Department of Chemistry, Virginia Commonwealth University, 1001 West Main Street, Richmond, Virginia 23284-3028, United States.
Org Lett. 2023 Mar 10;25(9):1425-1430. doi: 10.1021/acs.orglett.3c00157. Epub 2023 Feb 27.
Herein, we report the development of an improved system for the Cu-catalyzed enantioselective reductive coupling of ketones and allenamides through the optimization of the allenamide to avoid an on-cycle rearrangement. High enantioselectivities could be obtained for a variety of ketones. Use of the acyclic allenamides described herein selectively generated -diastereomers in contrast to cyclic allenamides that were previously shown to favor the -form. A rationale for this change in diastereoselectivity is also presented.
本文报道了一种改进的铜催化酮和烯丙酰胺的对映选择性还原偶联系统，通过优化烯丙酰胺以避免循环重排。该方法可以高对映选择性地得到各种酮。使用本文所述的非环烯丙酰胺可以选择性地生成 -非对映异构体，而之前报道的环状烯丙酰胺则有利于 -形式。本文还提出了这种非对映选择性变化的原理。
