A SIMPLIFIED PROCEDURE FOR THE STEREOSPECIFIC TRANSFORMATION OF 1,2-DIOLS INTO EPOXIDES

被引：305
|
作者：
KOLB, HC [1 ]
SHARPLESS, KB [1 ]
机构：
[1] Scripps Res Inst, DEPT CHEM, 10666 N TORREY PINES RD, LA JOLLA, CA 92037 USA
来源：
TETRAHEDRON | 1992年 / 48卷 / 48期
关键词：
D O I：
10.1016/S0040-4020(01)88349-6
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A simple, 'one-pot' procedure for the conversion of vicinal diols into epoxides via halohydrin ester intermediates has been developed. This method tolerates a wide range of functionality including acid sensitive functional. The transformation proceeds via a, usually highly regioselective, nucleophilic opening of a cyclic acetoxonium intermediate, generated from a cyclic orthoacetate and Me3SiCl, acetyl bromide or acetyl chloride/NaI to form 1-acetoxy-2-chloride, 1-acetoxy-2-bromide or 1-acetoxy-2-iodide intermediates, respectively. No epimerization occurs, even with benzylic substrates. Subsequent base mediated methanolysis furnishes epoxides in excellent overall yield. Application of this method led to an efficient formal synthesis of the leukotriene antagonist SKF 104353, commencing with the highly enantioselective cis-dihydroxylation of methyl 3-[2-(8-phenyloctyl)phenyl]propenoate.
引用
收藏
页码：10515 / 10530
页数：16
相关论文
共 50 条
  • [31] STEREOCHEMICAL EQUILIBRATION OF THE LITHIUM DERIVATIVES OF 1,2-DIOLS
    SLEMON, CE
    YATES, P
    CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1979, 57 (03): : 304 - 313
  • [32] PROTECTION OF 1,2-DIOLS AS CYCLIC ORTHO ESTERS
    LAMM, B
    FRANTSI, M
    ACTA PHARMACEUTICA SUECICA, 1986, 23 (06): : 410 - 411
  • [33] REGIOCONTROLLED AND STEREOCONTROLLED SYNTHESES OF CYCLIC CHIRAL CIS-AMINO ALCOHOLS FROM 1,2-DIOLS OR EPOXIDES
    SENANAYAKE, CH
    DIMICHELE, LM
    LIU, J
    FREDENBURGH, LE
    RYAN, KM
    ROBERTS, FE
    LARSEN, RD
    VERHOEVEN, TR
    REIDER, PJ
    TETRAHEDRON LETTERS, 1995, 36 (42) : 7615 - 7618
  • [34] LONG-CHAIN 1,2-DIOLS AND THEIR PREPARATION
    RUTZEN, H
    FETTE SEIFEN ANSTRICHMITTEL, 1979, 81 (12): : 477 - 477
  • [35] CHROMIC ACID OXIDATION OF DIASTEREOISOMERIC 1,2-DIOLS
    HEINDEL, ND
    HANRAHAN, ES
    SINKOVIT.RJ
    JOURNAL OF ORGANIC CHEMISTRY, 1966, 31 (06): : 2019 - &
  • [36] LONG-CHAIN 1,2-DIOLS AND THEIR PREPARATION
    RUTZEN, H
    FETTE SEIFEN ANSTRICHMITTEL, 1980, 82 (01): : 23 - 29
  • [37] ENANTIOSELECTIVE SYNTHESIS OF 1-VINYL-1,2-DIOLS, VINYL EPOXIDES AND ALPHA,BETA-DIALKOXY ALDEHYDES
    MATSUMOTO, T
    KITANO, Y
    SATO, F
    TETRAHEDRON LETTERS, 1988, 29 (44) : 5685 - 5688
  • [38] THE DIELECTRIC SPECTRA OF SOME LINEAR 1,2-DIOLS
    ELSAMAHY, A
    GESTBLOM, B
    SJOBLOM, J
    FINNISH CHEMICAL LETTERS, 1984, (03): : 54 - 58
  • [39] CHEMILUMINESCENCE INDUCED BY MEDIATED OXIDATION OF 1,2-DIOLS
    KARATANI, H
    CHEMISTRY LETTERS, 1994, (03) : 623 - 626
  • [40] On the origin of the regioselectivity in glycosylation reactions of 1,2-diols
    Belen Cid, M.
    Alfonso, Francisco
    Alonso, Ines
    Martin-Lomas, Manuel
    ORGANIC & BIOMOLECULAR CHEMISTRY, 2009, 7 (07) : 1471 - 1481
12345