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Diastereo- and Enantioselective Synthesis of Homoallylic Amines Bearing Quaternary Carbon Centers
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-01-14 , DOI: 10.1021/jacs.9b11529
Jacob C Green 1 , Joseph M Zanghi 1 , Simon J Meek 1
Affiliation  

A Cu-catalyzed method for the efficient enantio- and diastereoselective synthesis of chiral homoallylic amines bearing a quaternary carbon and an alkenylboron is disclosed. Transformations are promoted by a readily prepared (phosphoramidite)-Cu complex, and involve bench-stable γ,γ,-disubstituted allyldiborons and benzyl imines; products are obtained in up to 82% yield, >20:1 dr, and >99:1 er. Reactions proceed via stereodefined boron-stabilized allylic Cu species formed by an enantioselective transmetalation. Utility of the 1-amino-3-alkenylboronate products is highlighted by a variety of synthetic transformations.

中文翻译:

带有季碳中心的同烯丙基胺的非对映选择性和对映选择性合成

公开了一种用于有效对映选择性和非对映选择性合成带有季碳和烯基硼的手性高烯丙基胺的铜催化方法。易于制备的(亚磷酰胺)-Cu 配合物促进了转化,包括长期稳定的 γ,γ,-二取代烯丙基二硼和苄基亚胺;产品的产率高达 82%,>20:1 dr,>99:1 er。反应通过对映选择性金属转移形成的立体定义的硼稳定烯丙基铜物种进行。1-氨基-3-链烯基硼酸酯产品的实用性通过各种合成转化得到强调。
更新日期:2020-01-14
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