Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles
Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles
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DOI：
10.1021/jo200368a
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发表时间：
2011-05-20
影响因子：
3.6
通讯作者：
Rubin, Michael
中科院分区：
文献类型：
--
作者：
Banning, Joseph E.;Prosser, Anthony R.;Rubin, Michael
A diastereoconvergent formal nucleophilic substitution of bromocyclopropanes with oxygen- and sulfur-based nucleophiles is described. The reaction proceeds via in situ formation of a highly reactive cyclopropene intermediate and subsequent diastereoselective addition of a nucleophile across the strained C=C bond. Three alternative means of controlling the diastereoselectivity of addition have been demonstrated: (1) thermodynamically driven epimerization of enolizable carboxamides, (2) steric control by bulky substituents, and (3) directing effect of carboxamide or carboxylate functions.
