STEREOCHEMICAL CONSEQUENCES OF THE LEWIS ACID-PROMOTED 3-AZA-COPE REARRANGEMENT OF N-ALKYL-N-ALLYL ENAMINES
STEREOCHEMICAL CONSEQUENCES OF THE LEWIS ACID-PROMOTED 3-AZA-COPE REARRANGEMENT OF N-ALKYL-N-ALLYL ENAMINES
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DOI：
10.1016/s0040-4020(01)86707-7
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发表时间：
1994-04-04
期刊：
影响因子：
2.1
通讯作者：
STILLE, JR
中科院分区：
文献类型：
--
作者：
COOK, GR;STILLE, JR
研究了亲电试剂促进取代n -烷基- n -烯丙基胺3-aza-Cope重排的内部和相对不对称诱导。一般来说，内部不对称感应是高度可变的，并且取决于亲电试剂和底物的性质。然而，在底物C-4的取代作用锚定了底物的过渡态，产物选择性通常为bbb95:5。当n -烷基取代基拴在C-4上时，得到了从五元环扩展到九元环的环。
Internal and relative asymmetric induction were examined for the electrophile promoted 3-aza-Cope rearrangement of substituted N-alkyl-N-allyl enamines. In general, internal asymmetric induction was highly variable, and was dependent both upon the nature of the electrophilic reagent and substrate. However, substitution at C-4 of the substrate served to anchor the transition state of the substrates, and product selectivity was typically >95:5. When the N-alkyl substituent was tethered to C-4, ring expansion from a five- to a nine-membered ring was obtained.