Issue 9, 2017

Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds

Abstract

The Suzuki–Miyaura cross-coupling has been widely recognized as one of the most important methods for the construction of C–C bonds. However, in contrast to traditional aryl halide or pseudohalide electrophiles, coupling reactions with unactivated C–N and C–O electrophiles have proven significantly more challenging. Here we report the first general palladium-catalyzed Suzuki–Miyaura cross-coupling of both common amides and aryl esters through the selective cleavage of the C–N and C–O bonds under exceedingly mild conditions. Notably, for the first time we demonstrate selective C(acyl)–N and C(acyl)–O cleavage/cross-coupling under the same reaction conditions. The reaction uses a commercially available, bench-stable and operationally-convenient (η3-1-t-Bu-indenyl)Pd(IPr)(Cl) precatalyst. Furthermore, we demonstrate that the reactivity of generic amides and aryl esters can be correlated with barriers to isomerization around the C(acyl)–X (X = N, O) bond, thus providing a blueprint for the development of a broad range of novel coupling reactions of ester and amide electrophiles by the selective activation of C–O and C–N bonds.

Graphical abstract: Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds

Supplementary files

Article information

Article type
Edge Article
Submitted
16 Jun 2017
Accepted
20 Jul 2017
First published
01 Aug 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, 6525-6530

Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds

P. Lei, G. Meng, S. Shi, Y. Ling, J. An, R. Szostak and M. Szostak, Chem. Sci., 2017, 8, 6525 DOI: 10.1039/C7SC02692G

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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