WO2003051865A1 - Dioxathianones - Google Patents

Abstract

The invention relates to 1,3,2-dioxathian-2-ones with an exocyclic double bond in the 5-position as in formula (I), a method for production of said dioxathianones and use thereof as synthetic component for the production of compounds of formula (II), (IV) and (V).

Description

 Dioxathianone

The present invention relates to [1, 3.2] dioxathian-2-ones with an exocyclic double bond in the 5-position, a process for the preparation of these dioxathianones and their use as a synthesis unit.

The conversion of 1, 2- or 1, 3-diols into the corresponding sulfites by reaction with thionyl chloride (GV Fischer, T. Zimmermann, Comprehensive Heterocyclic Chemistry, AR Katritzky, CW Rees, Ed., Pergamon, Oxford 1984, Vol. 6 , 851-867 - BB Lohray, JR Ahuja, J. Chem. Soc, Chem. Comm. 1991, 95-97) or dialkyl sulfites (SA King, B. Pipik, DA Colon, M. Bhupathy, Synth. Comm. 1997 , 27, 701-707) is known in principle and has been described for some examples.

oder

or

The resulting sulfite is usually oxidized to sulfate, which can then be opened with nucleophiles. Various oxidizing agents have been described for the oxidation. Ruthenium chloride / sodium periodate is used as the standard oxidizing agent (Y. Gao, K.B. Sharpless, J. Am. Chem. Soc. 1988, 110, 7538-7539). A direct ring opening of these cyclic sulfites with nucleophiles is not possible.

Surprisingly, it has now been found [1, 3,2] dioxathian-2-ones with exocyclic double bond in the 5-position, that of the below Correspond to formula I, can be opened easily with nucleophiles. The sulfites formed during the ring opening cannot be isolated; the corresponding alcohols are obtained directly.

Such compounds are important intermediate or output stages for

syntheses:

The following compound can, for example, be enantioselectively cyclized to pyrroles using a Zr catalyst (Y. Yamaura, M. Mori, Heterocycles

2000, 52, 595-598).

Fürstner and Weinritt (J. Am. Chem. Soc. 119, 2944 (1997)) use

OH CI

for the synthesis of an anti-tumor agent (roseophilin).

Therefore, there has been a need for easy access to connections of the type

This object is achieved by the preparation process given above using the intermediate stage of the [1, 3,2] dioxathian-2-one with an exocyclic double bond in the 5-position.

The present invention therefore firstly relates to compounds of the formula I

wobei

in which

R ¹ , R ² , R each independently of one another represent H, a branched or unbranched alkyl, cycloalkyl, alkylaryl radical each having up to 30 C atoms or Ar and Ar represents an unsubstituted or one or more times with -

R ^y , -Sub, -OR ^y , -NR ^y ₂ and / or -OCF ₃ substituted aromatic or heteroarmoatic, 5- or 6-atom ring or corresponding fused ring systems and Sub stands for F; CI; Br, Ar, cyano, tertiary amino, d-

C ₄ -dialkylamino, CC ₄ -alkyl or -COOalkyl and the R ^y each independently represent branched or unbranched radicals -alkyl, -perfluoroalkyl, -alkyl-Ar, -alkoxy, -alkenyl, -Ar or -alkynyl each with bis to 20 carbon atoms, cycloalkyl, cycloalkoxy, cycloalkenyl or bicyclic systems each with up to 10 carbon atoms, it being possible for one or more hydrogen atoms to be substituted by sub in all of these groups. In the case of compounds of the formula I which are preferred according to the invention, R ¹ and R ^{2 are} H and particularly preferably all R are H.

The [1,3,2] dioxathian-2-ones with exocyclic double bond in the 5-position according to formula I can be prepared by reacting the corresponding 1,3-diols with thionyl chloride or by transesterifying the 1,3-diols with dialkyl sulfites.

The present invention therefore furthermore relates to a process for preparing a compound of the formula I with radicals as defined above, which is characterized in that a compound of the formula II

where R, R ¹ and R ^{2 have} the meaning given above, with a

V Veerrbbiinndduunngg S (0) CI ₂ or a compound S (0) (OR ³ ) _{2 is} implemented, where

R ^J stands for a linear or branched Cι _-3 o-alkyl radical.

Because of the possibility of ring opening with nucleophiles shown above, it is also possible to use compounds of the formula I, where R, R ¹ and R ^{2 have} the meaning given above for preparing compounds of the formula III,

wobei R, R¹ und R² die oben gegebene Bedeutung haben und

where R, R ¹ and R ^{2 have} the meaning given above and

Nu stands for -N ₃ , -NR ^X ₂ , -OR ^x , -SR ^X or -CHXY and

X and Y each independently represent -Ar, -CN, -C0 ₂ R ^x

, -S0 ₂ R ^x , -C0R or -N0 ₂ , where in the case X = -N0 ₂ Y can also be R ^x , and Ar has the meaning given above, and

R ^x , in each case independently of one another, stand for H, an unbranched or a single or multiple branched Cι _-3 o-alkyl radical, in which one or more -CH ₂ -CH ₂ - groups can also be replaced by - CH = CH- or - C≡C and one or more CH ₂ groups can be replaced by -O-, -CO-, -NR ^x - and one or more CH ₃ groups can be replaced by -COO-R ^x , -CONR ^x ₂ , -CN, -OCOR ^x , -NR ^X ₂ or - Ar or cycloalkyl with 3 to 12 ring atoms, it being possible for one or more CH ₂ groups in the cycloalkyringen to be replaced by -O-, -CO-, - NR ^X - and in cycloalkyl rings with 5 to 12 ring atoms one or more - CH ₂ -CH ₂ - groups can be replaced by -CH = CH- and one or more H atoms in cycloalkyl can be substituted by R ^X , a further subject of the present invention ,

The present invention thus provides easy access to the valuable synthesis building blocks according to formula III.

In addition, the OH group of the compounds of the formula III can be converted into a leaving group known to the person skilled in the art, preferably halide, methanesulfonate, benzenesulfonate, tosylate, by simple transformation. This leaving reaction can in turn be substituted in a next reaction step by a second Nudeophil Nu. The selection of suitable implementation conditions does not pose any difficulties for the person skilled in the art.

The known oxidation of the cyclic sulfites leads to the corresponding sulfates with simultaneous dihydroxylation of the double bond in the compounds of the formula I according to the invention.

The reaction succeeds, for example, with RuCI ₃ / Nal0 ₄ as an oxidizing agent.

Therefore, the use of compounds of the formula I, where R, R ¹ and R ^{2 have} the meaning given above, with the proviso that R ^y does not represent an alkenyl or alkynyl radical for the preparation of compounds of the formula IV,

where R, R ¹ and R ² have the meaning given above, wherein R ^y does not represent an alkenyl or alkynyl radical, and R ⁴ and R ⁵ each independently represent H, -C (0) R ^X or -R ^x , where R ^{x has} the meaning given above, and a process for the preparation of a compound of the formula IV, in which a compound of the formula I is reacted with the aid of an oxidizing agent in a reaction step, further objects of the present invention.

The selection of a suitable oxidizing agent for this reaction does not pose any difficulties for the person skilled in the art. Particularly preferably, Nal0 is used as the oxidizing agent according to the invention in the presence of catalytically active amounts of RuCl ₃ .

The present invention also relates to the novel compounds of the formula IV accessible therewith, with radicals R, R ¹ , R ² and R ⁴ as defined above, where R ^{5 is} H. In particularly preferred compounds of the formula IV, R, R ⁴ and R ^{5 are} H. Others Compounds of formula IV preferred according to the invention are characterized in that R ¹ and R ^{2 are} identical. In a further preferred embodiment of the present invention, compounds of the formula IV are prepared in which at least one of the radicals R ¹ and R ^{2 is}

H stands.

Those solvents are selected as solvents in this reaction which are not attacked by the chosen oxidizing agent under the reaction conditions. If the preferred oxidizing agent Nal0 / RuCI _{3 is} used, the preferred solvents are carbon tetrachloride, chloroform, dichloromethane, acetonitrile, acetone, ethyl acetate and water and mixtures of these solvents.

It was found that the yield of the reaction depends on the solvent used. The best yields are achieved in a mixture of acetonitrile and water, in particular in a mixing ratio of 6: 1 (parts by volume). It is therefore particularly preferred according to the invention to use such a solvent mixture.

For R ¹ , R ² = H, a derivative of tetraol iso-erythritol is obtained in which two primary hydroxyl groups are protected as cyclic sulfate. This means that each of the four hydroxyl groups of the underlying iso- erythritol can be selectively derivatized (Scheme 1).

Scheme 1: (SG: protection group; AG: leaving group) This is possible, for example, through the following sequence of reaction steps:

-Protection of the primary hydroxy function -Opening of the sulfate by Nudeophil 1 -hydrolysis of the resulting sulfate (the sulfate is stable and can be isolated, see examples)

- Conversion of the free primary hydroxy function into a leaving group - Nucleophilic substitution with Nudeophil 2

The known derivatives of iso-erythritol obtainable in this way are mainly used as acyclic nucleoside analogues: the acydonucleosides shown below have antiviral activity (S. Bailey, MR Harnden, J. Chem. Soc, Perkin Trans. 1 1988, 10, 2767-2775) .:

R=Me, CH₂OBn, OH F, CH₂OH

R = Me, CH ₂ OBn, OH F, CH ₂ OH

Ganciclovir and its derivatives show anti-herpes effects (J. Hannah, R.

L. Tolman, J.D. Karkas, R. Liou, H.C. Perry, A.K. Field, J. Heterocycl.

Chem. 1989, 26, 1261-1271):

Ganciclovir: Z = 0, R = H 2'-carbagancilovir: Z = CH ₂ , R = H

A process for the preparation of compounds according to formula V

_c where R and R are each independently the one given above

R 7

Have meaning, and R and R each independently represent -N ₃ , -CN, -OH or toluenesulfonamide, -OS0 ₃ ^~ , which is characterized in that a compound of formula IV is used as the starting material is for the reasons mentioned another subject _{1 Q of} the present invention.

The examples given below for the compounds or production processes according to the invention serve only for illustration and do not restrict the present invention in any way. Otherwise, the invention described in FIG. _{1 can be implemented} in the entire claimed range.

0

5

0

5 Examples:

5-methylene- [1,2,2] -dioxathian-2-one (1) (route 1):

To an emulsion of 2.57 g (29.2 mmol) 2-methylene-1, 3-propanediol in

20 ml of carbon tetrachloride are added with vigorous stirring at 0 ° C. to a solution of 5.21 g (43.8 mmol) of thionyl chloride in 10 ml of carbon tetrachloride. Violent gas evolution begins. After 30 minutes, the HCI development is complete and the solvent is removed at 0 ° C. and 5 mbar. Distillation (bp 73 ° C / 25 mbar) gives 3.48 g (25.9 mmol, 89%) of 5-methylene- [1, 3,2] - dioxathian-2-one (1) as a colorless liquid. - IR (film): v = 3088 cm ^{- '} ', 2991, 2938, 2873, 1461, 1446, 1416, 1342, 1300, 1239, 1195, 1177, 982, 958, 926, 870, 759, 717, 692, 663. ¹ H-NMR (250 MHz, CDCI3): δ = 4.24 [d, 3j = 12.9 Hz, 2 H, 4 (6) -H _eq *], 5.14 (s, 2 H, = CH ₂ ), 5.35 [d, 3j = -12.9 Hz, 2 H, 4 (6) -H _ax ^* ]. - 1 Q-NMR (62.9 MHz, CDCI ₃ ,

DEPT): δ = 61.55 [-, 2 C, C-4 (6)], 114.40 (-, 1 C, = CH ₂ ), 135.50 (C _quart , 1 C, C-5). - MS (El, 70 eV), m / z (%): 134 (6) [M ⁺ ], 70 (50), 69 (24), 42 (100), 41 (82). - C ₄ H ₆ 0 ₃ S (134.2): calc. C 35.81, H 4.51, found. C 36.11, H 4.51.

5-methylene- [1,2,2] -dioxathian-2-one (1) (route 2):

10 ml of anhydrous cyclohexane are placed in a heated and nitrogen-purged 10 ml round-bottom flask with a tap, 10 cm column, micro still and a drying tube filled with calcium chloride, and successively with 2-methylene-1,3-propanediol (500 mg, 5.67 mmol) and

Dimethyl sulfite (654 mg, 5.94 mmol) was added. After adding a drop of methanesulfonic acid (approx. 5-6 mg, 0.057 mmol, 1 mol%) and 2

Hours, 20 minutes of stirring at 50 ° C., a mixture starts out within 1 hour in the subsequent distillation at 430 mbar

Methanol and cyclohexane at approx. 30 ° C, later pure cyclohexane at approx.

50 ° C above (distilled solvent volume approx. 7-8 ml). To neutralize the methanesulfonic acid, the yellow-brown residue is mixed with three drops of triethylamine (color change to yellow). Further cyclohexane is at 150 mbar / room temp. condensed off. The condensate does not yet contain any product.

Finally, the residue is fractionally recondensed. Fraction 1 (100 mbar / room temp) contains cyclohexane and dimethyl sulfite. Fraction 2 (25 mbar / 70-80 ° C) is a colorless liquid mixture of cyclohexane, dimethyl sulfite and the product. 493 mg of crude product (composition: 91% 5-methylene- [1,3,2] -dioxathian-2-one, 6% cyclohexane, 3% dimethyl sulfite), corresponding to 451 mg of pure substance, are obtained.

2-Azidomethylprop-2-en-1-ol (2):

233 mg (3.58 mmol) of sodium azide are added to a solution of 400 mg (2.98 mmol) of 5-methylene- [1,2,3] dioxathian-2-oxide (1) in 3 ml of N, N-dimethylformamide, the solution is heated to 80 ° C in a preheated oil bath. After 15 min, the mixture is poured into 20 ml of water and extracted with 3 x 10 ml of diethyl ether. The combined organic extracts are washed with 10 ml of water and dried over MgSO4. Flash chromatography on 25 g of silica gel (1.5 x 18 cm, mobile solvent petroleum ether / ethyl acetate 65:35, Rf = 0.23) provides 258 mg (2.28 mmol, 77%) of 2-azidomethylprop-2-en-1-ol (2) as colorless liquid. - IR (film): v = 3270 cm ^~ 1 (OH), 2937, 2877, 2100, 1659, 1455, 1440, 1244, 1068, 1033, 915, 883. - 1 H-NMR (250 MHz, CDCI3): δ = 1.72 (s, 1 H, OH), 3.86 (s, 2 H, CH2N3), 4.19 (s, 2 H, 1-H), 5.18 (s, 1 H, 3-H), 5.28 (s, 1 H, 3-H). - 3C-NMR (62.9 MHz, CDCI3, DEPT): δ = 53.27 (-, 1 C, CH ₂ N ₃ ), 63.95 (-, 1 C, C-1), 114.59 (-, 1 C, C-3 ), 142.71 (C _quart , 1 C, C-

2). - MS (CI, NH3), m / z (%): 148 (72) [M + NH ₄ ⁺ + NH ₃ ], 131 (100) [M + NH ₄ ⁺ ]. - C4H7N3O (113.1): calc. C 42.47, H 6.24, N 37.15; gef. C 42.67, H 6.18, N 37.00. N- (2-hydroxymethylallyl) phthalimide (3):

1.38 g (7.45 mmol) of phthalimide potassium salt are added to a solution of 500 mg (3.73 mmol) of 5-methylene- [1,2,3] dioxathian-2-oxide (1) in 2 ml of N, N-dimethylformamide. the suspension is heated to 100 ° C. After 1 h, the mixture is poured into 14 ml of water, extracted with 3 × 10 ml of diethyl ether and the organic phase is washed with 10 ml of water. Drying the organic phase over MgS0 ₄ , removal of the solvent i. Vak. and subsequent flash chromatography on 60 g of silica gel (3 × 20 cm, mobile solvent petroleum ether / ethyl acetate 70:30, Rf = 0.17) yields 558 mg (2.57 mmol, 69%) of N- (2-hydroxymethylallyl) phthalimide (3) as white Solid (mp 83 ° C). - IR (KBr): v = 3509 crrH (OH), 3103, 2924, 2799, 1764, 1699, 1435, 1397, 1331, 1090, 1174, 1116, 1061, 950, 911, 729, 712. - 1 H- NMR (250 MHz, CDCI ₃ ): δ = 2.44 (t, 3j = 6.2 Hz, 1 H, OH), 4.13 (d, 3j = 6.2 Hz, 2 H, CH2OH), 4.36 (s, 2 H, 1- H), 5.11 (d, 2j = 0.5 Hz, 1 H, 3-H), 5.18 (d, ² J = 0.5 Hz, 1 H, 3-H), 7.26-7.76 (m, 2 H, ph-H ), 7.83-7.88 (m, 2 H, ph-H). - 1 C-NMR (62.9 MHz, CDCI3, DEPT): δ = 39.46 (-, 1 C, C-1), 64.22 (-, 1 C, CH ₂ OH), 114.12 (-, 1 C, C-3 ), 123.44 (+, 2 C, C-3 '), 131.90 (C _quart , 2 C, C-2'), 134.15 (+, 2 C, C-4 ¹ ), 142.90 (C _quart , 1 C , C-2), 168.32 (C _quart , 2 C, C-1 '). - MS (El, 70 eV), m / z (%): 217 (5) [M ⁺ ], 160 (37), 130 (40), 104 (58), 77 (72), 76 (100)

[CeH ₄ ⁺ ], 50, (50), 41 (45). - C-12HH NO3 (217.2): calc. C 66.35, H 5.14, N 6.45; gef. C 66.13, H 4.93, N 6.38.

2-phenoxymethylprop-2-en-1-ol (4) and 3-phenoxy-2-phenoxymethylpropene (5):

A suspension of 64.4 mg (2.68 mmol) sodium hydride in 3 ml tetrahydrofuran is cooled to 0 ° C. and 253 mg (2.69 mmol) phenol are added. After the evolution of hydrogen has ended, the solvent is removed i. Vak. and takes up the resulting sodium phenolate in 2 ml of N, N-dimethylformamide. This solution is added to a solution of 300 mg (2.24 mmol) of 5-methylene- [1,3,2] -dioxathian-2-oxide (1) in 1 ml of N, N-dimethylformamide and heated to 50 ° C. After 2.5 h, the mixture is poured into 20 ml of water and extracted with 3 x 10 ml of diethyl ether. The United organic extracts are washed with 5 ml of water and dried over MgSO ₄ . Distillation of the solvent i. Vak. and subsequent flash chromatography on 30 g of silica gel (2 × 20 cm, mobile solvent petroleum ether / ethyl acetate 75:25) gives two fractions. Fraction I (Rf = 0.22): 255 mg (1.55 mmol, 69%) 2-phenoxymethylprop-2-en-1-ol (4) as a colorless liquid. - IR (film): v = 3346 cm ^" 1 (OH),

3064, 3040, 2923, 2868, 1599, 1587, 1496, 1457, 1400, 1241, 1172, 1079, 1060, 1031, 916, 754, 691. - 1 H-NMR (250 MHz, CDCI ₃ ): δ = 1.74 (s, 1 H, OH), 4.27 (s, 2 H, 1-H), 4.60 (s, 2 H, CH ₂ OPh), 5.29 (s, 2 H, 3-H), 6.92-7.00 (m , 3 H, ph-H), 7.26-7.32 (m, 2 H, ph-H). - 13C-NMR (62.9 MHz, CDCI3, DEPT): δ = 63.92 (-, 1 C, C-1), 68.89 (-,

1 C, CH2θPh), 113.74 (-, 1 C, C-3 '), 114.64 (+, 2 C, C-2'), 121.00 (+, 1 C, C-4 '), 129.42 (+, 2 C , C-3 '), 144.07 (C _quart , 1 C, C-2), 158.40 (C _quart , 1 C, C-1'). - MS (El, 70 eV), m / z (%): 164 (30) [M +], 145 (29), 133 (32), 131 (23), 95 (30), 94 (100) [C ₆ H ₆ 0 ⁺ ], 77 (20), 43 (18), 41 (30). Fraction II (R _f = 0.67): 21 mg (8.74 μmol, 4%) 3-phenoxy-2-phenoxymethylpropene (5) as a colorless liquid. - 1 H-NMR (250 MHz, CDCI3): δ = 4.65 (s, 4 H, 3-H), 5.42 (s, 2 H, 1-H), 6.90-7.02 (m, 6 H, ph-H ), 7.25-7.37 (m, 4 H, ph-H). - 3C-NMR (62.9 MHz, CDCI3, DEPT): 'δ = 68.47 (-, 2 C, C-3), 114.74 (+, 4 C, C-2'), 115.67 (-, 1 C, C- 1), 120.98 (+, 2 C, C-4 '), 129.43 (+, 4 C, C-3'), 140.40 (C _quart , 1 C, C-2), 158.48 (C _quart ,

2 C, C-1 ').

2-acetoxymethylprop-2-en-1-ol (6) and 1, 3-diacetoxy-2-methylene propane (7):

367 mg (4.47 mmol) of sodium acetate and 6.0 mg are added to a solution of 300 mg (2.24 mmol) of 5-methylene- [1,3,2] -dioxathian-2-oxide (1) in 3 ml of N, N-dimethylformamide (2.24 μmol) 18-crown-6. The solution is heated to 100 ° C and stirred for 1 h. Cool to 25 ° C and give up

10 ml water. Extracting with 3 x 10 ml of ethyl acetate, washing the organic phase with 5 ml of water and drying over MgS0 gives after evaporation of the solvent i. Vak. and subsequent flash chromatography on 20 g of silica gel (1.5 20 cm, mobile solvent petroleum ether / ethyl acetate 50:50) two fractions. Fraction I (Rf = 0.45): 201 mg (1.55 mmol, 69%) 2-acetoxymethylprop-2-en-1-ol (6) as a colorless liquid. - IR (film): v = 3433 cm- ¹ (OH), 3095, 2936, 2875, 1744, 1660, 1455, 1376, 1243, 1029, 951, 916, 844. - 1 H-NMR (250 MHz, CDCI ₃ ): δ = 1.91 (bs, 1 H, OH), 2.10 (s, 3 H, COCH3) 4.14 (s, 2 H, 1-H), 4.64 (s, 2 H, CH ₂ OAc), 5.18 ( s, 1 H, 3-H), 5.24 (s, 1 H, 3-H). - 13C-NMR (62.9 MHz, CDCI3, DEPT): δ = 20.89 (+, 1 C, COCH3)

63.67 (-, 1 C, C-1), 64.74 (-, 1 C, CH ₂ OAc), 114.42 (-, 1 C, C-3), 143.32 (Cquart. 1 C, C-2), 171.02 ( C _qua rt. 1 C, COMe). - MS (CI, NH3), m / z (%): 165 (15) [M + NH ₄ ⁺ + NH3], 148 (100) [M + NH ₄ ⁺ ], 131 (5) [M + H ⁺ ]. Fraction II (Rf = 0.65): 35 mg (202 μmol, 9%) 1, 3-diacetoxy-2-methylene propane (7) as a colorless liquid. Spectral data see above.

Ethyl 2- (2-hydroxymethylallyl) malonate (8) and ethyl 5-methylene-2-oxotetraydropyran-3-ylacetate (9):

A suspension of 67 mg (2.79 mmol) of sodium hydride in 2 ml of tetrahydrofuran is cooled to 0 ° C. and a solution of 430 mg (2.68 mmol) of malonic acid diethyl ester in 2 ml of tetrahydrofuran is added. After the evolution of hydrogen has ended, the solvent j is removed. Vak. and takes the resulting diethyl sodium malonate in 2 ml

N, N-dimethylformamide. This solution is added to a solution of 300 mg (2.24 mmol) of 5-methylene- [1,3,2] -dioxathian-2-oxide (1) in 2 ml of N, N-dimethylformamide and heated to 100 ° C. After 1 h, the mixture is poured into 20 ml of water and extracted with 3 x 10 ml of diethyl ether. The combined organic extracts are washed with 5 ml of water and dried over MgSO ₄ . Distillation of the solvent i. Vak. and subsequent flash chromatography on 30 g of silica gel (2 × 20 cm, mobile solvent petroleum ether / ethyl acetate 60:40) gives two fractions. Fraction I (Rf = 0.38): 113 mg (493 μmol, 22%) 2- (2-hydroxymethylallyl) malonic acid diethyl ester (8) as colorless

Liquid. - IR (film): v - 3448 cm- ¹ (OH), 3081, 2984, 2938, 2874, 1599, 1734, 1466, 1447, 1393, 1370, 1335, 1234, 1153, 1036, 908, 860, 790. - 1 H-NMR (250 MHz, CDCI3): δ = 1.26 (t, ³ J = _{7 1 H} z, 6 H, CO2CH2CH3) 1.75 (bs, 1 H, OH), 2.69 (d, 3j = 7.8 Hz, 2 H, 1-H), 3.65 (t, 3j = 7.8 Hz, 1 H, CHC0 ₂ Et), 4.10 (bs, 2 H, CH ₂ OH), 4.22 (q, j = 7.1 Hz, 4 H, C0 ₂ CH ₂ Me), 4.93 (s, 1 H, 3-H), 5.10 (s, 1 H, 3-H). - 13C-NMR (62.9 MHz, CDCI ₃ , DEPT): δ = 14.02 (+, 2 C, C0 ₂ CH ₂ CH3), 31.68 (-, 1 C, C-1), 50.74 (+, 1 C, CHC0 ₂ Et), 61.53 (-, 2 C, CO2CH2CH3), 65.84 (-, 1 C, CH ₂ OH), 112.37 (-, 1 C, C-3), 145.11 (Cquart. ¹ C, C-2), 169.07 (C _quart , 2 C, C0 ₂ Et). - MS (El, 70 eV),

5 m / z (%): 230 (1) [M ⁺ ], 185 (35), 160 (90), 139 (40), 111 (100), 82 (27), 67

(20), 55 (22), 41 (15).

Fraction II (Rf = 0.38): 107 mg (581 μmol, 26%) 5-methylene-2-oxotetrahydropyran-3-ylacetic acid ethyl ester (9) as a colorless liquid. -

IR (film): v = 3085 cm ^-1 , 2986, 2939, 1735, 1467, 1444, 1379, 1345,

^" 10 1244, 1203, 1149, 1042, 913, 857, 831, 749. - ¹ H-NMR (250 MHz,

CDCI3): δ = 1.26 (t, 3j = 7.ι Hz, 3 H, CO2CH2CH3) 2.84 (dd, 2J = 16.1, ³ J = 6.9 Hz, 1 H, 4-H), 3.05 (dd, 2j = 16.1 , 3j = 8.5 Hz, 1 H, 4-H), 3.66 (dd, ² J = 8.5, ³ J = 6.9 Hz, 1 H, 3-H), 4.19-4.31 (m, 2 H, CH ₂ Me) , 4.79 (s, 2 H, 6-H), 5:11 to 5:14 (m, 2 H, = CH _2). - ^{1 3} C-NMR (62.9 MHz, CDCI3,

¹ 5 DEPT): δ = 14.03 (+, 1 C, CH3), 29.30 (-, 1 C, C-4), 47.21 (+, 1 C, C-3),

62.08 (-, 1 C, CH2Me), 71.90 (-, 1 C, C-6), 113.39 (-, 1 C, = CH ₂ ), 135.68 (Cquart. ¹ C, C-5), 167.58 (C _quar t, 1 C, C-2 ^* ), 168.02 (C _quart , 1 C, C0 ₂ Et *). - MS (El, 70 eV), m / z (%): 184 (3) [M ⁺ ], 138 (17), 111 (100), 82 (17), 67 (20), 55 (12). - CgHι ₂ 0 ₄ (184.2): calc. C 58.69.15, H 6.57; gef. 0 C 58.92, H 6.55.

5-hydroxymethyl-5-hydroxy-2,2-dioxo- [1, 3,2] -dioxathian-5-ol (10):

5 A solution of 15 mg (74.6 μmol) is added to a solution of 500 mg (3.73 mmol) of 5-methylene- [1,2,3] dioxathian-2-one (1) in 60 ml of acetonitrile at 0 ° C. Ruthenium (III) chloride and 1.59 g (7.45 mmol) sodium periodate in 10 ml water. After 3 min, filter through 1 cm of Celite and remove the solvent by distillation. Subsequent flash chromatography on 15 g of 0 silica gel (1.5 x 20 cm, eluent petroleum ether / ethyl acetate 35:65, Rf = 0.26) gives 591 mg (3.21 mmol, 86%) of 5-hydroxymethyl-5-hydroxy-2,2-dioxo - [1, 3,2] -dioxathian-5-ol (10) as white crystals. - IR (KBr) v = 3399 cm ^"1 (OH), 2959, 1453, 1391, 1354, 1316, 1197, 1152, 1111, 1032, 997, 979, 921, 901, 847, 806, 782, 690. - ¹ H-NMR (250 MHz, DMSO-dö): 5 δ = 3.34 (s, 2 H, CH ₂ OH), 4.42 [d, ² J = 10.6 Hz, 2 H, 4 (6) -H _ax *] , 4.79 [d, 2j = 10.6 Hz, 2 H, 4 (6) -H _eq *], 5.24 (bs, 1 H, OH), 5.73 (bs, 1 H, OH). - ³ C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 62.40 (-, 1 C, CH ₂ OH), 66.44 (Cquart. 1 C, C-5), 78.98 [-, 2 C, C-4 (6)]. - MS (CI, NH ₃ ), m / z (%): 403 (3) [2M + NH3 + NH ₄ ⁺ ], 386 (10) [2M + NH ₄ ⁺ ], 236 (22) [M + 2NH ₃ + NH ₄ ⁺ ], 219 (100) [M + NH3 + NH ₄ ⁺ ], 202 (16) [M + NH ₄ ⁺ ] .- C ₄ H ₈ 0 ₆ S (184.2): calc. C 26.09, H 4.38; gef. C 26.20, H 4.32.

Acetic acid 5-hydroxy-2,2-dioxo- [1, 3,2] -dioxathian-5-ylmethyl ester (11):

607 are added to a solution of 706 mg (3.83 mmol) of 5-hydroxymethyl-5-hydroxy-2,2-dioxo- [1, 3,2] -dioxathian-5-ol (10) in 10 ml of anhydrous ethyl acetate mg (7.67 mmol) pyridine and 783 mg (7.67 mmol) acetic anhydride and stir at 25 ° C. After 20 h the solution is i. Vak. concentrated. Column filtration over 15 g of silica gel (1.5 x 20 cm, mobile solvent petroleum ether / ethyl acetate 50:50) gives a mixture of the desired product with pyridine. The pyridine is condensed off at 10-3 mbar overnight, the product crystallizes out in colorless crystals. 832 mg (3.68 mmol, 96%) of 5-hydroxy-2,2-dioxo-acetic acid [1,3,2] -dioxathian-5-ylmethyl ester (11) are obtained. - IR (KBr) v = 3378 cm-1 (OH), 2957, 1717 (CO), 1465, 1405, 1386, 1321, 1268, 1197,

1175, 1109, 1058, 1009, 988, 941, 823, 776, 706. ¹ H-NMR (250 MHz, DMSO-de): δ = 2.05 (s, 3 H, COCH3), 4.04 (s, 2 H) , CH ₂ OAc), 4.49 [d, ² J = 11.2 Hz, 2 H, 4 (6) -H _ax ^* ], 4.75 [d, ² J = 11.2 Hz, 2 H, 4 (6) -H _eq ^* ], 6.10 (bs, 1H, OH). - 13C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.78 (+, 1 c, COCH3), 63.90 (-, 1 C, CH ₂ OAc), 65.00 (C _quar t. 1 C, C -5), 77.84 [-,

2 C, C-4 (6)], 170.23 (C _quart , 1 C, COMe). - MS (CI, NH ₃ ), m / z (%): 470 (10) [2M + NH ⁺ ], 261 (43) [M + NH3 + NH ₄ ⁺ ], 244 (100) [M + NH ₄ ⁺ ]. - C6H10O7S (226.2): calc. C 31.86, H 4.46; gef. C 32.20, H 4.35.

Sodium 2-acetoxymethyl-2-hydroxy-3-toluenesulfonylaminopropyl sulfate (12):

To a solution of 50 mg (221 μmol) acetic acid-5-hydroxy-2,2-dioxo-

[1, 3,2] -di-oxathian-5-ylmethyl ester (11) in 5 ml of tetrahydrofuran, _{44 m} g (221 μmol) of sodium toluenesulfonamide are added and the mixture is stirred for 15 h. you removes the solvent i. Vak. and receives 94 mg (221 µmol, 100%) sodium 2-acetoxymethyl-2-hydroxy-3-toluenesulfonylaminopropyl sulfate (12) as a white solid. - IR (KBr): v = 3500 cm ^"1 (OH), 3359, 3261, 1739 (CO), 1653, 1599, 1528, 1457, 1388, 1307, 1257, 1161, 1097, 1070, 1005, 904, 817 , 704. ¹ H NMR (250 MHz, DMSO-d6): δ = 2.02 (s, 3 H, OAc), 2.34 (s, 3 H, 5'-H), 2.76 (d, ² J = 6.9 Hz, 1 H, 3-H), overlaid by 2.78 (d,

2j = 6.9 Hz, 1 H, 3-H), 3.76 (d, ² j ₌ n .2 Hz, 1 H, 1-H), 3.84 (d, 2j = 11.2 Hz, 1 H, 1-H), 4.01 (d, ² J = 12.1 Hz, 1 H, CH ₂ OAc), 4.25 (d, 2j = 12.1 Hz, 1 H, CH ₂ OAc), 6.90 (bs, 1 H, OH), 7.32 (d, j = 8.1 Hz, 2 H, 3'-H), 7.68 (d, ³ J = 8.1 Hz, 2 H, 2'-H). - ¹ 3C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.78 (+, 1 C, COCH ₃ ), 21.15 +, 1 C, 5'-C), 48.81 (-, 1 C, C -

3), 56.23 (C _qu art. 1 C, C-2), 63.38 (-, 1 C, C-1), 66.04 (-, 1 C, CH ₂ OAc), 125.84 (+, 2 C, C- 2 '), 129.42 (+, 2 C, C-3'), 141.65 (C _qua rt. 1 C, C-1 '), 142.50 (Cquart. 1 C, C-4'), 170.30 (C _qu art , 1 C, COMe). - MS (ESI), m / z (%), anions: 397 (100) [A ^~ ], 525 (17), 696 (22), 816 (8) [M + A ^" ]; cations: 443 (54 ) [M + Na ⁺ ], 622 (86), 741 (76), 861 (100) [2M + Na ⁺ ].

Sodium 2-acetoxymethyl-2-hydroxy-3-azidopropyl sulfate (13):

29 mg are added to a solution of 100 mg (442 μmol) of 5-hydroxy-2,2-dioxo [1,3,2] dioxathian-5-ylmethyl acetate (11) in 5 ml of N, N-dimethylformamide (442 μmol) sodium umazid and stirred at 25 ° C. After 1 h, the solvent is removed by distillation, 129 mg (442 μmol) of sodium 2-acetoxymethyl-2-hydroxy-3-azidopropyl sulfate (13) are obtained as a white solid. - IR (KBr): v = 3467 crrH (OH), 21 13, 1734 (CO), 1662, 1457, 1387,

1254, 1137, 1071, 1049, 1015, 936, 829. - 1 H-NMR (250 MHz, DMSO- d ₆ ): δ = 2.03 (s, 3 H, OAc), 3.28 (s, 2 H, 3- H), 3.72 (s, 2 H, 1-H), 3.88 (d, 2j = 9.8 Hz, 1 H, CH ₂ OAc), 3.97 (d, ² J = 9.8 Hz, 1 H, CH2OAC), 5.51 ( s, 1H, OH). - 13C-NMR (62.9 MHz, DMSO-dö, DEPT): δ = 20.94 (+, 1 C, COCH3), 53.87 (-, 1 C, C-3), 65.21 (-, 1 C, C-1) , 67.40 (-, 1 C, CH ₂ OAc),

72.83 (Cq _U art. 1 C, C-2), 170.44 (C _qU art. 1 C, COMe). - MS (ESI), m / z (%), anions: 269 (100) [A-], 560 (84) [M + A ~]; Cations: 314 (16) [M + Na ⁺ ], 605 (54) [2M + Na ⁺ ], 896 (100) [3M + Na ⁺ ]. Acetic acid 2-hydroxy-2-hydroxymethylbutanenitrile (14):

A solution of 50 mg (221 μmol) acetic acid 5-hydroxy-2,2-dioxo [1,2,3] dioxathian-5-ylmethyl ester (11) and 16 mg (243 μmol) potassium cyanide in 1.5 ml N, N-dimethylformamide is stirred at 25 ° C. for 18 h. The solvent is i. Vak. removed and taken up in 5 ml of tetrahydrofuran. 8 μl of water and 12 μl of concentrated sulfuric acid are added and the mixture is stirred for 2 d. It is neutralized with 200 mg of solid sodium hydrogen carbonate, filtered and the solvent is removed by distillation. Subsequent flash chromatography on 5 g of silica gel (0.5 x 20 cm, mobile solvent petroleum ether / ethyl acetate 25:75, Rf = 0.15) gives 30 mg (173 μmol, 78%) acetic acid-2-hydroxy-2-hydroxymethylbutanenitrile (14) as colorless Liquid. - IR (KBr): v = 3387 cm- (OH), 2937, 2252, 1737, 1727, 1378, 1249, 151, 989, 836. - 1 H-NMR (250 MHz, DMSO-d ₆ ): δ = 2.02 (s, 3 H, COCH ₃ ), 2.63 (s, 2 H, 3-H), 3.25-3.42 (m, 2 H, CH ₂ OH), 3.90 (d, ² J = 11.2 Hz, 1 H, 1-H), 4.00

(d, 2j = 11.2 Hz, 1 H, 1-H), 5.07 (t, 3j = 5.7 Hz, 1 H, CH ₂ OH), 5.40 (s, 1 H, 2-OH). - 13C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.92 (+, 1 C, COCH3), 23.97 (-, 1 C, C-3), 64.10 (-, 1 C, CH ₂ OH ), 66.23 (-, 1 C, C-1), 71 -64 (Cquart, ¹ C, C-2), 118.41 (C _qU art. ¹ C, C-4), 170.43 (C _qua rt. ¹ C , COMe). MS (CI, NH3), m / z (%): 364 (5) [2M + NH ⁺ ], 191 (100)

[M + NH ₄ ⁺ ].

Acetic acid 2-hydroxy-2-hydroxymethylbutanenitrile (15) and 4-hydroxy-4-hydroxymethyldihydrofuran-2-one (16):

A solution of 100 mg (442 μmol) of acetic acid 5-hydroxy-2,2-dioxo [1,2,3] dioxathian-5-ylmethyl ester (11) and 32 mg (486 μmol) of potassium cyanide in 2 ml of N, N-dimethylformamide is stirred at 25 ° C. for 18 h. The solvent is i. Vak. removed, and take in 5 ml

Tetrahydrofuran. 80 μl of water and 12 μl of concentrated sulfuric acid are added and the mixture is stirred for 30 min. It is neutralized with 200 mg of solid sodium hydrogen carbonate, filtered and the solvent is removed by distillation. Subsequent flash chromatography on 5 g of silica gel (0.5 x 20 cm, eluent petroleum ether / ethyl acetate 25:75) gives two fractions:

Fraction I (Rf = 0.15): 13 mg (73.8 μmol, 17%) acetic acid-2-hydroxy-2-hydroxymethyl-butanenitrile (15) as a colorless liquid. Spectral data see above.

5 Fraction II (Rf = 0.15): 23 mg (177 μmol, 40%) 4-hydroxy-4-hydroxymethyldihydrofuran-2-one (16) as a colorless liquid. ¹ H-NMR (250 MHz, DMSO-dβ): δ = 2.22 (d, 2j = 15.9 Hz, 1 H, 3-H), 2.73 (d, 2j = 15.9 Hz, 1 H, 3-H), 3.37 (d, ³ J = 6.8 Hz, 2 H, CH ₂ OH), 3.98 (d, ² J = 8.3 Hz, 1 H, 5-H), 4.25 (d, j = 8.3 Hz, 1 H, 5- H), 5.13 (t, j = 6.8 Hz,

¹ 0 1 H, CH ₂ OH), 5.37 (s, 1 H, 4-OH). - ³ C-NMR (62.9 MHz, DMSO-d ₆ ,

DEPT): δ = 38.80 (-, 1 C, C-3), 64.20 (-, 1 C, CH ₂ OH), 76.16 (-, 1 C, C- 5), 76.92 (Cquart, ¹ C, C- 4), 176.38 (C _qua rt. C, C-2).

^" 15 Acetic acid 2-azidomethyl-2,3-dihydroxypropyl ester (17) and acetic acid 3-acetoxy-2-azidomethyl-2-hydroxypropyl ester (18):

A solution of 100 mg (442 µmol) of 5-hydroxy-2,2-dioxo [1,3,2] dioxathian-5-ylmethyl acetate (11) and 43 mg (663 mmol) of sodium azide

20 in 2 ml of N, N-dimethylformamide is stirred at 25 ° C. After 1 h, the solvent is removed i. Vac., Takes up in 5 ml of tetrahydrofuran and adds 10 μl of water and 10 μl of concentrated sulfuric acid. After 1 h, the mixture is neutralized with 100 mg of sodium hydrogen carbonate, filtered through Celite and the solvent is removed by distillation. Subsequent flash

25 Chromatography on 2 g of silica gel (0.5 x 20 cm, mobile solvent petroleum ether / ethyl acetate 25:75) gives two fractions: Fraction I (Rf = 0:27): 40 mg (212 μmol, 48%) acetic acid-2-azidomethyl-2 , 3-dihydroxypropyl ester (17). - IR (film): v = 3420 cm ^{~ 1} (OH), 2943, 2886, 2107, 1728 (CO), 1445, 1378, 1243, 1118, 1047, 992, 927, 795. -

30 1 H-NMR (250 MHz, DMSO-dö): δ = 2.01 (s, 3 H, COCH3), 3.24 (s, 2 H, 1 '-

H), 3.33 (d, 3j = 5.6 Hz, 2 H, 3-H), 3.88 (d, ² J = 11.1 Hz, 1 H, 1-H), 3.97 (d, 2j = 1 1.1 Hz, 1 H , 1-H), 4.86 (t, 3j = 5.6 Hz, 1 H, 3-OH), 5.12 (s, 1 H, 2-OH). - ^{1 3} C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.97 (+, 1 C, COCH3), 53.75 (-, 1 C, C-1 '), 62.85 (-, 1 C, C-3), 65.27 (-, 1 C, C-1), 5 73.92 (Cquart. ¹ C, C-2), 170.51 (C _qua rt, ¹ C, COMe). - MS (CI, NH ₃ ), m / z (%): 396 (34) [2M + NH ₄ ⁺ ], 207 (100) [M + NH ₄ ⁺ ]. Fraction II (Rf = 0.47): 8 mg (35.4 μmol, 8%) 3-acetoxy-2-azidomethyl-2-hydroxypropyl acetate (18). - ¹ H-NMR (250 MHz, DMSO-dö): δ = 2.02 (s, 6 H, COCH3), 3.32 (s, 2 H, 1'-H), 3.93 [d, ² J = 11.3 Hz, 1 H, 1 (3) -H], 4.01 [d, 2j = ι. 3 Hz, 1 H, 1 (3) -H], 5.60 (s, 1 H, OH). - ¹ 3c-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.82 (+, 2 C, COCH3), 53.77 (-, 1 C, C-1 '), 64.74 (-, 2 C, C -1 (3)), 72.33 (Cq _U art. ¹ C, C-2), 170.27 (Cquart, 1 C, COMe). MS (CI, NH3), m / z (%): 480 (5) [2M + NH ₄ ⁺ ], 249 (100) [M + NH ₄ ⁺ ].

10

3-acetoxy-2-acetoxymethylpropane-1,2-diol (19):

To a solution of 100 mg (442 μmol) acetic acid-5-hydroxy-2,2-dioxo-

^" 15 [1, 3,2] -dioxathian-5-ylmethyl ester (11) in 5 ml of tetrahydrofuran are added

94 mg (486 μmol) sodium toluenesulfonic acid amide and stirred for 2 h. 8 μl of water and 12 μl of concentrated sulfuric acid are added and the mixture is stirred for 32 min. It is neutralized with 100 mg of solid sodium hydrogen carbonate, filtered and the solvent is removed by distillation. Subsequent flash

20 Chromatography on 5 g of silica gel (0.5 x 20 cm, eluent

Petroleum ether / ethyl acetate 25:75, Rf = 0.25) gives 32 mg (154 μmol, 35%) 3-acetoxy-2-acetoxymethylpropane-1,2-diol (19) as a colorless liquid. - ¹ H NMR (250 MHz, DMSO-de): δ = 2.01 (s, 6 H, COCH3), 3.35 (d, ³ J = 5.8 Hz, 2 H, 1-H), 3.92 (d, ² J = 12.9 Hz, 2 H, 3-H), 5 overlaid by 3.97 (d, ² J = 12.9 Hz, 2 H, 3-H), 4.80 (t, 2j = 15.8 Hz, 1 H,

1-OH), 4.96 (s, 1H, OH). - ^{1 3} C-NMR (62.9 MHz, DMSO-d ₆ , DEPT): δ = 20.95 (+, 2 C, COCH3), 62.74 (-, 1 C, C-1), 65.02 (-, 2 C, C -. 3), 72.23 (Cquart ¹ C, C-2), 170.52 (C _qu art, 2 C, COMe). - MS (CI, NH3), m / z (%): 430 (3) [2M + NH ₄ ⁺ ], 224 (100) [M + NH ₄ ⁺ ]. 0

2-Chloromethyl-2,3-dihydroxypropyl acetate (20):

A solution of 112 mg (495 μmol) acetic acid-5-hydroxy-2,2-dioxo-5 [1, 3,2] -dioxathian-5-ylmethyl ester (11) and 93 mg (743 μmol) Glycine methyl ester hydrochloride in 2 ml of N, N-dimethylformamide is stirred with 150 mg (1.49 mmol) of triethylamine for 3 h at 60 ° C. The solvent is i. Vak. removed and taken up in 5 ml of tetrahydrofuran. You give 20 ul 20 percent. Sulfuric acid and 100 μl water and stir for 1 h. It is neutralized with 100 mg of solid sodium hydrogen carbonate, filtered and the solvent is removed by distillation. Subsequent flash

Chromatography on 5 g of silica gel (0.5 x 20 cm, eluent petroleum ether / ethyl acetate 25:75, Rf = 0.15) gives 14 mg (76.7 μmol, 15%) of 2-chloromethyl-2,3-dihydroxypropyl acetate (20) as a colorless liquid , - IR (KBr): v = 3378 cm ^{~ 1} (OH), 2958, 2886, 1725, 1430, 1391, 1371, 1246, 1045, 990, 962, 917, 863, 800.-

¹ H NMR (250 MHz, DMSO-d ₆ ): δ = 2.02 (s, 3 H, COCH ₃ ), 3.37 (d,

3j = 6.7 Hz, 2 H, 3-H), 3.58 (s, 2 H, 1'-H), 3.94 (d, ² J = 11.2 Hz, 1 H, 1-H),

4.00 (d, ² J = 11.2 HZ, 1 H, 1-H), 4.89 (t, 3j = 6.7 Hz, 1 H, 3-OH), 5.11 (s,

1 H, 2-OH). - ¹ 3c-NMR (62.9 MHz, DMSO-d6, DEPT): δ = 20.96 (+, 1 C, COCH3), 47.48 (-, 1 C, C-1 '), 62.62 (-, 1 C, C- 3), 65.12 (-, 1 C, C-1),

72.90 (Cq _U art, 1 C, C-2), 170.49 (C _qu art, 1 C, COMe). MS (CI, NH3), m / z (%): 384/382 (1/5) [2M + NH ₄ ⁺ ], 202/200 (32/100) [M + NH ₄ ⁺ ].

Claims

claims 1. compound according to formula I,

in which R ¹ , R ² , R each independently represent H, a branched or unbranched alkyl, cycloalkyl, alkylaryl radical each having up to 30 carbon atoms or Ar and Ar stands for an unsubstituted or one or more times with - R ^y , -Sub, -OR ^y , -NR ^y ₂ and / or -OCF ₃ substituted aromatic or heteroarmoatic, 5- or 6-atom Ring or corresponding condensed ring systems and Sub stands for F; CI; Br, Ar, cyano, tertiary amino, d- C ₄ -dialkylamino, -CC ₄ -alkyl or -COOalkyl and the R ^y each independently represent branched or unbranched radicals -alkyl, -perfluoroalkyl, -alkyl-ar, -alkoxy, -alkenyl, -ar or -alkynyl each with up to 20 carbon atoms, cycloalkyl, cycloalkoxy, cycloalkenyl or bicyclic systems each with up to 10 carbon atoms, in all of these groups one or more hydrogen atoms can also be substituted by sub. 2. A compound according to claim 1, characterized in that R ¹ and ^{2 are} H, and preferably all R are H. 3. Process for the preparation of a compound of formula I with Residues as defined in claim 1, characterized in that a compound according to formula II,

where R, R ¹ and R ^{2 have} the meaning given above, with a Compound S (0) CI ₂ or a compound S (0) (OR) _{2 is} reacted, wherein R ^J stands for a linear or branched C _-30 alkyl radical. 4. Use of compounds of the formula I, where R, R ¹ and R ² have the meaning given in claim 1 for the preparation of compounds of the formula III,

wherein R, R ¹ and R ^{2 have} the meaning given in claim 1 and Nu stands for -N ₃ , -NR ^X ₂ , -OR ^x , -SR ^X or -CHXY and X and Y each independently represent -Ar, -CN, -C0 ₂ R ^x , -S0 ₂ R ^x , -COR ^x or -N0 ₂₎ where in the case X = -N0 ₂ Y can also be R ^x , and Ar has the meaning given in claim 1, R ^x , in each case independently of one another, stand for H, an unbranched or a single or multiple branched Cι _-3 o-alkyl radical, in which one or more -CH ₂ -CH ₂ - groups can also be replaced by -CH = CH- or - C≡C and one or more CH ₂ groups can be replaced by -O-, -CO-, -NR ^X - and one or more CH ₃ groups can be replaced by -COO-R ^x , -C0NR ^X ₂ , -CN, - OCOR ^x , -NR ^X ₂ or -Ar or cycloalkyl with 3 to 12 ring atoms, one or more CH ₂ groups being replaced in the cycloalkyringes can be replaced by -O-, -CO-, -NR ^X - and in cycloalkyl rings with 5 to 12 ring atoms one or more -CH ₂ -CH ₂ - groups can be replaced by -CH = CH- and one or more H atoms may be substituted by R ^x in cycloalkyl. 5. Use of compounds of the formula I, where R, R ¹ and R ^{2 have} the meaning given in claim 1 with the proviso that R ^y does not represent an alkenyl or alkynyl radical for the preparation of compounds of the formula IV,

where R, R ¹ and R ² have the meaning given in claim 1, wherein R ^y does not represent an alkenyl or alkynyl radical, and R ⁴ and R ⁵ each independently represent H, -C (0) R ^x or -R ^x , where R ^{x has} the meaning given in claim 4. 6. A process for the preparation of a compound according to formula IV, where all radicals have the meaning according to claim 5, characterized in that in a reaction cut a compound of formula I having radicals according to claim 1 with the proviso that R ^y does not represent an alkenyl or alkynyl radical is reacted with the aid of an oxidizing agent. 7. The method according to claim 6, characterized in that Nal0 mixed with RuCI _{3 is} used as the oxidizing agent. 8. A compound according to formula IV, with radicals R, R ¹ , R ² and R ⁴ according to claim 5, characterized in that R ^{5 is} H. 9. A compound according to claim 8, characterized in that R, R ⁴ and R ^{5 are} H. 10. A compound according to at least one of the preceding claims, characterized in that R ¹ and R ^{2 are the} same. 11. A compound according to at least one of claims 8 or 9, characterized in that at least one of the radicals R ¹ and R ^{2 is} H. 0 12. Process for the preparation of compounds according to formula V

wherein R ⁴ and R ⁵ each independently have the meaning given in claim 5, and R ⁶ and R ⁷ each independently represent -N ₃ , -CN, -OH Q or toluenesulfonamide, -OS0 ₃ ^" , characterized in that the starting material is a compound of the formula IV in which the radicals given in claim 5 Have meaning is used. 5 0 5