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两个配体从 Ag 转移到 Pd:通向(SIPr)Pd(CFH)(X)及其在一锅 C-H 硼化/二氟甲基化反应中的应用。

Two Ligands Transfer from Ag to Pd: En Route to (SIPr)Pd(CFH)(X) and Its Application in One-Pot C-H Borylation/Difluoromethylation.

机构信息

Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China.

Bayer AG, Research & Development, Pharmaceuticals, 178 Müllerstraße, Berlin 13342, Germany.

出版信息

J Org Chem. 2020 Mar 6;85(5):3596-3604. doi: 10.1021/acs.joc.9b03296. Epub 2020 Feb 4.

Abstract

A process for the concurrent transfer of both the NHC ligand and the difluoromethyl group from [(SIPr)Ag(CFH)] to PdX (X = Cl, OAc, and OPiv) for the preparation of [(SIPr)Pd(CFH)X] complexes is described. These complexes were air-stable and easily underwent transmetalation with aryl pinacol boronate/reductive elimination to generate ArCFH in high yields. Based on this discovery, the first one-pot C-H borylation and difluoromethylation process for the preparation of difluoromethylated (hetero)arenes was developed.

摘要

描述了一种从[(SIPr)Ag(CFH)]同时转移 NHC 配体和二氟甲基到 PdX(X = Cl、OAc 和 OPiv)以制备[(SIPr)Pd(CFH)X]配合物的方法。这些配合物在空气中稳定,并且很容易与芳基频哪醇硼酸酯/还原消除进行转金属反应,以高产率生成 ArCFH。基于这一发现,开发了首例用于制备二氟甲基化(杂)芳基的一锅 C-H 硼化和二氟甲基化反应。

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