for the preparation of 1 ,2- diamines from alkenes.

SUMMARY OF THE INVENTION

The inventor has found a process for the preparation of diamines based on carrying out a metal-catalysed intermolecular diamination of alkenes, which can be applied to a great variety of alkenes, either terminal or internal.

The disclosed preparation process advantageously uses commercially available molecules as nitrogen sources. Moreover, the reaction proceeds under mild conditions, and requires low amounts of catalyst.

A main advantage of the herein disclosed preparation process is the high chemoselectivity and complete regioselectivity of the diamination reactions, which proceeds with high yields under mild conditions.

Thus, an aspect of the present invention is the provision of a process for the intermolecular transfer of two nitrogen groups onto an alkene compound to yield a 1 ,2-diamino compound comprising reacting the alkene with two nitrogen sources, in the presence of an oxidant reagent and a catalytic amount of metal salt or a chelated metal salt, wherein one nitrogen source is a bis(sulfonyl)imide or /V-halo-bis(sulfonyl)imide and the other nitrogen source is selected from the group consisting of an amide compound, an imide compound, a sulfonylcarbonylimide compound, and a carbamate compound. Another aspect of the present invention relates to a compound of formula (I) as defined below.

Furthermore, another aspect of the present invention relates to a process for the preparation of a compound of formula (III), or a salt thereof, wherein R_m and R_n are H or an amino protective group and R₂, R₃, and R₄ are as defined above for compound (I)

(III) comprising submitting the compound of formula (I) to at least one

deprotection reaction in order to deprotect the two amino groups, and if necessary, submitting the compound obtained to an amine protection reaction in order to yield a compound of formula (III) with a different amino protective group than the one of the corresponding compound of formula (I).

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

For the sake of clarity, the term diamination reaction is used in the present invention for the transfer of two nitrogen groups onto an alkene, involving two different nitrogen sources.

The preparation process of the present invention takes place under mild conditions, i.e. at room temperature and in short reaction times.

In a preferred embodiment, the preparation process of the invention relates to the preparations of the 1 ,2-diamino compound of formula (I),

R₄

(I) the process comprising reacting the alkene of formula (II),

(II) with (a) a compound of formula XH, and (b) a bis(sulfonyl)imide of formula R₅S02NZ(S0₂ 5'), in the presence of a catalytic amount of a metal salt, and in the presence of an oxidant compound of formula Rn l(0₂CRi₂)2, wherein:

Ri, R₂ and R₃ are radicals independently selected from the group consisting of H; (Ci-C₆)-alkyl; (d-C₆)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, and S0₂R_a;

(C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, and S0₂R_a; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy;

R_a is a radical selected from the group consisting of (Ci-C₆)-alkyl, (Ci- C₃)-alkylphenyl, phenyl (Ci-C₃)-alkyl, and phenyl;

R_b and R_c are radicals independently selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₃)-alkylphenyl;

R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, COR_d, hydroxy, N0₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, 0, N, NH, and NR_f; and -CH(R_x)0(R_y);

R_d is a radical selected from the group consisting of (d-C₆)-alkyl,

(C₃-C₆)-cycloalkyl, and phenyl;

R_e is a radical selected from the group consisting of (Ci-C₆)-alkyl,,

(Ci-C₆)-alkoxy, -CN, halide, and -N0₂; R_f is selected from the group consisting of SO₂R9, -COR_a, and -COOR_a.

R_x is selected from the group consisting of H; (Ci-C₆) alkyl; (Ci-C₆)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, and SO₂R_a; phenyl; and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R_y is a radical selected from the group consisting of H; phenyl-(Ci-C₆)-alkyl; (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide,

CORd, hydroxy, NO₂, and OR_a; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and benzoyl;

R₅ and R₅< are each independently selected from the group consisting of (Ci-Ci₂)-alkyl, phenyl, phenyl substituted by a radical selected from the group consisting of (d-C₆)-alkyl, and (Ci-C₆)-alkoxy; (Ci-C₃)-alkylphenyl; phenyl- (Ci-C₃)-alkyl; (Ci-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl and (Ci-C₆)-alkoxy; and (Ci-C₄)-alkyl-tri- (Ci-C₄)-alkyl silane;

Z is H or a halide;

X a radical is selected from:

n is 0 or 1 ; n' is 1 , 2, 3, or 4; R₆ is a radical selected from the group consisting of H; (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of halide, and COOR_a; phenyl; phenyl mono-, di- or tri-substituted with a radical selected from the group consisting of_N0₂, halide, (Ci-C₄)-alkyl, and (Ci-C₄)- oxyalkyl; S0₂R₉ and C(0)R₉;

R₇ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, phthalimido, and SO₂R_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having

5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and ORi₀;

R₈ is a radical selected from the group consisting of (Ci-C₆)-alkyl; H; halide; and NO₂; Y is selected from C(O) and S0₂;

R₉ is a radical selected from the group consisting of (d-C₆)-alkyl; (Ci-C₆)-alkyl substituted by an halide or an (Ci-C₄)-alkoxy; phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)- alkyl (Ci-C₄)-alkoxy, and an halide;

R₁₀ is a radical selected from the group consisting of a (Ci-C₆)-alkyl; and phenyl;

Rn is a radical selected from the group consisting of phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, halide and N0₂;

R₁₂ is a radical selected from the group consisting of a (Ci-C₆)-alkyl; (Ci-C₆)- alkyl substituted by an halide; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl (Ci-C₄)-alkoxy, halide and N0₂.

In a particular embodiment, R₈ is halide, and n' is 4. Preferably, R₈ is fluor and n' is 4.

In a more preferred embodiment, the preparation process of the present invention relates to the preparation of the 1 ,2-diamino compound of formula

(I) the process comprising reacting the alkene of formula (II), R,

R_a is a radical selected from the group consisting of (Ci-C₆)-alkyl, (Ci- C₃)-alkylphenyl, phenyl(Ci-C₃)-alkyl, and phenyl;

R_b and R_c are radicals independently selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₃)-alkylphenyl; R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, N0₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, 0, N, NH, and NR_f; and -CH(R_x)0(R_y);

R_d is a radical selected from the group consisting of (d-C₆)-alkyl,

(C₃-C₆)-cycloalkyl, and phenyl; R_e is a radical selected from the group consisting of (Ci-C₆)-alkyl,

(Ci-C₆)-alkoxy, -CN, halide, and -N0₂;

R_f is selected from the group consisting of SO₂R9, -COR_a, and -COOR_a; R_x is selected from the group consisting of H; (Ci-C₆) alkyl; (Ci-C₆)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, and S0₂R_a; phenyl; and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R_y is a radical selected from the group consisting of H; phenyl-(Ci-C₆)-alkyl; (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, CORd, hydroxy, NO₂, and OR_a; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a,

CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and benzoyl; R₅ and R₅< are each independently selected from the group consisting of

(Ci-Ci₂)-alkyl, phenyl, phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₆)-alkoxy; (Ci-C₃)-alkylphenyl; phenyl- (Ci-C₃)-alkyl; (d-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl and (Ci-C₆)-alkoxy; and (Ci-C₄)-alkyl-tri- (Ci-C₄)-alkyl silane; Z is H or a halide;

X a radical is selected from:

n is 0 or 1 ; R₆ is a radical selected from the group consisting of H; (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of halide, and COOR_a; phenyl; phenyl mono-, di- or tri-substituted with a radical selected from the group consisting of N0₂, halide, (Ci-C₄)-alkyl, and (Ci-C₄)- oxyalkyl; S0₂R₉ and C(0)R₉;

R₇ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, phthalimido, and SO₂R_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and ORi₀;

R₈ is a radical selected from the group consisting of H; (Ci-C₆)-alkyl; H;

halide; and NO₂;

Y is selected from C(O) and SO₂;

R₉ is a radical selected from the group consisting of (Ci-C₆)-alkyl; (Ci-C₆)-alkyl substituted by an halide or an (Ci-C₄)-alkoxy; phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)- alkyl (Ci-C₄)-alkoxy, and an halide;

R₁₀ is a radical selected from the group consisting of a (d-C₆)-alkyl; and phenyl;

Rn is a radical selected from the group consisting of phenyl, and phenyl mono-, di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, halide and N0₂;

R₁₂ is a radical selected from a (Ci-C₆)-alkyl; (Ci-C₆)-alkyl substituted by an halide; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl (Ci-C₄)-alkoxy, halide and N0₂. In a still more preferred embodiment, the preparation process of the present invention relates to the preparation of a compound of formula (I) wherein, R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; phenyl, phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy; and -CH(R_x)0(R_y);

R_x is selected from the group consisting of H; (Ci-C₆) alkyl; (Ci-C₆) alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, and SO₂R_a; phenyl; and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R_y is a radical selected from the group consisting of H; phenyl-(Ci-C₆)-alkyl; (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, hydroxy, NO₂, and OR_a; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, hydroxy, NO₂, and OR_a; phenyl, benzoyl, and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R₅ and R₅', are each independently selected from the group consisting of (Ci-Ci₂)-alkyl; phenyl; phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl, and (d-C₆)-alkoxy; (Ci-C₃)-alkylphenyl;

(Ci-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₆)-alkoxy; and

(Ci-C₄)-alkyl-tri-(Ci-C₄)-alkyl silane;

Z is H or a halide;

R₆ is a radical selected from the group consisting of H; (Ci-C₆)-alkyl;

(Ci-C₆)-alkyl substituted by a radical selected from the group consisting of halide, and COOR_a; phenyl; phenyl mono-,di- or tri-substituted with a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy; SO₂R₉; and C(0)R₉; and,

R₇ is a radical selected from the group consisting of (Ci-C₆)-alkyl; (Ci-C₆)- alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bRc, halide, phthalimido, and S0₂R_a; ORi₀; phenyl; and phenyl mono- ,di- or tri-substituted by a radical selected from the group consisting of (Ci- C₄)-alkyl, and (Ci-C₄)-alkoxy. In a particular embodiment, R₆ is the following radical

and R₅ and R₅' are the following radical

wherein n" is 0 or 1 .

In a more preferred embodiment of the above embodiment, the preparation process is performed with a compound of formula XH which is phthalimide or saccharin.

The diamine preparation process of the compound of formula (I) of the present invention can be performed using any salt of a metal as catalyst. In a preferred embodiment the catalyst is a salt of Pdll. In a still more preferred embodiment, the catalyst is selected from Pd(NCMe)₂CI₂,

Pd(hexafluoroacetylacetonate)₂, and Pd(NCPh)₂CI₂. Furthermore, amounts of catalyst as low as 1 mol% could be used which is very low compared to related alkene oxidation reactions (between 5 and 10mol%).

Furthermore, the diamination process of the compound of formula (I), takes place in the presence of an oxidant. The oxidant used is an hypervalent iodo(lll) reagent. In particular, the oxidant is the Rnl(0₂CRi₂)₂, wherein Rn is a radical selected from the group consisting of phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)- alkyl, (Ci-C₄)-alkoxy, halide and N0₂; and R₁₂ is a radical selected from the group consisting of a (d-C₆)-alkyl; (Ci-C₆)-alkyl substituted by an halide; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl (Ci-C₄)-alkoxy, halide and N0₂. In a more preferred embodiment, the oxidant reagent is Phl(0₂CRi₂)₂, wherein R₁₂ is methyl or butyl.

In a preferred embodiment the above preparation process is directed to the preparation of a compound of formula (I) wherein R₂, and R₃ are H, and R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a,

CONRbRc, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; (Ci-C₆)-phenylalkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; phenyl, phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy.

In another preferred embodiment the above preparation process is directed to the preparation of a compound of formula (I) wherein Ri and R₂ are H; R₃ is selected from the group consisting of H, (Ci-C₆)-alkyl, and (C₃-C₆)-cycloalkyl; R₄ is CH(R_x)0(Ry); and R_x is a radical selected from the group consisting of H, phenyl and phenyl mono-,di- tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, halide, and N0₂, Tables 1 -5 below illustrate some particular examples. In another preferred embodiment, the above preparation process is directed to the preparation of a compound of formula (I) wherein and R₂ are H; R₃ is selected from the group consisting of H, (d-C₆)-alkyl, and (C₃-C₆)-cycloalkyl; R₄ is CH(R_x)0(Ry); and R_x is a radical selected from the group consisting of H, phenyl mono-,di- tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, halide, and N0₂, Tables 1 -5 below illustrate some particular examples.

In another preferred embodiment the above preparation process is directed to the preparation of a compound of formula (I) wherein R₂ and/or R₄ are not H.

Other preferred embodiments relate to the above preparation process wherein the alkene of formula (II) is 1 -(prop-1 -enyl)benzene, 1 -(3- methoxyprop-1 -enyl)benzene, 1 -allylbenzene, 1 -octene, 1 -hexene, 1 -decene,

1 - duodecene, 4-phenylbutene, vinylcyclohexane, 3-methylhexene, methyl undec-10-enoate, 2-(dec-9-enyl)isoindoline-1 ,3-dione, (pent-4- enylsulfonyl)benzene, 1 1 -bromoundecene, 7-bromoheptene, 7-azidoheptene,

2- allyl-diethyl malonate, ((allyloxy)methyl)benzene, 1 -(allyloxy)butane, 1 - (allyloxy)propane, 1 -(allyloxy)methane, 1 -(allyloxy)ethane, 1 -(allyloxy)octane, allyl benzoate, (1 -(benzyloxy)allyl)benzene, prop-2-en-1 -ol, ((2- methylallyloxy)methyl)benzene, and hept-6-enenitrile.

Other preferred embodiments relates to the above preparation process wherein the alkene of formula (II) is 1 -octene, 1 -hexene, 1 -decene, 1 - duodecene, 4-phenylbutene, vinylcyclohexane, 3-methylhexene, methyl undec-10-enoate, 2-(dec-9-enyl)isoindoline-1 ,3-dione, (pent-4- enylsulfonyl)benzene, 1 1 -bromoundecene, 7-bromoheptene, 7-azidoheptene, 2-allyl-diethyl malonate, ((allyloxy)methyl)benzene, 1 -(allyloxy)butane, 1 - (allyloxy)propane, 1 -(allyloxy)methane, 1 -(allyloxy)ethane, 1 -(allyloxy)octane, allyl benzoate, (1 -(benzyloxy)allyl)benzene, prop-2-en-1 -ol, ((2- methylallyloxy)methyl)benzene, and hept-6-enenitrile.

The alkene of formula (II) which are commercially available can be stabilized with a stabilizer. In a preferred embodiment, the alkene of formula (II) further comprises a stabilizer. A suitable stabilizer includes tert-butyldiphenol.

In particular, and without limitation, the above preparation process yields the preparation of Λ/-(1 -bistosylamido-2-octyl)-saccharide, Λ/-(1 -bistosylamido-2- hexyl)-saccharide, Λ/-(1 -bistosylamido-2-decyl)-saccharide, Λ/-(1 - bistosylamido-2-duodecyl)-saccharide, /V-(1 -bistosylamido-4-phenyl-but-2-yl)- saccharide, Λ/-(1 -cyclohexyl-2-bistosylamido-ethyl)-saccharide, syn/anti-/V-(1 - bistosylamido-3-methyl-hex-2-yl)-saccharide, Λ/-(1 -bistosylamido-10- (methyloxycarbony)-decan-2-yl)-saccharide, Λ/-(1 -bistosylamido-10-phthaloyl- dec-2-yl)-saccharide, Λ/-(1 -bistosylamido-10-bromo-dec-2-yl)-saccharide, N- (1 -bistosylamido-7-bromo-hept-2-yl)-saccharide, Λ/-(1 -bistosylamido-7-azido- hept-2-yl)-saccharide, /V-(1 -bistosylamido-5-phenylsulfonyl-pent-2-yl)- saccharide, /V-(1 -bistosylamido-4,4-bis(ethyloxycarbonyl)-but-2-yl)- saccharide, /V-(3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-/V-

(phenylsulfonyl)benzenesulfonamide, /V-(3-(butyloxy)-2-(1 ,3-dioxoisoindolin- 2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, /V-(3-(propyloxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(3- (benzyloxy)-2-(1 , 1 -dioxido-3-oxobenzo[d]isothiazol-2(3/-/)-yl)propyl)-/V- (phenylsulfonyl)benzenesulfonamide, /V-(3-(butyloxy)-2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)propyl)-/V-

(phenylsulfonyl)benzenesulfonamide, /V-(3-(propyloxy)-2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)propyl)-/V-

(phenylsulfonyl)benzenesulfonamide, N-(3-(benzyloxy)-2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3H)-yl)propyl)-N-

(phenylsulfonyl)benzenesulfonamide, /V-(3-(methoxy)-2-(1 ,3-dioxoisoindolin- 2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, /V-(3-(ethoxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(3- (octyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-/V- (phenylsulfonyl)benzenesulfonamide, /V-(3-(benzoyloxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, N-((2R, S, 3R, S)-3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-/V- (phenylsulfonyl)benzenesulfonamide, Λ/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(2-(1 , 1 -dioxido-3-oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-/V- (methylsulfonyl)methanesulfonamide, Λ/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-4-methyl-/V- (methylsulfonyl)benzenesulfonamide, Λ/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-2-(trimethylsilyl)-/V-((2- (trimethylsilyl)ethyl)sulfonyl)ethanesulfonamide, Λ/-(2-(1 ,3-dioxoisoindolin-2- yl)octyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(6-cyano-2-(1 ,3- dioxoisoindolin-2-yl)hexyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(3- (benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-2-methylpropyl)-N- (phenylsulfonyl)benzenesulfonamide, N-(2-(1 ,3-dioxoisoindolin-2-yl)-3- hydroxypropyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(-2-(1 ,3- dioxoisoindolin-2-yl)-3-methoxy-1 -phenylpropyl)-N- (methylsulfonyl)methanesulfonamide, N-(-2-(1 ,3-dioxoisoindolin-2-yl)-3- methoxy-1 -phenylpropyl)-4-methyl-N-tosylbenzenesulfonamide, N-(-2-(1 ,3- dioxoisoindolin-2-yl)-1 -phenylpropyl)-4-methyl-N-tosylbenzenesulfonamide or N-(2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-4-methyl-N- tosylbenzenesulfonamide.

Among the several advantages of the preparation process of the present invention, are the chemoselectivity and regioselectivity of the reaction.

Regarding the chemoselectivity, subproducts, such as enamides, are not significatively produced as result of the reaction; in fact, the enamide formation accounts for less that 15%. With respect to the regioselectivity, the nitrogen of the compound of formula XH, wherein X is as defined above, enters into the distal carbon of the terminal alkene, whereas the nitrogen of the bis(sulfonyl)imide enters into the proximal carbon of the terminal alkene. In cases of internal alkenes, the regioselectivity is depending on the radical substituents. For example, for internal alkenes with a phenyl substituent the nitrogen of the bis(sulfonyl)imide enters into the proximal carbon next to the phenyl substituent, while the nitrogen of the compound of formula XH, wherein X is as defined above, enters into the distal carbon.

Table 1

Pd(PhCN)₂CI₂ (5 mol%)

Alkene Yield [%] compound (l)^:

a

wherein ^{[ J} represents the isolated yield; ^{[ J} preparation process with 10 mol% of catalyst, 1 .5 equivalents of oxidant, and 2 equivalents of bistosylimide; and ^[cl 3:2 ratio of diasteroisomers. All products (ll)a-n of Table 1 display spectroscopic data in agreement with the expected vicinal diamine motif. Their constitution is unambiguously assured from an X-ray structure determination of derivative (l)f.

Table 2

Diamine Yield [%]^a

Wherein ^[al represents the isolated yield. All products (l)o-t of Table 2 display spectroscopic data in agreement with the expected vicinal diamine motif.

Table 3

(ll)o, (ll)r,

Ra Rx Diamine Yield [%]^a

n-Pr H H (l)s

Me H H (i)t 65

Et: H H (l)u 69

n-Bu H H (1)99 65

n-Oct H H l)v 67

wherein ^[aJ represents the isolated yield; ^{1 J} 100% diastereomeric excess. All products (l)o, (l)r, (l)s, (l)u-y of Table 3 display spectroscopic data in agreement with the expected vicinal diamine motif. Their constitution is unambiguously assured from an X-ray structure determination of derivative (l)u.

Table 4

Diamine Yield [%]^a

Wherein ^{[ J} represents the isolated yield; All products (l)a, (l)b, (l)aa, (l)bb and (l)cc of Table 4 display spectroscopic data in agreement with the expected vicinal diamine motif.

Table 5

(ll)a, (ll)ee EtOAc, 70°C, 16 h (l)dd, (l)ee

R. Diamine Yield [%]^a

wherein ^{[ J} represents the isolated yield. All products (l)dd and (l)ee of Table 5 display spectroscopic data in agreement with the expected vicinal diamine motif. Table 6

(ll)

Diamine Yield [%]^a

(l)kk

wherein ^{[ J} represents the isolated yield. All products (l)hh-(l)kk of Table 6 display spectroscopic data in agreement with the expected vicinal diamine motif.

As mentioned above, the two nitrogens incorporated into the alkene by the diamination process of the present invention can be easily deprotected, even in a selective manner to obtain the corresponding free primary amine groups, i.e. a compound of formula (III) described above, wherein R_m and R_n are H. In a preferred embodiment the compound of formula (I) is submitted to a first deprotection reaction using iodotrimethylsilane in an adequate solvent, and, then to a second deprotection reaction using HBr and HOAc, to yield a compound of formula (III) wherein R_m and R_n are H.

In a still more preferred embodiment, the compound of formula (I) wherein R₂ and R₃ are H, R₄ is an hexyl, R₅ and R₅< are 2-trimethylsilylethyl, and X is saccharinyl is reacted with CsF and DMF to yield a compound of formula (III) wherein R^ R₂ and R₃ are H, R₄ is an hexyl; R_n is H and R_m is 2- trimethylsilylethylsulphonyl.

Examples of amino protective groups are for instance sulfonamides, a benzyl and a mono or a di-substituted benzyl; in particular, t-butoxycarbonyl (BOC), 9-fluorenylmethoxycarbonyl (Fmoc), benzyloxycarbonyl (Cbz), 4- methoxybenzyl, 2,4-dimethoxybenzyl and N-benzylamine

The protective groups can be introduced and removed by procedures known in the art (Greene and Wuts, "Protective Groups in Organic Synthesis", Chapter 7 "Protection for the Amino group", "Wiley-lnterscience, third edition, (1999), pp 495-653). The specific reaction conditions depend on the protective group used.

Throughout the description and claims the word "comprise" and variations of the word, are not intended to exclude other technical features, additives, components, or steps. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples and drawings are provided by way of illustration, and they are not intended to be limiting of the present invention. Furthermore, the present invention covers all possible combinations of particular and preferred embodiments described herein.

EXAMPLES

Example 1. Intermolecular palladium-catalysed diamination of terminal alkenes, with 5 mol% catalyst (Table 1 , compounds (l)a-d, and (l)h-n; and Table 4, compounds (l)aa, (l)z, (l)bb, and (Pec).

A Pyrex tube equipped with a stirrer bar was charged with 183 mg saccharin (1.1 mmol, 1.1 eq.), 447 mg iodosobenzene dipivalate (1.1 mmol, 1.1 eq.), corresponding bis(sulfonyl)imide (1.3 mmol, 1.3 eq.), and 19 mg

bis(benzonitrile)palladiumdichloride (0.05 mmol, 5 mol%).0.75 mL of absolute dichloromethane was added and the solution was stirred, while 1 mmol of the alkene was added directly via syringe. An additional 0.5 mL of

dichloromethane were added, the resulting solution was sealed and stirred at room temperature for 16h. After that, the solution was transferred into a round bottom flask and all volatile material was evaporated under reduced pressure. If not stated otherwise, the remaining solid was directly purified by column chromatography (silica gel, n-hexane/ethyl acetate, 3/1, v/v). /V-(1-Bistosylamido-2-octyl)-saccharide (compound (l)a)

IR v(cm^"1): 2954, 2926, 2857, 1725, 1595, 1458, 1373, 1335, 1291, 1253, 1163, 1125, 1083, 1060, 972, 813, 783, 751, 721, 676, 661, 583, 547, 509. HRMS (ESI-MS): calculated for C29H₃₄N₂0₇NaS₃: 641.1426; found: 641.1436.

/V-(1-Bistosylamido-2-hexyl)-saccharide (compound (l)b)

IR v(cm^"1): 2959, 2873, 2381, 1721, 1595, 1460, 1355, 1307, 1294, 1187, 1123, 1053, 958, 817, 809, 753, 701, 677, 659, 600, 583, 532, 510.

HRMS (ESI-MS): calculated for

613.1113, found: 613.1115.

/V-(1-Bistosylamido-2-decyl)-saccharide (compound (l)b)

IR v(cm^"1): 2952, 2924, 2855, 1724, 1595, 1460, 1375, 1355, 1335, 1295, 1265, 1171, 1165, 1122, 1084, 960, 816, 807, 786, 756, 721, 700, 678, 659, 599, 582, 549, 532, 511.

HRMS (ESI-MS): calculated for CsiHseNzOyNaSs: 669.1739; found: 669.1760. /V-(1-Bistosylamido-2-duodecyl)-saccharide (compound (l)d)

IR v(cm^"1): 2924, 2854, 1726, 1596, 1460, 1374, 1336, 1292, 1254, 1163, 1125, 1084, 1061, 1018, 971, 813, 786, 751, 721, 676, 661, 583, 547, 509. HRMS (ESI-MS): calculated for CssH^IS^NaSs : 697.2052, found: 697.2051.

/V-(1-Bistosylamido-10-(methyloxycarbony)-decan-2-yl)-saccharide

(compound (l)h)

IRv(cm^"1): 2927, 2856, 1727, 1596, 1460, 1438, 1373, 1335, 1292, 1253, 1163, 1123, 1084, 1060, 814, 785, 752, 721, 677, 661, 583, 647, 509.

HRMS (ESI-MS): calculated for

727.1794; found: 727.1788. /V-(1-Bistosylamido-10-phthaloyl-dec-2-yl)-saccharide (compound (l)i)

IRv(cm^"1): 2924, 2854, 1771, 1707, 1596, 1464, 1438, 1396, 1371, 1334, 1292, 1253, 1163, 1083, 1060, 1018, 966, 814, 786, 751, 719, 703, 676, 661, 583, 547, 509. HRMS (ESI-MS): calculated for

828.2059; found: 828.2024.

Λ/-(1 -Bistosylamido-10-bromo-undec-2-yl)-saccharide (compound (l)j)

IRv(cm^"1): 2931, 2862, 1725, 1596, 1458, 1373, 1334, 1308, 1292, 1254, 1162, 1125, 1083, 1060, 1018, 969, 813, 786, 749, 721, 702, 676, 660, 583, 546, 509, 481. HRMS (ESI-MS): calculated for C₃2H39N₂0₇NaS₃Br: 761.1000; found: 761.0999.

Λ/-(1 -Bistosylamido-7-bromo-hept-2-yl)-saccharide (compound (l)k)

¹H-NMR (400MHz, CDCI₃): δ = 1.35-1.44 (m, 4H), 1.76-1.81 (m, 3H), 2.12- 2.20 (m, 1H), 2.41 (s, 6H), 3.35 (t, J = 6.8 Hz, 2H), 4.10 (dd, J = 15.7, 5.3 Hz, 1H), 4.22 (dd, J= 15.7, 7.4 Hz, 1H), 4.47 (m, 1H), 7.31 (d, J = 8.5 Hz, 4H), 7.77-7.83 (m, 3H), 7.91 (d, J = 8.3 Hz, 4H), 8.01 (dd, J = 6.6, 1.3 Hz, 1 H). ¹³C-NMR (100MHz, CDCI₃): 5 = 21.5, 25.2,27.4, 29.0, 32.2, 33.5, 48.0, 54.1, 120.7, 124.8, 127.1, 128.0, 128.7, 129.4, 129.7, 134.1, 134.5, 135.6, 137.1, 145.1, 159.2.

HRMS (ESI-MS): calculated for CzeHsiNzO^aSsBr: 705.0374; found:

705.0374.

Λ/-(1 -Bistosylamido-7-azido-hept-2-yl)-saccharide (compound (l)l) IRv(cm^"1): 2928, 2862, 2093, 1726, 1596, 1457, 1373, 1334, 1291, 1253, 1162, 1123, 1084, 1060, 1018, 968, 813, 786, 751, 721, 676, 660, 583, 546, 509. HRMS (ESI-MS): calculated for C28H₃iN₅0₇NaS₃: 668.1283; found:

668.1292.

Λ/-(1 -Bistosylamido-5-phenylsulfonyl-pent-2-yl)-saccharide (compound (l)m)

IRv(cm^"1): 2962, 2874, 1726, 1613, 1595, 1554, 1492, 1480, 1446, 1370, 1334, 1291, 1254, 1161, 1142, 1083, 1017, 969, 863, 813, 784, 750, 727, 688, 675, 661 , 582, 547. HRMS (ESI-MS): calculated for C32H₃₂N₂0₉NaS₄: 739.0888; found: 739.0901.

/V-(1-Bistosylamido-4,4-bis(ethyloxycarbonyl)-but-2-yl)-saccharide (compound (l)n)

IRv(cm^"1): 3055, 2987, 1732, 1598, 1562, 1422, 1375, 1341, 1264, 1168, 896, 731, 703, 664, 553. HRMS (ESI-MS): calculated for

729.1222; found: 729.1208. /V-(1-Bismesylamido-oct-2-yl)-saccharide (compound (l)aa)

IRv(cm^"1): 2954, 2928, 2858, 1727, 1462, 1360, 1326, 1292, 1254, 1183, 1154, 1095, 1061, 964, 842, 810, 783, 751, 676, 603, 585, 533, 506.

HRMS (ESI-MS): calculated for Ci₇H26N₂0₇NaS₃: 489.0800; found: 489.0796.

Λ/-(1 -Bisphenylsulfonylamido-oct-2-yl)-saccharide (compound (l)z)

IRv(cm^"1): 3057, 2957, 2929, 2858, 1728, 1449, 1377, 1337, 1293, 1264, 1170, 1085, 1061, 800, 732, 703, 686, 583, 551.

HRMS (ESI-MS): calculated for

613.1113; found: 613.1093.

/V-(1-Mesyl-tosylamido-oct-2-yl)-saccharide (compound (l)bb)

¹H-NMR (400 MHz, CDCI₃): δ = 0.89 (t, J = 7.0 Hz, 3H), 1.24-1.47 (m, 8H), 1.77-1.86 (m, 1H), 2.10-2.19 (m, 1H), 2.47 (s, 3H), 3.68 (s, 3H), 3.76 (d, J = 13.5 Hz, 1H), 4.24-4.36 (m, 2H), 7.37 (d, J = 8.2 Hz, 2H), 7.87-7.97 (m, 3H), 7.91 (d, J = 8.2 Hz, 2H), 8.11-8.14 (m, 1H). ¹³C-NMR (100 MHz, CDCI₃): δ = 14.0, 21 .6, 22.5, 26.2, 28.7, 29.8, 31 .5, 45.6, 54.4, 120.9, 124.9, 127.7, 128.8, 129.7, 134.3, 134.3, 134.5, 137.0, 145.4, 159.6.

HRMS (ESI-MS): calculated for C₂₃H₃oN₂0₇NaS₃: 565.6783; found: 565.6791 .

Λ/-(1 -Bis(trimethylsilylethyl)amido-oct-2-yl)-saccharide (compound (l)cc)

IR v(cm^"1): 2955, 2929, 2858, 1730, 1558, 1464, 1402, 1362, 1336, 1295, 1252, 1 181 , 1 161 , 1 147, 1061 , 844, 753.

HRMS (ESI-MS): calculated for C₂₀H₃3N₂O₅NaS₂ (M⁺-SES): 496.1498; found: 496.1502.

Example 2. Intermolecular palladium-catalysed diamination of terminal alkenes, with 10 mol% catalyst (Table 1 , compounds (l)e-g').

A Pyrex tube equipped with a stirrer bar was charged with 240 mg saccharin (1 .3 mmol, 1 .3 eq.), 609 mg iodosobenzene dipivalate (1 .5 mmol, 1 .5 eq.), 650 mg bistosylamide (2 mmol, 2 eq.) and 38 mg

bis(benzonitrile)palladiumdichloride (0.10 mmol, 10 mol%). 0.75 ml_ of absolute dichloromethane was added and the solution was stirred, while 1 mmol of the alkene was added directly via syringe. An additional 0.5 mL of dichloromethane were added, the resulting solution was sealed and stirred at room temperature for 16h. After that, the solution was transferred into a round bottom flask and all volatile material was evaporated under reduced pressure. The remaining solid was directly purified by column chromatography (silica gel, n-hexane/ethyl acetate, 3/1 , v/v).

Λ/-(1 -Bistosylamido-4-phenyl-but-2-yl)-saccharide (compound (l)e) After column chromatography, the compound is obtained together with a small amount of ditosylamide. Crystallization from methanol gives the title

compound in pure form as an off-white solid.

IR v(cm^"1): 3063, 3026, 2951 , 2928, 1724, 1595, 1563, 1493, 1453, 1371 , 1336, 1291 , 1253, 1 162, 1082, 1058, 812, 785, 751 , 722, 700, 660, 586, 547. HRMS (ESI-MS): calculated for C₃iH3oN₂0₇NaS₃: 661 .1 1 13; found: 661 .1 1 14. Λ/-(1 -Cyclohexyl-2-bistosylamido-ethyl)-saccharide (compound (l)f)

IR v(cm^"1): 2942, 2923, 2854, 1716, 1656, 1596, 1382, 1357, 1334, 1309, 1293, 1259, 1 176, 1 162, 1083, 1024, 987, 953, 825, 816, 792, 754, 741 , 714, 696, 674, 660, 647, 612, 584, 546, 534, 507, 474.

HRMS (ESI-MS): calculated for

639.1269; found: 639.1270. syn/anti-N-^ -Bistosylamido-3-methyl-hex-2-yl)-saccharide (compound (l)g/g') IR n(cm-1 ): 3055, 2961 , 2931 , 1725, 1597, 1459, 1374, 1338, 1293, 1264, 1 187, 1 165, 1085, 984, 815, 787, 733, 702, 677, 662, 585, 552.

HRMS (ESI-MS): calculated for C28H32N207NaS3: 627.1269; found:

627.1278. Major isomer:

1 H-NMR (400 MHz, CDCI3): d = 0.98 (t, J = 7.1 Hz, 3H), 1 .20 (d, J = 6.6 Hz, 3H), 1 .22-1 .35 (m, 2H), 1 .43-1 .53 (m, 1 H), 1 .71 -1 .77 (m, 1 H), 2.24-2.34 (m, 1 H), 2.48 (s, 6H), 3.92-4.17 (m, 2H), 4.46-4.52 (m, 1 H), 7.37 (d, J = 8.0 Hz, 4H), 7.80-7.86 (m, 3H), 7.97 (d, J = 8.0 Hz, 4H), 8.07-8.08 (m, 1 H).

13C-NMR (100 MHz, CDCI3): d = 14.0, 16.9, 20.0, 21 .5, 33.1 , 36.0, 45.6, 58.9, 120.8, 124.6, 127.3, 128.9, 129.3, 133.8, 134.1 , 135.5, 144.9, 159.8.

Minor isomer:

1 H-NMR (400 MHz, CDCI3): d = 0.89 (t, J = 7.0 Hz, 3H), 1 .01 (d, J = 6.7 Hz, 3H), 1 .22-1 .35 (m, 2H), 1 .43-1 .53 (m, 1 H), 1 .71 -1 .77 (m, 1 H), 2.24-2.34 (m, 1 H), 2.48 (s, 6H), 3.92-4.17 (m, 2H), 4.46-4.52 (m, 1 H), 7.37 (d, J = 8.0 Hz, 4H), 7.80-7.86 (m, 3H), 7.97 (d, J = 8.0 Hz, 4H), 8.06-8.07 (m, 1 H).

13C-NMR (100 MHz, CDCI3): d = 13.7, 16.2, 19.6, 21 .5, 32.8, 36.0, 45.5, 59.7, 120.7, 124.5, 127.4, 128.9, 129.3, 133.8, 134.1 , 136.9, 144.9, 159.9.

Example 3. Intermolecular palladium-catalysed diamination of compounds of formula (l)p/(l)r (Table 2, compounds (l)p and (l)r).

Palladium-bis(hexafluoroacetylacetonate) (0.028 mmol, 14.5 mg), saccharin (0.4 mmol, 73.2 mg), N-fluorobis(phenylsulfonyl)amine (0.64 mmol, 200 mg) and compounds of formula (ll)p/(ll)r (0.8 mmol) were suspended in 0.4 mL of ethyl acetate (EtOAc) in a pyrex tube. The mixture was heated at 70 °C for 12 hours. After cooling, the solution was evaporated under reduced pressure and the crude product was purified by chromatography on silical gel to give the corresponding product in analytically pure form. Compound (l)p

¹H NMR (400 MHz, CDCI₃) δ 7.28-8.10 (m, 19H), 4.78 (dd, J

1 H), 4.57 (s, 2H), 4.42 (dd, J = 8.1 , 16.2 Hz, 2H), 4.26 (dd, J

2H), 3.96 (d, J = 7.2 Hz, 2H).

Compound (l)r

¹H NMR (400 MHz, CDCI₃) δ 7.5-8.1 (m, 14H), 4.68 (dd, J = 3.4, 7.0 Hz, 1 H), 4.41 (dd, J = 8.1 , 15.9 Hz, 2H), 4.25 (dd, J = 4.1 , 15.9 Hz, 2H), 3.87 (dd, J = 4.1 , 7.5 Hz, 2H), 3.46 (dt, J = 3.1 , 6.6 Hz, 2H), 1 .54-1 .58 (m, 2H), 1 .31 -1 .36 (m, 2H), 0.88 (t, J= 7.5 Hz, 3H).

Example 4. Intermolecular palladium-catalysed diamination of benzyl allyl ethers compounds (Table 3, compounds (Do, (l)gg, (l)s, (l)t, (l)u, (l)v, (l)w,

(I) x. (I)v.and (l)ff).

Palladium-bis(hexafluoroacetylacetonate) (0.028 mmol, 14.5 mg), phthalimide (0.4 mmol, 60 mg), Phl(OC(0)'Bu)₂ (0.64 mmol, 260 mg), N- fluorobis(phenylsulfonyl)amine (0.64 mmol, 200 mg) and compounds

(II) o/(ll)gg/(ll)s/(ll)t/(ll)u/(ll)v/(ll)w/(ll)x/(ll)y/(ll)ff (0.8 mmol) were suspended in 0.4 mL of ethyl acetate (EtOAc) in a pyrex tube. The mixture was heated at 70 °C for 12 hours. After cooling, the solution was evaporated under reduced pressure and the crude product was purified by chromatography on silical gel to give the corresponding product in analytically pure form. N-(3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)o)

IR (KBr): 3065, 3033, 2902, 2872, 1769, 1706, 1451 , 1 164, 1025, 717, 548 cm^"1. HRMS: calcd for C₃oH₂₆N₂0₇S₂Na : 613.108, found: 613.109 .

N-(3-(butyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)gg)

IR (KBr): 2958, 2933, 2871 , 1775, 1709, 1448, 1 166, 1083, 753, 546 cm^"1. HRMS: calcd for C₂₇H₂₈N₂0₇S₂Na: 579.124, found:579.125.

N-(3-(propyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N-(phenylsulfonyl)benzen esulfonamide (compound (l)s), IR (KBr): 2963, 2932, 2875, 1774, 1708, 1448, 1369, 1 166, 1083, 753, 546 cm^"1. HRMS: calcd for C₂₆H₂₆N₂0₇S₂Na : 565.107, found: 565.105.

N-(3-(methoxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)t)

IR (KBr): 3060, 2927, 1772, 1708, 1369, 1 166, 1051 , 740, 547 cm^"1. HRMS: calcd for C₂₄H₂₂N₂0₇S₂Na : 537.076, found: 537.075.

N-(3-(ethoxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)u),

IR (KBr): 2975, 2925, 1773, 1708, 1369, 1 167, 1085, 754, 547 cm^"1.

HRMS: calcd for C₂₅H₂₄N₂0₇S₂Na : 551 .092, found: 551 .089. N-(3-(octyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)v), IR (KBr): 2926, 2856, 1775, 1708, 1448, 1370, 1 167, 1084, 788, 753, 547 cm^"

N-(3-(benzoyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)w),

IR (KBr): 3065, 2927, 1775, 1710, 1448, 1370, 1267, 1 166, 1083, 753, 545 cm^"1. HRMS: calcd for CsoH^C^Na : 627.087, found: 627.091 . N-(-3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-N- (phenylsulfonyl)benzenesulfonamide (compound (l)x).

¹H NMR (500 MHz, CDCI3) δ 7.81 - 7.78 (m, 2H), 7.77 - 7.73 (m, 4H), 7.72 - 7.69 (m, 2H), 7.51 (dd, J = 16.6, 9.3 Hz, 7H), 7.42 - 7.36 (m, 4H), 7.1 1 (t, J = 7.3 Hz, 1 H), 7.03 (t, J = 7.5 Hz, 2H), 6.91 (d, J = 7.4 Hz, 2H), 5.03 (t, J = 9.6 Hz, 1 H), 4.85 (d, J = 10.1 Hz, 1 H), 4.51 (dd, J = 16.0, 10.6 Hz, 1 H), 4.33 (d, J = 12.1 Hz, 1 H), 4.06 (d, J = 12.1 Hz, 1 H), 3.41 (dd, J = 15.9, 1.5 Hz, 1 H). ¹³C NMR (125 MHz, CDCI₃) δ 168.90, 168.01 , 138.50, 137.87, 137.61 , 133.72, 133.65, 129.02, 128.89, 128.85, 128.49, 128.43, 127.99, 127.42, 127.31 , 123.47, 122.93, 69.99, 56.33, 45.27, 27.01 .

Λ/-(2-(1 ,3-dioxoisoindolin-2-yl)-3-hydroxypropyl)-/V- (phenylsulfonyl)benzenesulfonamide (compound (l)y) IR (KBr): 3436, 3067, 2945, 1767, 1687, 1447, 1370, 1 167, 1083, 784, 752, 544 cm^"1.

/V-(3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-2-methylpropyl)-/V- (phenylsulfonyl)benzenesulfonamide (compound (l)ff)

IR (KBr): 3067, 2923, 2852, 1740, 1713, 1448, 1369, 1 161 , 1082, 742, 682, 546 cm^"1.

Example 5. Intermolecular palladium-catalysed diamination of compounds of fiormula (ll)dd/(ll)ee using phthalimide (Table 5, compounds (Odd, (Dee)

Palladium-bis(hexafluoroacetylacetonate) (0.08 mmol), phthalimide (0.8 mmol, 120 mg), Phl(OC(0)'Bu)₂ (0.64 mmol, 260 mg), N- fluorobis(phenylsulfonyl)amine (1.28 mmol, 400 mg) and compound

(ll)dd/(ll)ee (0.8 mmol) were suspended in ethyl acetate (EtOAc) in a pyrex tube. The mixture was heated at 70 °C for 16 hours. After cooling, the solution was evaporated under reduced pressure and the crude product was purified by chromatography on silical gel to give the corresponding product in analytically pure form.

Λ/-(2-(1 ,3-dioxoisoindolin-2-yl)octyl)-/V-(phenylsulfonyl)benzenesulfonamide (compound (l)dd)

IR (KBr): 2955, 2928, 2857, 1773, 171 1 , 1448, 1373, 1 169, 1084, 805, 740, 522 cm^"1. /V-(6-cyano-2-(1 ,3-dioxoisoindolin-2-yl)hexyl)-/V-

(phenylsulfonyl)benzenesulfonamide (compound (l)ee)

IR (KBr): 3069, 2941 , 2859, 2246, 1769, 1704, 1448, 1369, 1 165, 1084, 783, 752, 544 cm^"1.

Example 6. Deprotection reaction of N-(1 -Bistosylamido-2-octyl)-saccharide.

To a slurry of sodium iodide (4 mmol) in 10 mL absolute acetonitrile under argon at 0 oC was added trimethylsilyl chloride (4 mmol) via syringe. An acetonitrile solution of N-(1 -Bistosylamido-2-octyl)-saccharide (1 mmol) is added over 5 min, the cooling bath is removed and the mixture heated at 75 oC oil bath temperature overnight. Alter cooling to 30 oC, all volatile material was removed under reduced pressure into an external trap. The remaining yellowish residue was taken up in acetic acid (5 mL) and HBr/HOAc was added. The resulting solution was again refluxed overnight at 75 °C oil bath temperature. It was cooled down to room temperature, extracted with ethyl acetate (2 x 20 mL) and dichloromethane (2 x 20 mL). The aqueous phase was made alkaline (pH 14) was extracted with three portions of

dichloromethane (20 mL each). The combined solutions were dried over magnesium sulfate, concentrated under vacuum to yield the free diamino compound. Example 7. Deprotection reaction of N-(1 -bis(tnmethylsilylethyl)amido-oct-2- yl)-saccharide.

A solution of N-(1 -bis(trimethylsilylethyl)amido-oct-2-yl)-saccharide (0.5 mmol) was dissolved in 5 ml_ absolute DMF under argon. Caesium fluoride (950 mg, 6.25 mmol) was added carefully against a positive stream of argon. The Schlenk flask was sealed and heated overnight at 100 °C oil bath temperature. After that time, the solution is cooled to room temperature, taken up in 50 ml_ brine and 20 ml_ 14N NaOH solution, and extracted with ethylacetate (3 x 15 ml_). The organic phase was dried over magnesium sulfate and evaporated to dryness under reduced pressure to leave the N-(2- aminooctyl)-2-(trimethylsilyl)ethanesulfonamid compound as a yellowish oil (1 1 1 mg, 72%). Example 8. Intermolecular palladium-catalysed diamination of terminal alkenes, with 10 mol% catalyst (Table 6, compounds (l)hh-kk).

A Pyrex tube equipped with a stirrer bar is charged with 31 mg phatalimide (0.21 mmol, 1.0 eq), 8 mg bis(benzonitrile)palladiumdichloride (0.021 mmol, 10%) and 0.3 ml_ of absolute dichloroethane and the solution is stirred at 70°C for 1 h. Then, 81 mg bistosylamide (0.25 mmol, 1 .2 eq), 170 mg iodosobenzene dipivalate (0.42 mmol, 2.0 eq) and compounds

(ll)hh/(ll)ii/(ll)jj/(ll)kk (0.21 mmol) were added, the resulting solution is sealed and stirred at 70°C for 20h. After that, the solution is transfered into a round botton flask and all volatile material is evaporated under reduced pressure. If not stated otherwise, the remaining solid is directly purified by column chromatography (silica gel, n-hexane/ethyl acetate, 3/1 , v/v) to give the corresponding product in analytically pure form. N-(-2-(1 ,3-dioxoisoindolin-2-yl)-1 -phenylpropyl)-4-methyl-N- tosylbenzenesulfonamide (l)hh

¹H NMR (400 MHz, CDCI₃): 51 .01 (d, J = 6.9 Hz, 3H), 2.30 (s, 3H), 2.48 (s, 3H), 5.85 (dq, J = 1 1 .1 , 6.9 Hz, 1 H), 6.49 (d, J = 1 1 .1 hz, 1 H), 6.97 (d, J = 8.3 Hz, 2H), 7.02 (d, J = 8.6 Hz, 2H), 7.27-7.25 (m, 3H), 7.44 (d, J = 8.1 Hz, 2H), 7.63-7.60 (m, 2H), 7.71 (br, 2H), 7.78 (dd, J = 6.5, 3.0 Hz, 2H), 8.28 (d, J = 8.4 Hz, 2H). ¹³C NMR (400 MHz, CDCI₃): δ = 15.7, 21 .6, 21 .9, 47.9, 63.6, 128.2, 128.6, 128.7, 128.9, 129.7, 129.9, 130.2, 134.1 , 135.1 , 136.5, 138.7, 144.1 , 145.5, 167.2, 168.7. IR (KBr): 3066, 2990, 1708, 1365, 1 165 cm^"1. HRMS: calcd for C₃iH₂₈N₂0₆S₂Na: 61 1 .1295, found: 61 1 .1287. N-(-2-(1 ,3-dioxoisoindolin-2-yl)-3-methoxy-1 -phenylpropyl)-N- (methylsulfonyl)methanesulfonamide (l)ii

¹H NMR (400 MHz, CDCI₃): δ = 2.40 (s, 3H), 3.40 (s, 3H), 3.49 (s, 3H), 3.90 (dd, J = 9.9, 4.5 Hz, 1 H), 4.21 (dd, J = 9.9, 8.8 Hz, 1 H), 5.88 (ddd, J = 1 1 .5, 8.8, 4.5 Hz, 1 H), 6.85 (d, J = 1 1 .8 Hz, 1 H), 7.29-7.26 (m, 2H), 7.35-7.31 (m, 2H), 7.68.7.63 (m, 4H), 7.74 (br, 1 H). ¹³C NMR (400 MHz, CDCI₃): δ= 43.7, 44.3, 50.1 , 59.2, 59.6, 70.4, 123.4, 123.6, 129.1 , 129.4, 129.6, 131 .8, 131 .5, 133.8, 134.2, 167.8, 168.4. IR (KBr): 3040, 2942, 1712, 1390, 1364, 1007 cm ¹. HRMS: calcd for C₂oH₂₂N₂0₇S₂Na: 489.0758, found: 489.0766.

N-(-2-(1 ,3-dioxoisoindolin-2-yl)-3-methoxy-1 -phenylpropyl)-4-methyl-N- tosylbenzenesulfonamide (l)jj

¹H NMR (400 MHz, CDCI₃): δ = 2.31 (s, 3H), 2.49 (s, 3H), 3.06 (s, 3H), 3.1 1 (m, 1 H), 3.30 (dd, J = 10.2, 3.9 Hz, 1 H), 6.03-5.93 (m, 1 H), 6.46 (d, J = 1 1 .2 Hz, 1 H), 6.99 (q, J = 8.7 Hz, 4H), 7.28-7.26 (m, 3H), 7.48 (d, J = 8.1 Hz, 2H), 7.66-7.60 (m, 2H), 7.70 (ddd, J = 5.4, 3.1 , 0.7 Hz, 1 H), 7.75-7.73 (m, 1 H), 7.79-7.77 (m, 2H), 8.28 (d, J = 8.4 Hz, 2H). ¹³C NMR (400 MHz, CDCI₃): δ = 21 .6, 21 .9, 50.9, 58.6, 60.6, 68.9, 123.1 , 123.7, 128.3, 128.7, 128.8, 128.9, 129.8, 129.9, 130.2, 131 .5, 131 .9, 134.0, 134.1 , 134.5, 134.6, 136.3, 138.3,

144.3, 145.8, 167.8, 168.8. IR (KBr): 3065, 2962, 2924, 2814, 1712, 1308 cm ¹. HRMS: calcd for C₃₂H₃₀N₂O₇S₂Na: 641 .1361 , found: 641 .1392.

N-(2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-4-methyl-N- tosylbenzenesulfonamide (l)kk

¹H NMR (400 MHz, CDCI₃): δ = 2.42 (s, 6H), 3.12 (dd, J = 13.8 and 6.3 Hz, 1 H), 3.26 (dd, J = 13.8 and 10.4 Hz, 1 H), 3.95 (dd, J = 15.8 and 2.8 Hz, 1 H), 4.40 (dd, J = 15.8 and 9.3 Hz, 1 H), 5.0-4.94 (m, 1 H), 7.14-7.1 1 (m, 3H), 7.20- 7.17 (m, 3H), 7.30 (d, J = 8.0 Hz, 4H), 7.63 (br, 3H), 7.87-7.85 (m, 4H). ¹³C NMR (400 MHz, CDCI₃): δ = 21 .8, 36.2, 47.8, 52.7, 123.1 , 123.7, 126.9, 128.6, 128.8, 129.1 , 129.7, 133.8, 134.4, 135.9, 136.8, 145.2, 167.7, 169.3.. HRMS: calcd for C23H₂₄N0₄S₂: 442.1 147, found,

REFERENCES CITED IN THE APPLICATION

Zhao et al., "Synthetic and mechanistic studies of Pd(0)-catalyzed

diamination of conjugated dienes", J. Am. Chem. Soc. (2010) vol. 132:3523- 3532. Sibbald et al., "Palladium-catalyzed diamination of unactivated alkenes using N-fluorobenzenesulfonimide as source of electrophilic nitrogen", Organic letters (2009) vol. 1 1 : 1 147-1 149.

Muniz et al., "Oxidative diamination of alkenes with ureas as nitrogen sources: mechanistic pathways in the presence of a high oxidation state palladium catalyst", J. Am. Chem. Soc. (2008) vol. 130:763-773.

C.J.M. Stirling, "Intramolecular Aminolysis of Amides", Journal of the

Chemical Society. (1958): 4531 -4536.

Claims

1 . - A process for the intermolecular transfer of two nitrogen groups onto an alkene compound to yield a 1 ,2-diamino compound comprising reacting the alkene with two nitrogen sources, in the presence of an oxidant reagent and a catalytic amount of metal salt or a chelated metal salt, wherein one nitrogen source is a bis(sulfonyl)imide or /V-halo-bis(sulfonyl)imide and the other nitrogen source is selected from the group consisting of an amide compound, an imide compound, a sulfonylcarbonylimide compound, and a carbamate compound.

2. - The process according to claim 1 , wherein the 1 ,2-diamino compound has the formula (I),

(I) the process comprising reacting the alkene of formula (II),

(II) with (a) a compound of formula XH, and (b) a bis(sulfonyl)imide of formula R₅S0₂NZ(S0₂ 5'), in the presence of a catalytic amount of a metal salt, and in the presence of an oxidant compound of formula Rn l(0₂CRi₂)₂, wherein:

R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and -CH(R_x)O(R_y);

R_d is a radical selected from the group consisting of (Ci-C₆)-alkyl,

(C₃-C₆)-cycloalkyl, and phenyl;

R_e is a radical selected from the group consisting of (Ci-C₆)-alkyl,,

(Ci-C₆)-alkoxy, -CN, halide, and -NO₂;

R_f is selected from the group consisting of SO₂R9, -COR_a, and -COOR_a. R_x is selected from the group consisting of H; (Ci-C₆) alkyl; (d-C₆)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, and S0₂R_a; phenyl; and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R_y is a radical selected from the group consisting of H; phenyl-(Ci-C₆)-alkyl; (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, CORd, hydroxy, N0₂, and OR_a; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and benzoyl;

R₅ and R₅< are each independently selected from the group consisting of (Ci-Ci₂)-alkyl, phenyl, phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₆)-alkoxy; (Ci-C₃)-alkylphenyl; phenyl- (Ci-C₃)-alkyl; (Ci-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl and (Ci-C₆)-alkoxy; and (Ci-C₄)-alkyl-tri- (Ci-C₄)-alkyl silane;

Z is H or a halide;

X a radical is selected from:

n is 0 or 1 ; n' is 1 , 2, 3, or 4;

R₆ is a radical selected from the group consisting of H; (Ci-Ci₂)-alkyl;

R₇ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, phthalimido, and SO₂R_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and ORi₀; R₈ is a radical selected from the group consisting of (d-C₆)-alkyl; H; halide; and NO₂;

Y is selected from C(O) and SO₂; R₉ is a radical selected from the group consisting of (Ci-C₆)-alkyl; (Ci-C₆)-alkyl substituted by an halide or an (Ci-C₄)-alkoxy; phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)- alkyl (Ci-C₄)-alkoxy, and an halide; R₁₀ is a radical selected from the group consisting of a (Ci-C₆)-alkyl; and phenyl;

R₁₂ is a radical selected from the group consisting of a (d-C₆)-alkyl; (Ci-C₆)- alkyl substituted by an halide; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl (Ci-C₄)-alkoxy, halide and N0₂.

3.- The process according to claim 1 , wherein the 1 ,2-diamino compound has the formula (I),

R₅S0₂ R₅.S0₂

N X

(I) the process comprising reacting the alkene of formula (II),

with (a) a compound of formula XH, and (b) a bis(sulfonyl)imide of formula R₅S0₂NZ(S0₂ 5'), in the presence of a catalytic amount of a metal salt, and in the presence of an oxidant compound of formula Rn l(0₂CRi₂)₂, wherein:

Ri , R₂ and R₃ are radicals independently selected from the group consisting of H; (Ci-C₆)-alkyl; (d-C₆)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, and S0₂R_a;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONR_bRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bRc, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and

OR_a; (Ci-Ci₂)-alkynyl; (Ci-Ci₂)-alkynyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, COR_d, hydroxy, NO₂, and OR_a; a C-radical derived from one of the known ring systems with 1 -2 rings, the rings being saturated, partially unsaturated or aromatic, the rings being isolated or fused and having 5-6 members, each member being independently selected from the group consisting of C,CH, CR_e, O, N, NH, and NR_f; and -CH(R_x)O(R_y);

R_d is a radical selected from the group consisting of (Ci-C₆)-alkyl,

(C₃-C₆)-cycloalkyl, and phenyl;

R_e is a radical selected from the group consisting of (Ci-C₆)-alkyl,, (Ci-C₆)-alkoxy, -CN, halide, and -N0₂;

R_y is a radical selected from the group consisting of H; phenyl-(Ci-C₆)-alkyl; (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, CORd, hydroxy, N0₂, and OR_a; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a,

(Ci-Ci₂)-alkyl, phenyl, phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl, and (Ci-C₆)-alkoxy; (Ci-C₃)-alkylphenyl; phenyl- (Ci-C₃)-alkyl; (Ci-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl and (Ci-C₆)-alkoxy; and (Ci-C₄)-alkyl-tri- (Ci-C₄)-alkyl silane;

Z is H or a halide;

X a radical is selected from:

n is 0 or 1 ;

R₆ is a radical selected from the group consisting of H; (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of halide, and COOR_a; phenyl; phenyl mono-, di- or tri-substituted with a radical selected from the group consisting of_N0₂, halide, (Ci-C₄)-alkyl, and (Ci-C₄)- oxyalkyl; S0₂R₉ and C(0)R₉; R₇ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

R₈ is a radical selected from the group consisting of (d-C₆)-alkyl; H; halide; and NO₂;

Y is selected from C(O) and SO₂;

R₁₀ is a radical selected from the group consisting of a (Ci-C₆)-alkyl; and phenyl; Rn is a radical selected from the group consisting of phenyl, and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, halide and N0₂; R₁₂ is a radical selected from the group consisting of a (d-C₆)-alkyl; (Ci-C₆)- alkyl substituted by an halide; phenyl; and phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl (Ci-C₄)-alkoxy, halide and N0₂.

4.- The process according to claim 3, wherein:

R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl;

(Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COORa, CONRbRc, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; phenyl (Ci-C₆)-alkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, S0₂R_a, -CN, phthalimide, hydroxy, N0₂, and OR_a; phenyl, phenyl mono-, di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy; and -CH(R_x)0(R_y);

R_x is selected from the group consisting of H; (Ci-C₆) alkyl; (Ci-C₆) alkyl substituted by a radical selected from the group consisting of COOR_a,

CONRbRc, halide, azide, and SO₂R_a; phenyl; and phenyl mono-,di-, or tri- substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, and (Ci-C₄)-alkoxy;

R₅ and R₅' are each independently selected from the group consisting of (Ci-Ci₂)-alkyl, phenyl, phenyl substituted by a radical selected from the group consisting of (d-C₆)-alkyl, and (Ci-C₆)-alkoxy; (Ci-C₃)-alkylphenyl; phenyl- (Ci-C₃)-alkyl; (Ci-C₃)-alkyl phenyl substituted by a radical selected from the group consisting of (Ci-C₆)-alkyl and (Ci-C₆)-alkoxy; and (Ci-C₄)-alkyl-tri- (Ci-C₄)-alkyl silane;

Z is H or a halide;

R₆ is a radical selected from the group consisting of H; (Ci-C₆)-alkyl;

(Ci-C₆)-alkyl substituted by a radical selected from the group consisting of halide, and COOR_a; phenyl; phenyl mono-,di- or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy; SO₂R₉; and C(0)R₉; and,

R₇ is a radical selected from the group consisting of (Ci-C₆)-alkyl; (Ci-C₆)- alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, phthalimido, and S0₂R_a; ORi₀; phenyl; and phenyl mono- ,di- or tri-substituted by a radical selected from the group consisting of (Ci- C₄)-alkyl, and (Ci-C₄)-alkoxy.

5.- The process according to claim 4, wherein R^ R₂, and R₃ are H, and R₄ is a radical selected from the group consisting of (Ci-Ci₂)-alkyl; (Ci-Ci₂)-alkyl substituted by a radical selected from the group consisting of COOR_a, CONRbRc, halide, azide, SO₂R_a, -CN, phthalimide, hydroxy, NO₂, and OR_a; (Ci-C₆)-phenylalkyl; (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl substituted by a radical selected from the group consisting of COOR_a, CONR_bR_c, halide, azide, SO₂R_a, -CN, phthalimide, hydroxy, NO₂, and OR_a; phenyl, phenyl mono-,di-, or tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl and (Ci-C₄)-alkoxy.

6.- The process according to claim 4, wherein Ri and R₂ are H; R₃ is selected from the group consisting of H, (Ci-C₆)-alkyl, and (C₃-C₆)-cycloalkyl; R₄ is CH(R_x)O(Ry); and R_x is a radical selected from the group consisting of H, phenyl and phenyl mono-,di- tri-substituted by a radical selected from the group consisting of (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy,halide, and NO₂,

7.- The process according to claim 4, wherein the alkene of formula (II) is selected from the group consisting of of 1 -octene, 1 -hexene, 1 -decene, 1 - duodecene, 4-phenylbutene, vinylcyclohexane, 3-methylhexene, methyl undec-10-enoate, 2-(dec-9-enyl)isoindoline-1 ,3-dione, (pent-4- enylsulfonyl)benzene, 1 1 -bromoundecene, 7-bromoheptene, 7-azidoheptene,

8. - The process according to any of the claims 1 -7, wherein XH is saccharin or phthalamide.

9. - The process according to any of the claims 1 -8, wherein the catalyst is a Pd(ll) salt.

10.- The process according to claim 9, wherein the catalyst is Pd(NCPh)₂CI₂, Pd(NCMe)₂CI₂ or Pd(hexafluoroacetylacetonate)₂.

1 1 . - The process according to any of the claims 1 -10, wherein Rn is phenyl, and R₁₂ is butyl or methyl.

12. - A compound of the formula (I) as defined in any of the claims 3-4.

13. - The compound according to claim 12, which is one of the following:

Λ/-(1 -bistosylamido-2-octyl)-saccharide, Λ/-(1 -bistosylamido-2-hexyl)- saccharide, /V-(1 -bistosylamido-2-decyl)-saccharide, /V-(1 -bistosylamido-2- duodecyl)-saccharide, Λ/-(1 -bistosylamido-4-phenyl-but-2-yl)-saccharide, N- (1 -cyclohexyl-2-bistosylamido-ethyl)-saccharide, syn/anti-/V-(1 -bistosylamido-

3- methyl-hex-2-yl)-saccharide, Λ/-(1 -bistosylamido-10-(methyloxycarbony)- decan-2-yl)-saccharide, Λ/-(1 -bistosylamido-10-phthaloyl-dec-2-yl)- saccharide, Λ/-(1 -bistosylamido-10-bromo-dec-2-yl)-saccharide, Λ/-(1 - bistosylamido-7-bromo-hept-2-yl)-saccharide, /V-(1 -bistosylamido-7-azido- hept-2-yl)-saccharide, /V-(1 -bistosylamido-5-phenylsulfonyl-pent-2-yl)- saccharide, /V-(1 -bistosylamido-4,4-bis(ethyloxycarbonyl)-but-2-yl)- saccharide, /V-(3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-/V- (phenylsulfonyl)benzenesulfonamide, /V-(3-(butyloxy)-2-(1 ,3-dioxoisoindolin- 2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, /V-(3-(propyloxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(3- (benzyloxy)-2-(1 , 1 -dioxido-3-oxobenzo[d]isothiazol-2(3/-/)-yl)propyl)-/V- (phenylsulfonyl)benzenesulfonamide, /V-(3-(butyloxy)-2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)propyl)-/V-

(phenylsulfonyl)benzenesulfonamide, /V-(3-(methoxy)-2-(1 ,3-dioxoisoindolin- 2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, /V-(3-(ethoxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(3- (octyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)propyl)-/V- (phenylsulfonyl)benzenesulfonamide, /V-(3-(benzoyloxy)-2-(1 ,3- dioxoisoindolin-2-yl)propyl)-/V-(phenylsulfonyl)benzenesulfonamide, N-((2R, S, 3R, S)-3-(benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-/V- (phenylsulfonyl)benzenesulfonamide, Λ/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-/V-(phenylsulfonyl)benzenesulfonamide, Λ/-(2-(1 , 1 -dioxido-3-oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-/V- (methylsulfonyl)methanesulfonamide, Λ/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-4-methyl-/V- (methylsulfonyl)benzenesulfonamide, A/-(2-(1 , 1 -dioxido-3- oxobenzo[d]isothiazol-2(3/-/)-yl)octyl)-2-(trimethylsilyl)-/V-((2- (trimethylsilyl)ethyl)sulfonyl)ethanesulfonamide, Λ/-(2-(1 ,3-dioxoisoindolin-2- yl)octyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(6-cyano-2-(1 ,3- dioxoisoindolin-2-yl)hexyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(3- (benzyloxy)-2-(1 ,3-dioxoisoindolin-2-yl)-2-methylpropyl)-N-

(phenylsulfonyl)benzenesulfonamide, N-(2-(1 ,3-dioxoisoindolin-2-yl)-3- hydroxypropyl)-N-(phenylsulfonyl)benzenesulfonamide, N-(-2-(1 ,3- dioxoisoindolin-2-yl)-3-methoxy-1 -phenylpropyl)-N- (methylsulfonyl)methanesulfonamide, N-(-2-(1 ,3-dioxoisoindolin-2-yl)-3- methoxy-1 -phenylpropyl)-4-methyl-N-tosylbenzenesulfonamide, N-(-2-(1 ,3- dioxoisoindolin-2-yl)-1 -phenylpropyl)-4-methyl-N-tosylbenzenesulfonamide or N-(2-(1 ,3-dioxoisoindolin-2-yl)-3-phenylpropyl)-4-methyl-N- tosylbenzenesulfonamide.

14.- A process for the preparation of a compound of formula (III), or a salt thereof, wherein R_m and R_n are H or an amino protective group and R₂, R₃, and R₄ are as defined above for compound (I)

R2 R3

(III) comprising submitting the compound of formula (I) to at least one

15. - The preparation process according to claim 14, wherein the compound of formula (I) is submitted to a first deprotection reaction using

iodotrimethylsilane in an adequate solvent, and, then to a second

deprotection reaction using HBr and HOAc, to yield a compound of formula (III) wherein R_m and R_n are H.

16. - The preparation process according to claim 14, wherein a compound of formula (I) wherein R₂ and R₃ are H, R₄ is an hexyl, R₅ and R₅< are 2- trimethylsilylethyl, and X is saccharinyl is reacted with CsF and DMF to yield a compound of formula (III) wherein R^ R₂ and R₃ are H, R₄ is an hexyl; R_n is H and R_m is 2-trimethylsilylethylsulphonyl.