Asymmetric Catalytic Coupling of Organoboranes, Alkynes, and Imines with a Removable (Trialkylsilyloxy)ethyl Group—Direct Access to Enantiomerically Pure Primary Allylic Amines


  • This work was supported by the National Institute of General Medical Sciences (GM-063755). We also thank the NSF (CAREER CHE-0134704), Merck Research Laboratories, Pfizer, Amgen, Boehringer-Ingelheim, Johnson & Johnson, GlaxoSmithKline, 3M, and MIT for generous financial support. NSF grants CHE-9809061 and DBI-9729592 and NIH grant 1S10RR13886-01 provided partial support for the MIT Department of Chemistry Instrumentation Facility (DCIF). We thank Elizabeth A. Colby and Johann Chan for assistance with the preparation of phosphane ligands.


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The aryl substituent on the catalyst is central to the success of the title reaction (see scheme) which affords allylic amines in up to 89 % ee and 91 % yield with a catalyst derived from [Ni(cod)2] and a P-chiral ferrocenyl phosphane (e.g. 1). The coupling products are easily deprotected to enantiomerically enriched, tetrasubstituted primary allylic amines, which can be recrystallized to optical purity.