Issue 4, 2017

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

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. 31P NMR studies provided an understanding of the inefficient activation of the Pd(OAc)2/(R,R)-QuinoxP* pre-catalyst to form the active bis-phosphine mono-oxide–Pd(0) catalyst with competitive formation of a less active (R,R)-QuinoxP*·PdBr2 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.

Graphical abstract: A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Dec 2016
Accepted
15 Jan 2017
First published
19 Jan 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 2841-2851

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

Y. Ji, H. Li, A. M. Hyde, Q. Chen, K. M. Belyk, K. W. Lexa, J. Yin, E. C. Sherer, R. T. Williamson, A. Brunskill, S. Ren, L. Campeau, I. W. Davies and R. T. Ruck, Chem. Sci., 2017, 8, 2841 DOI: 10.1039/C6SC05472B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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