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分子内 Umpolung 级联 Kukhtin-Ramirez 反应/迈克尔加成引发的环化:四取代环丙基稠合 1-茚酮的立体选择性合成。

An Intramolecular Umpolung Cascade Kukhtin-Ramirez Reaction/Michael Addition-Initiated Cyclization: Stereoselective Synthesis of Tetrasubstituted Cyclopropane Fused 1-Indanones.

机构信息

Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal By-pass Road, Bhauri, Bhopal 462066, India.

出版信息

Org Lett. 2023 Mar 24;25(11):1946-1951. doi: 10.1021/acs.orglett.3c00494. Epub 2023 Mar 15.

Abstract

Herein, we disclose a fascinating highly stereoselective P(NMe) mediated intramolecular deoxygenative umpolung cascade Michael addition-initiated cyclopropanation with a diverse substrate adaptability. This methodology creates a new horizon for expedient access to valuable 6,5,3-fused scaffolds having an all-carbon quaternary stereocenter via Kukhtin-Ramirez (K-R) adduct formation, with excellent diastereoselectivity and yields under metal-free ambient conditions. A few functional group transformations have also been performed successfully. Additionally, an asymmetric catalytic attempt using ()-(+)-H8-BINOL has delivered good enantioselectivity.

摘要

在此,我们揭示了一种引人入胜的高度对映选择性 P(NMe)介导的分子内脱氧重排级联迈克尔加成引发的环丙烷化反应,具有广泛的底物适应性。这种方法通过 Kukhtin-Ramirez (K-R) 加合物形成,为通过简便途径获得具有全碳季立体中心的有价值的 6,5,3 稠合支架提供了新的途径,在无金属的环境条件下具有优异的非对映选择性和收率。还成功进行了一些官能团转化。此外,使用 ()-(+)-H8-BINOL 的不对称催化尝试也实现了良好的对映选择性。

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