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

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• 作者：Dionicio Martinez-Solorio ; Bruno Melillo ; Luis Sanchez ; Yong Liang ; Erwin Lam ; K. N. Houk ; Amos B. Smith III
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 17, 2016
• 年：2016
• 卷：138
• 期：6
• 页码：1836-1839
• 全文大小：394K
• ISSN：1520-5126

文摘

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.