Donald Clayton P, Boylan Amy, Nguyen Truong N, Chen Po-An, May Jeremy A
Department of Chemistry, University of Houston, 3585 Cullen Blvd, Fleming Bldg 112, Houston, Texas 77204-5003, United States.
Pfizer, 280 Shennecossett Rd, Groton, Connecticut 06340, United States.
Org Lett. 2022 Sep 23;24(37):6767-6771. doi: 10.1021/acs.orglett.2c02612. Epub 2022 Sep 13.
(IPr)GaCl/AgSbF, AgSbF, and GaCl catalyzed substitution of the hydroxyl of secondary and tertiary propargylic alcohols with organoboronic acids via C-C bond formation, and GaCl effectively synthesized all-carbon quaternary propargylic centers. These catalysts performed the substitution at carbons bearing alkyl substituents, which has been problematic for other systems. Highly hindered carbon stereocenters were thus produced, including quaternary centers bearing doubly ortho-substituted aryl rings, that are difficult to access with traditional methods.
（IPr）GaCl/AgSbF₆、AgSbF₆和GaCl通过碳-碳键形成催化仲和叔炔丙醇的羟基与有机硼酸发生取代反应，并且GaCl有效地合成了全碳季炔丙基中心。这些催化剂能在带有烷基取代基的碳上进行取代反应，而这对于其他体系来说是个难题。由此产生了高度受阻的碳立体中心，包括带有双邻位取代芳环的季中心，这些是传统方法难以得到的。
