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WO1989002428A1 - Procede enantioselectif - Google Patents

Procede enantioselectif Download PDF

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Publication number
WO1989002428A1
WO1989002428A1 PCT/AU1988/000345 AU8800345W WO8902428A1 WO 1989002428 A1 WO1989002428 A1 WO 1989002428A1 AU 8800345 W AU8800345 W AU 8800345W WO 8902428 A1 WO8902428 A1 WO 8902428A1
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WO
WIPO (PCT)
Prior art keywords
group
process according
compound
alkoxy
formula iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU1988/000345
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English (en)
Inventor
Matt Gredley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orica Australia Pty Ltd
Original Assignee
ICI Australia Operations Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ICI Australia Operations Pty Ltd filed Critical ICI Australia Operations Pty Ltd
Priority to KR1019890700811A priority Critical patent/KR890701536A/ko
Publication of WO1989002428A1 publication Critical patent/WO1989002428A1/fr
Priority to FI892394A priority patent/FI892394L/fi
Priority to NO90901159A priority patent/NO901159L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form

Definitions

  • the present invention relates to a process for preparation of diol intermediates of use in preparation of biologically active compounds.
  • the present invention relates to an enantioselective process for preparation of such diols of formula I
  • Ar is selected from aryl, heteroaryl, substituted aryl and substituted heteroaryl, and R is a carboxylic acid group or ester or a group capable of being converted to a carboxylic acid or ester;
  • R is a carboxylic acid group or ester or a group capable of being converted to a carboxylic acid or ester;
  • Diltiazem a benzothiazepine derivative which is well known as a vasodilator is one of four possible optical isomers.
  • Diltiazem a benzothiazepine derivative which is well known as a vasodilator.
  • Diltiazem is the isomer of commercial interest as a vasodilator.
  • the desired (2S,3S) isomer can be obtained in at most a 25% yield, and hence workers in the area have concentrated on stereoselective synthetic routes which require the starting materials, such as the diol of formula I, to have a high optical purity.
  • Sharpiess and Hentges have described an enantioselective process for preparation of vicinal diols involving reaction of an olefinic hydrocarbon with a stoichiometric amount of osmium tetroxide in pyridine, followed by reductive hydrolysis. Despite the efficiency of this process, the toxicity of osmium tetroxide and its considerable cost mean that such a process would be uneconomic and produce a considerable waste problem in large scale preparations.
  • osmium tetroxide may be used to prepare compounds of formula I from the corresponding Q ⁇ - nsaturated acid, ester or precursor thereto with a high degree of enantioselectivity.
  • Ar is selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl;
  • R is a carboxyl group, an esterified carboxyl group or a group capable of being converted to said carboxyl or esterified carboxyl; the process comprising; reacting a compound of formula III
  • Ar is preferably selected from the group of formula IV
  • X is independently selected from the group consisting of halogen, C, to C ⁇ alkyl, C.. to C ⁇ alkoxy, C. to C g alkylthio, and more preferably C, to C. alkyl and C- to C. alkoxy, and n is an integer of from 0 to 3 inclusive and preferably n is 0 or 1.
  • Ar is heteroaryl include; furyl, pyridyl, thenyl, pyrolyl and benzofuranyl and substituted heteroaryl include such groups substituted by C. to C ⁇ alkyl or C. to C ⁇ alkoxy.
  • Ar is p-(C, to C ⁇ alkoxy)phenyl, for example p-methoxyphenyl;
  • R is selected from the group
  • G is chosen from the group consisting of: hydrogen, hydroxy, mercapto, C. to C 1Q alkoxy, C, to C, 0 haloalkoxy, C 2 to C, Q alkenyloxy, C- to C, Q alkynyloxy, C, to C, Q alkynylthio, C- to C_ cycloalkoxy, C ⁇ to C_ cycloalkoxy substituted with one or two C. to C.
  • alkyl groups phenoxy, phenylthio, benzyloxy, benzylthio, the group C, to C fi alkoxy substituted with a substituent chosen from the group consisting of C. to C fi alkoxy, amino, ammonio, cyano, N-CC. to C fi alkyl)amino and N,N,N-tri(C 1 to C g alkyl) mmonio, the groups phenoxy, phenylthio, benzyloxy and benzylthio wherein in each group the phenyl ring is substituted with from 1 to 3 substituents chosen from the group consisting of halogen, nitro, cyano, C. to C fi alkyl, C.
  • R is cyano, the group -C-G wherein
  • G is selected from hydrogen, hydroxy, C. to C ⁇ alkyl, C, to C, alkoxy and the group CH, wherein Z is hydroxy, chloro or C, to C ⁇ alkoxy.
  • R are the group -C-G where G is hydroxy or C, to C ⁇ alkoxy (e.g. methoxy) .
  • the compound of formula III may be the cis- or trans- geometrical isomer.
  • the compound of formula III is the trans- geometrical isomer.
  • composition of the compound of formula III comprise at least 85% (more preferably at least 95%) of one of the cis or trans geometrical isomers.
  • the trans imsomer is predominant, that is preferably the composition of the compound of formula III will comprise at least 85% (more preferably at least 95%) of the trans- geometrical isomer.
  • the compound of fo-rmula III consists essentially of the trans geometrical isomer.
  • osmium tetroxide forms adducts with many different types of amino compound and tertiary amines in particular form stable complexes with OsO..
  • the osmylation is carried out in the presence of a chiral nitrogen compound.
  • the mechanism of the reaction in the present process is not known.
  • the asymmetric induction may then result from steric interactions between the chiral nitrogen ligand and the substituents on the alkene.
  • the optically active nitrogen compound used in the process be of a type which complexes reasonably strongly with the osmium tetroxide.
  • the most effective and hence more preferred chiral nitrogen compounds are those in which a centre of chirality is located adjacent to the complexing nitrogen atom.
  • Figure V represents the preferred chiral a ine for providing high levels of asymmetric induction:
  • R.. , R ⁇ and R g are three different groups on the chiral centre; and A., and A_ are alkyl or substituted alkyl groups and one or more of R., R-,
  • R-. , ,- and 2 may link together to form one or more rings.
  • optically active amines examples include trisubstituted nitrogen-containing compounds, and in particular compounds having a tertiary bridgehead amine group such as a guinuclidine group.
  • Particularly preferred catalysts include dihydroguinine esters and dihydroquinidine esters.
  • esters examples include dihydroguinine acetate, dihydroquinine p-chlorobenzoate, dihydroquinidine acetate and dihydroquinidine p-chlorobenzoate.
  • the molar ratio of the osmium tetroxide to said nitrogen containing compound will be in the range of from 1:10 to 10:1.
  • the molar ratio of osmium tetroxide to said nitrogen containing compound is in the range of from 1:1 to 1:2 and we have generally found that a ratio of about 1:1.5 gives the best results.
  • osmium tetroxide may be generated in situ from osmium (III) halides such osmium (III) chloride under the reaction conditions of the process of the invention. Hence in carrying out the process of the invention osmium tetroxide may be replaced by an equimolar amount of the halide and in particular osmium (III) chloride.
  • oxidant examples include amine oxides and peroxides.
  • said oxidant is selected such that it is capable of reoxidising osmium tetroxide which is reduced during the course of the reaction.
  • Preferred oxidants are amine oxides such as N-methylmorpholine— -oxide.
  • Suitable solvents are generally selected from the group of aliphatic hydrocarbons such as C . to C, Q alkanes; aromatic hydrocarbons such as xylene, toluene and benzene; chlorinated hydrocarbons such as C. to C ⁇ haloalkanes; alcohols such as C 1 to C ⁇ alcohols; ketones such as C, to C ⁇ ketones; and esters such as ethyl acetate.
  • Specific examples of preferred solvents include dichloromethane, toluene, benzene, acetone, and butanol.
  • the reaction be carried out in the presence of at least one mole equivalent of water, based on the compound of formula III.
  • water Most commerically available solvents will contain adequate amounts of water unless thoroughly dried.
  • water-immiscible organic phases are aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and esters.
  • Preferred water-immiscible solvents include dichloromethane, toluene and benzene.
  • osmium tetroxide levels of 5 mole percent and less provide a product of high enantioselectivity. This is particularly surprising as might be expected from the paper of Sharpies and Hentges that stoichiometric amounts may be necessary to provide the degree of enantioselectivity which was observed.
  • the osmium tetroxide will be used in an amount equal to at least 0.01 mole % based on the compound of formula III. Smaller quantities may be used if desired; however, the chemical yields and enantiomeric excess of product are generally reduced.
  • reaction is carried out at a temperature in the range of from -20 to 80°C.
  • Convenient working temperatures may differ depending on the reactant and other conditions. However, the preferred temperature is generally in the range of from -5° to 40°C, although higher or lower temperatures may be used if desired. In some instances the optical purity of the compound of formula I is enhanced by carrying out the process at a temperature lower than ambient, for example in the range -5° to 10 , and we have found this temperature range generally provides excellent results in terms of both chemical yield and optical purity.
  • Example 1 The process of Example 1 was repeated using different conditions.
  • OsO4. Mole % of OsO4. based on substrate.
  • Oxid - Molar equivalents of oxidant (N-methyl morpholine-N-oxide) based on substrate.
  • N-methyl morpholine-N-oxide 50mg, 0.42m mole
  • 35 Dihydroquinidine acetate 3mg, 0.008m mole
  • Toulene 0.5ml
  • Example 13 The reaction was worked-up following the procedure given in Example 1 to give 82mg of crude erythro diol (80%). Nuclear magnetic reasonance spectroscopy showed no trace of starting cinnamate and the diol was found to be enantiomertically enriched (ee 12% major isomer 2R, 3R) by using the procedure described in Example 1.
  • Example 13
  • Example 1 The process of Example 1 may be repeated using a composition of 2-furylacrylonitrile comprising a majority of the trans-isomer to provide an enantiomerically enriched diol (3 furyl-2,3-dihydroxypropionitrile predominant in the (2S, 3R) isomer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé énantiosélectif de préparation de diols de formule (I), dans lequel Ar est choisi parmi l'aryle, l'hétéroaryle, l'aryle substitué et l'hétéroaryle substitué et où R représente un groupe carboxyle, un carboxyle estérifié ou un groupe susceptible d'être transformé en ce carboxyle ou en carboxyle estérifié. Ce procédé consiste à faire réagir un composé de formule (III): Ar-H C=C H R, avec 20 moles pour cent au maximum, sur la base dudit composé de formule (III), de tétroxyde d'osmium en présence d'un composé optiquement actif contenant de l'azote et d'un oxydant. Les composés de formule (I) sont utiles comme intermédiaires dans la préparation de composés biologiquement actifs et en particulier du Diltiazem pharmaceutique.
PCT/AU1988/000345 1987-09-18 1988-09-06 Procede enantioselectif Ceased WO1989002428A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1019890700811A KR890701536A (ko) 1987-09-18 1988-09-06 좌우상 선택적 제조방법
FI892394A FI892394L (fi) 1987-09-18 1989-05-18 Enantioselektivt foerfarande.
NO90901159A NO901159L (no) 1987-09-18 1990-03-13 Enantioselektiv fremgangsmaate.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPI445887 1987-09-18
AUPI4458 1987-09-18

Publications (1)

Publication Number Publication Date
WO1989002428A1 true WO1989002428A1 (fr) 1989-03-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1988/000345 Ceased WO1989002428A1 (fr) 1987-09-18 1988-09-06 Procede enantioselectif

Country Status (5)

Country Link
KR (1) KR890701536A (fr)
CN (1) CN1032783A (fr)
FI (1) FI892394L (fr)
WO (1) WO1989002428A1 (fr)
ZA (1) ZA886624B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4965364A (en) * 1988-02-23 1990-10-23 Massachusetts Institute Of Technology Ligand-accelerated catalytic asymmetric dihydroxylation
US5126494A (en) * 1988-01-11 1992-06-30 Massachusetts Institute Of Technology Methods for catalytic asymmetric dihydroxylation of olefins
US5227543A (en) * 1988-01-11 1993-07-13 Massachusetts Institute Of Technology Facilitation of turnover in the ADH by additives which catalyze the hydrolysis of the OS(VI) glycolate esters
US5260461A (en) * 1988-01-11 1993-11-09 Massachusetts Institute Of Technology Ligands for ADH: cinchona alkaloids and moderately sized organic substituents linked through a planar aromatic spacer group
US5419817A (en) * 1992-02-21 1995-05-30 Sepracor Inc. Electrocatalytic asymmetric dihydroxylation of olefinic compounds
US5516929A (en) * 1988-01-11 1996-05-14 Massachusetts Institute Of Technology Method for catalytic asymmetric dihydroxylation of olefins using heterocyclic chiral ligands
US5998637A (en) * 1997-02-27 1999-12-07 Tanabe Seiyaku Co., Ltd. Process for preparing optically active trans-3-substituted glycidic acid ester
US6495217B2 (en) * 1998-10-02 2002-12-17 Merck Patent Gmbh Chiral compounds
US6852874B2 (en) * 2000-10-02 2005-02-08 The Scripps Research Institute Second cycle asymmetric dihydroxylation reaction

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187448A (ja) * 1986-02-12 1987-08-15 Nippon Iyakuhin Kogyo Kk スレオ−２−ヒドロキシ−３−（４−メトキシフエニル）−３−（２−ニトロフエニルチオ）−プロピオン酸の製法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187448A (ja) * 1986-02-12 1987-08-15 Nippon Iyakuhin Kogyo Kk スレオ−２−ヒドロキシ−３−（４−メトキシフエニル）−３−（２−ニトロフエニルチオ）−プロピオン酸の製法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume 102, No. 12, pages 4263-4265, issued June 1980, S.G. HENTGES, K.B. SHARPLESS, "Asymmetric Induction in the Reaction of Osmium Tetroxide with Olefins". *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume 109, No. 20, pages 6213-6215, issued 1987, K. TOMIOKA, N. MAKOTO, K. KENJI, "Enantioface Differentiation in Cis Dihydroxylation of C-C double Bonds by Osmium Tetroxide with Use of a Chiral Amine with D2 Symmetry. *
JOURNAL OF THE CHEMICAL SOCIETY (Sec.B), pages 803-807, issued 1966, H.B. HENBEST, W.R. JACKSON, B.C.G. ROBB, "Electronic Effects in the Reactions of Olefins with Permanganate Ion and with Osmium Tetroxide". *
JOURNAL OF THE INDIAN CHEMICAL SOCIETY, Volume 59, No. 2, pages 119-123, issued February 1982, R.RAY, D.S. MATTESON, "A Highly Efficient Osmium Tetroxide Catalysed Oxidation of Sterically Hindered Olefins to Diols". *
PATENT ABSTRACTS OF JAPAN, C-474, page 6; & JP,A,62 187 448 (NIPPON IYAKUHIN KOGYO KK), 15 August 1987 (15.08.87). *
TETRAHEDRON LETTERS, Volume 24, No. 37, pages 3951-3954, issued 1983, G. STORK, M. KAHN, "A Highly Stereoselective Osmium Tetroxide-Catalysed Hydroxylation of delta-Hydroxyl beta-Unsaturated Esters". *
TETRAHEDRON LETTERS, Volume 27, No. 34, pages 3951-3954, issued 1986, M. TOKLES, J.K. SNYDER, "Assymetric Oxidation of Olefins to Vicinal Diols with Osmium Tetroxide". *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5126494A (en) * 1988-01-11 1992-06-30 Massachusetts Institute Of Technology Methods for catalytic asymmetric dihydroxylation of olefins
US5227543A (en) * 1988-01-11 1993-07-13 Massachusetts Institute Of Technology Facilitation of turnover in the ADH by additives which catalyze the hydrolysis of the OS(VI) glycolate esters
US5260461A (en) * 1988-01-11 1993-11-09 Massachusetts Institute Of Technology Ligands for ADH: cinchona alkaloids and moderately sized organic substituents linked through a planar aromatic spacer group
US5516929A (en) * 1988-01-11 1996-05-14 Massachusetts Institute Of Technology Method for catalytic asymmetric dihydroxylation of olefins using heterocyclic chiral ligands
US4965364A (en) * 1988-02-23 1990-10-23 Massachusetts Institute Of Technology Ligand-accelerated catalytic asymmetric dihydroxylation
US5419817A (en) * 1992-02-21 1995-05-30 Sepracor Inc. Electrocatalytic asymmetric dihydroxylation of olefinic compounds
US5998637A (en) * 1997-02-27 1999-12-07 Tanabe Seiyaku Co., Ltd. Process for preparing optically active trans-3-substituted glycidic acid ester
US6197953B1 (en) 1997-02-27 2001-03-06 Tanabe Seiyaku Co., Ltd. Process for preparing optically active trans-3-substituted glycidic acid ester
US6495217B2 (en) * 1998-10-02 2002-12-17 Merck Patent Gmbh Chiral compounds
US6852874B2 (en) * 2000-10-02 2005-02-08 The Scripps Research Institute Second cycle asymmetric dihydroxylation reaction

Also Published As

Publication number Publication date
KR890701536A (ko) 1989-12-20
ZA886624B (en) 1989-04-26
FI892394A0 (fi) 1989-05-18
CN1032783A (zh) 1989-05-10
FI892394A7 (fi) 1989-05-18
FI892394L (fi) 1989-05-18

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