文献类型：期刊文献

英文题名：Rhodium/Chiral-Diene-Catalyzed Switchable Asymmetric Divergent Arylation of Enone-Diones

作者：Li, Junbao[1];Sun, Jinghui[1];Ren, Wenzhu[1];Lei, Jinhua[1];Shen, Runpu[2];Huang, Yinhua[1]

机构：[1]Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Minist Educ, Key Lab Organosilicon Chem & Mat Technol, Hangzhou 311121, Peoples R China;[2]Shaoxing Univ, Zhejiang Engn Res Ctr Fatsoluble Vitamin, Shaoxing 312000, Peoples R China

年份：2022

卷号：24

期号：12

起止页码：2420

外文期刊名：ORGANIC LETTERS

收录：SCI-EXPANDED(收录号：WOS:000780673100028)、、Scopus(收录号：2-s2.0-85127447867)、WOS

基金：We gratefully acknowledge the Natural Science Foundation of Zhejiang Province (ZJNSF) (LY19B020005, GG21E030023) and the Zhejiang Engineering Research Center of Fat-soluble Vitamin for financial support.

语种：英文

外文摘要：A rhodium/chiral diene catalytic system is reported for the reaction of enone-diones and arylboronic acids that allows the switchable synthesis of chiral bicyclic products and acyclic products in a controlled manner. The production of bicyclic products containing four contiguous stereocenters is assumed to proceed through the enantioselective arylrhodation of enone-diones with Cs2CO3, forming a rhodium-enolate intermediate, followed by desymmetrization of the diastereotopic diones via aldol cydization with quantitative diastereoselection and excellent enantiomeric excess. The production of acyclic products is assumed to proceed through the enantioselective hydroarylation of enone-diones with excellent enantiomeric excess in which the aldol cydization is significantly inhibited by the choice of Et3N as a base. The selectivity for bicyclic products (via tandem arylation-aldol cyclization and acyclic products (via hydroarylation) is rationalized by the proposed model.