Design, Synthesis, and Validation of an Effective, Reusable Silicon-Based Transfer Agent for Room-Temperature Pd-Catalyzed Cross-Coupling Reactions of Aryl and Heteroaryl Chlorides with Readily Available Aryl Lithium Reagents

Journal of the American Chemical Society
Dionicio Martinez-SolorioAmos B Smith

Abstract

A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this "green" CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups.

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Citations

Sep 8, 2016·The Journal of Organic Chemistry·Akimichi OhtsukiNaoto Chatani
Sep 28, 2018·Organic & Biomolecular Chemistry·Miao HuHuanfeng Jiang
Aug 31, 2017·The Journal of Antibiotics·Yike Zou, Amos B Smith
Jan 23, 2018·Chemical Communications : Chem Comm·José M Gil-NegreteLuis A Sarandeses
Sep 18, 2020·Angewandte Chemie·Xinlan A F CookMichael C Willis
May 18, 2021·Chinese Chemical Letters Zhongguo Hua Xue Kuai Bao·Yu ChenYong Liang
Apr 10, 2020·Accounts of Chemical Research·Yifan Deng, Amos B Smith
Feb 27, 2018·The Journal of Organic Chemistry·Minh H NguyenAmos B Smith

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