On the Absolute Configurational Stability of Bromonium and Chloronium Ions

被引:163
作者
Denmark, Scott E. [1 ]
Burk, Matthew T. [1 ]
Hoover, Andrew J. [1 ]
机构
[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA
基金
美国国家科学基金会;
关键词
ASYMMETRIC CHLOROHYDRIN SYNTHESIS; STABLE CARBONIUM IONS; NEIGHBORING HALOGEN PARTICIPATION; ELECTROPHILIC BROMINATION; HALONIUM IONS; ACCEPTOR OLEFINS; PALLADIUM(II); OXIDATION; ADAMANTYLIDENEADAMANTANE; HALOCYCLIZATION;
D O I
10.1021/ja909965h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Halonium ions have long been established as the critical intermediates in halogenation and halo functionalization of alkenes. Although these workhorse reactions have been extensively studied mechanistically and employed synthetically, the paucity of enantioselective variants is striking. A central problem in the development of catalytic enantioselective halofunctionalizations is the reversible formation of halonium ions and the facile olefin-to-olefin transfer. In this report, configurationally defined and enantiomerically enriched bromonium and chloronium ions are generated (by solvolysis of enantiomerically enriched precursors) and shown to be intercepted intermolecularly with high enantio- and diastereospecificity by various nucleophiles. Most importantly, the stereospecificity of capture is not significantly eroded in the presence of olefins.
引用
收藏
页码:1232 / +
页数:4
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