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用于双膦单氧化物钯催化反应的合理预催化剂设计。

A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions.

作者信息

Ji Yining, Li Hongming, Hyde Alan M, Chen Qinghao, Belyk Kevin M, Lexa Katrina W, Yin Jingjun, Sherer Edward C, Williamson R Thomas, Brunskill Andrew, Ren Sumei, Campeau Louis-Charles, Davies Ian W, Ruck Rebecca T

机构信息

Department of Process Research & Development , Merck & Co., Inc. , Rahway , New Jersey 07065 , USA . Email:

出版信息

Chem Sci. 2017 Apr 1;8(4):2841-2851. doi: 10.1039/c6sc05472b. Epub 2017 Jan 19.

DOI:10.1039/c6sc05472b
PMID:28553522
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5427683/
Abstract

Significant catalyst loading reduction and increased reaction robustness have been achieved for a Pd-catalyzed asymmetric intramolecular C-N coupling through comprehensive mechanistic studies. Detailed kinetic, spectroscopic, and crystallographic analyses revealed that the mono-oxidation of the bis-phosphine ligand is critical for a successful transformation. P NMR studies provided an understanding of the inefficient activation of the Pd(OAc)/(,)-QuinoxP* pre-catalyst to form the active bis-phosphine mono-oxide-Pd(0) catalyst with competitive formation of a less active (,)-QuinoxP*·PdBr complex. Based on these detailed mechanistic studies, a new series of bis-phosphine mono-oxides (BPMO)-ligated Pd(ii) pre-catalysts have been rationally developed that allow for reliable and complete catalyst activation which should have general utility in academic and industrial settings.

摘要

通过全面的机理研究，在钯催化的不对称分子内C-N偶联反应中实现了显著的催化剂负载量降低和反应稳健性提高。详细的动力学、光谱学和晶体学分析表明，双膦配体的单氧化对于成功转化至关重要。磷核磁共振研究有助于理解Pd(OAc)₂/(R,R)-QuinoxP预催化剂的低效活化，形成活性双膦单氧化物-Pd(0)催化剂，同时竞争性地形成活性较低的(R,R)-QuinoxP·PdBr络合物。基于这些详细的机理研究，合理开发了一系列新的双膦单氧化物（BPMO）连接的Pd(ii)预催化剂，可实现可靠且完全的催化剂活化，这在学术和工业环境中应具有广泛的实用性。

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