ALLENES AND ACETYLENES .28. ON THE MECHANISM OF REDUCTION OF PROPARGYLIC ETHERS AND ACETATES WITH ORGANOCUPRATES

被引:15
作者
SAHLBERG, C [1 ]
CLAESSON, A [1 ]
机构
[1] UNIV UPPSALA, CTR BIOMED, DEPT ORGAN PHARMACEUT CHEM, S-75123 UPPSALA, SWEDEN
关键词
D O I
10.1021/jo00196a003
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The amounts of substitution and reduction products from the reactions of 2 types of propargylic methyl ethers and acetates with organocuprates were determined. The methyl ethers give rise to more of the reduction products than the acetates. Reduced allenes are formed by hydrolysis of an organometallic intermediate whereas reduced acetylenes are formed mainly by another mechanistic pathway. The mechanisms of these reduction reactions are discussed in terms of stabilized, transient Cu(III)-intermediates and concerted .beta.-hydride transfer in the formation of the acetylene. [These reactions can be applied to the synthesis of allenic prostaglandins and amines.].
引用
收藏
页码:4120 / 4122
页数:3
相关论文
共 19 条
  • [1] SOLUTION COMPOSITION OF THE NORMANT REAGENT - IDENTIFICATION OF NEW THF-SOLUBLE MAGNESIUM METHYLCUPRATES CUNMGMME2M+N
    ASHBY, EC
    GOEL, AB
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1983, 48 (13) : 2125 - 2130
  • [2] SYNTHESIS OF NEW ALLENIC PROSTANOIDS
    BARET, P
    BARREIRO, E
    GREENE, AE
    LUCHE, JL
    TEIXEIRA, MA
    CRABBE, P
    [J]. TETRAHEDRON, 1979, 35 (24) : 2931 - 2938
  • [3] MECHANISTIC ASPECTS OF REDUCTIONS OF ALLYLIC ETHERS AND ACETATES WITH ORGANOCUPRATES
    CLAESSON, A
    SAHLBERG, C
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1979, 170 (03) : 355 - 363
  • [4] CLAESSON A, 1975, TETRAHEDRON LETT, P1509
  • [5] SYNTHESIS OF ALLENYL PROSTAGLANDINS
    CRABBE, P
    CARPIO, H
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1972, (15) : 904 - &
  • [6] CONTROLLED FORMATION OF ALLENES WITH ORGANOCUPRATES
    CRABBE, P
    BARREIRO, E
    DOLLAT, JM
    LUCHE, JL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1976, (05) : 183 - 184
  • [7] CIS REDUCTION OF ACETYLENES BY ORGANOCOPPER REAGENTS
    CRANDALL, JK
    COLLONGES, F
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (26) : 4089 - 4092
  • [8] deMontellano P.R. Ortiz., 1973, J CHEM SOC CHEM COMM, P709
  • [9] SYNTHETIC USE OF AN UNUSUAL ORGANOCUPRATE INTERMEDIATE
    DOLLAT, JM
    LUCHE, JL
    CRABBE, P
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (21) : 761 - 762
  • [10] HOUSE HO, 1975, J ORG CHEM, V40, P788, DOI 10.1021/jo00894a023