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Chiral phosphoramide-catalyzed aldol additions of ketone trichlorosilyl enolates. Mechanistic aspects

SE Denmark, SM Pham, RA Stavenger…

文献索引:Denmark, Scott E.; Stavenger, Robert A.; Winter, Stephen B. D.; Wong, Ken-Tsung; Barsanti, Paul A. Journal of Organic Chemistry, 1998 , vol. 63, # 25 p. 9517 - 9523

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被引用次数: 61

摘要

The mechanism of the catalytic, enantioselective addition of trichlorosilyl enolates to aldehydes has been investigated. Kinetic studies using ReactIR and rapid injection NMR (RINMR) spectroscopy have confirmed the simultaneous operation of dual mechanistic pathways involving either one or two phosphoramides bound to a siliconium ion organizational center. This mechanistic dichotomy was initially postulated on the basis of ...