Liang Ren-Xiao, Tang Heng-Wei, Liu Jia-Liang, Xu Jian-Feng, Chen Ling-Jia, Jia Yi-Xia
College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology Chaowang Road 18# Hangzhou 310014 China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai 200032 P. R. China.
Chem Sci. 2023 May 15;14(23):6393-6398. doi: 10.1039/d3sc00119a. eCollection 2023 Jun 14.
A highly enantioselective cobalt-catalyzed desymmetrizing reductive cyclization of alkynyl cyclodiketones has been developed. Under mild reaction conditions by employing HBpin as a reducing agent and ferrocene-based PHOX as a chiral ligand, a series of polycyclic tertiary allylic alcohols bearing contiguous quaternary stereocenters are achieved in moderate to excellent yields with excellent enantioselectivities (up to 99%). Broad substrate scope and high functional group compatibility are observed in this reaction. A CoH-catalyzed pathway involving alkyne hydrocobaltation followed by nucleophilic addition to the C[double bond, length as m-dash]O bond is proposed. Synthetic transformations of the product are conducted to demonstrate the practical utilities of this reaction.
已开发出一种高度对映选择性的钴催化炔基环二酮的去对称还原环化反应。在温和的反应条件下，使用HBpin作为还原剂，以二茂铁基PHOX作为手性配体，一系列带有相邻季碳立体中心的多环叔烯丙醇以中等至优异的产率和优异的对映选择性（高达99%）得以实现。该反应具有广泛的底物范围和高官能团兼容性。提出了一种涉及炔烃氢钴化然后对C=O键进行亲核加成的CoH催化途径。对产物进行了合成转化，以证明该反应的实际应用价值。
