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

Peng Lei, Guangrong Meng, Shicheng Shi, Yun Ling, Jie An, Roman Szostak, Michal Szostak

Research output: Contribution to journalArticlepeer-review

84 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)6525-6530
Number of pages6
JournalChemical Science
Volume8
Issue number9
DOIs
StatePublished - 2017

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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