INTRAMOLECULAR ANODIC OLEFIN COUPLING REACTIONS AND THE USE OF VINYLSILANES

被引:34
作者
HUDSON, CM [1 ]
MOELLER, KD [1 ]
机构
[1] WASHINGTON UNIV,DEPT CHEM,ST LOUIS,MO 63130
关键词
D O I
10.1021/ja00087a021
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Intramolecular anodic olefin coupling reactions involving vinylsilane groups have been studied. It was found that the previously successful predictive model for olefin coupling reactions based on an electrophilic attack of a radical cation onto an olefin did not successfully predict product formation for olefin coupling reactions involving vinylsilane terminating groups. Instead, these reactions were best described by viewing the initial addition of the radical cation to an olefin as if it occurred in a reversible ''radical-like'' fashion, in addition, reactions using a temporary silicon tether were shown to be compatible with the formation of quaternary carbons with control of relative stereochemistry. These reactions helped highlight the compatibility of the anodic olefin coupling reactions with extremely sensitive substrates. Finally, the results reported suggest that the mass balance of the intramolecular anodic olefin coupling reaction depends on the ease with which the initially formed cyclized product undergoes the second oxidation step.
引用
收藏
页码:3347 / 3356
页数:10
相关论文
共 46 条
  • [1] BECKWITH ALJ, 1981, TETRAHEDRON, V31, P3070
  • [2] BECKWITH ALJ, 1980, REARRANGEMENTS GROUN, V1
  • [3] VINYLSILANE-TERMINATED AND ALKYNYLSILANE-TERMINATED CYCLIZATION REACTIONS
    BLUMENKOPF, TA
    OVERMAN, LE
    [J]. CHEMICAL REVIEWS, 1986, 86 (05) : 857 - 873
  • [4] ASSIGNMENTS OF THE H-1 AND C-13 NMR-SPECTRA OF PSEUDOSYMMETRIC HETEROCYCLES USING THE HMQC-TOCSY EXPERIMENT TO DIFFERENTIATE OVERLAPPING SPIN SYSTEMS
    CASTLE, LW
    JOHNSTON, MD
    CAMOUTSIS, CL
    CASTLE, RN
    [J]. JOURNAL OF HETEROCYCLIC CHEMISTRY, 1992, 29 (07) : 1805 - 1815
  • [5] INTRAMOLECULAR DIELS-ALDER REACTIONS OF SILYL ACETAL TRIENES - THE EFFECT ON STEREOSELECTIVITY OF ALLYLIC SUBSTITUTION
    CRAIG, D
    READER, JC
    [J]. TETRAHEDRON LETTERS, 1992, 33 (28) : 4073 - 4076
  • [6] Fleming I., 1989, ORG REACTIONS, V37, P57
  • [7] THE UNSYMMETRICAL SILAKETAL AS A NEUTRAL, REMOVABLE TETHER FOR EFFECTING INTRAMOLECULAR DIELS-ALDER REACTIONS
    GILLARD, JW
    FORTIN, R
    GRIMM, EL
    MAILLARD, M
    TJEPKEMA, M
    BERNSTEIN, MA
    GLASER, R
    [J]. TETRAHEDRON LETTERS, 1991, 32 (09) : 1145 - 1148
  • [8] Harwood L. M., 1985, ALDRICHIM ACTA, V18, P25
  • [9] INTRAMOLECULAR ANODIC OLEFIN COUPLING REACTIONS - A USEFUL METHOD FOR CARBON-CARBON BOND FORMATION
    HUDSON, CM
    MARZABADI, MR
    MOELLER, KD
    NEW, DG
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (19) : 7372 - 7385
  • [10] RADICAL CYCLIZATION OF (BROMOMETHYL)DIMETHYLSILYL PROPARGYL ETHERS - REGIOSELECTIVITY, CHEMOSELECTIVITY, AND STEREOSELECTIVITY
    JOURNET, M
    MALACRIA, M
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (11) : 3085 - 3093