ELECTROPHILIC CYCLOPROPANES IN ORGANIC-SYNTHESIS

ELECTROPHILIC CYCLOPROPANES IN ORGANIC-SYNTHESIS
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DOI:
10.1021/ar50134a004
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发表时间:
1979-01-01
影响因子:
18.3
通讯作者:
DANISHEFSKY, S
DANISHEFSKY, S
中科院分区:
化学1区
文献类型:
--
作者:
DANISHEFSKY, S

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我们自己在这方面的参与可以沿着以下几点来描述。12年前,罗伯特·卡瓦诺开始研究同源迈克尔反应。[5]他的目的是获得更多关于可能使用的亲核试剂范围的信息[6],并澄清在活化的乙烯基环丙烷的开环反应中1,5-加成与1,7-加成的问题[7]。乔治Rovnyak 7,8确定了1,5-加成发生在构型完全反转的情况下9,并研究了烷基取代对活化环丙烷开环方向的影响。10· 11在此基础上,约翰·戴纳克研究了分子内结构对开环能力的影响。[12]特别是,Dynak研究了螺环(参见,11)与稠合(参见,12)的相对优势。12)模式,
Our own involvement in this area can be described along the following lines. Twelve years ago Robert Cavanaugh began a study of thehomologous Michael reaction. 5 His purpose was to gain more information on the range of nucleophiles6 which might be employed and to clarify the issue of 1, 5-vs. 1, 7-additions7 in the opening of activated vinylcyclopropanes. George Rovnyak7, 8 determined that 1, 5-addition occurs with clean inversion of configuration9 and examined the effect of alkyl substitution on the direction of ring openings of activated cyclopropanes. 10· 11 From this basis, John Dynak investigated the effects of intramolecularity on the facility ofring opening. 12 In particular, Dynak studied the relative preponderance of the spiro (cf, 11) vs. the fused (cf. 12) mode of in-