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

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...

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Autores principales: Lei, Peng, Meng, Guangrong, Shi, Shicheng, Ling, Yun, An, Jie, Szostak, Roman, Szostak, Michal
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5628478/
https://www.ncbi.nlm.nih.gov/pubmed/28989678
http://dx.doi.org/10.1039/c7sc02692g
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author Lei, Peng
Meng, Guangrong
Shi, Shicheng
Ling, Yun
An, Jie
Szostak, Roman
Szostak, Michal
author_facet Lei, Peng
Meng, Guangrong
Shi, Shicheng
Ling, Yun
An, Jie
Szostak, Roman
Szostak, Michal
author_sort Lei, Peng
collection PubMed
description 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 (η(3)-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.
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spelling pubmed-56284782017-10-06 Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds Lei, Peng Meng, Guangrong Shi, Shicheng Ling, Yun An, Jie Szostak, Roman Szostak, Michal Chem Sci Chemistry 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 (η(3)-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. Royal Society of Chemistry 2017-09-01 2017-08-01 /pmc/articles/PMC5628478/ /pubmed/28989678 http://dx.doi.org/10.1039/c7sc02692g Text en This journal is © The Royal Society of Chemistry 2017 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Lei, Peng
Meng, Guangrong
Shi, Shicheng
Ling, Yun
An, Jie
Szostak, Roman
Szostak, Michal
Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title_full Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title_fullStr Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title_full_unstemmed Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title_short Suzuki–Miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around C–N and C–O bonds
title_sort suzuki–miyaura cross-coupling of amides and esters at room temperature: correlation with barriers to rotation around c–n and c–o bonds
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5628478/
https://www.ncbi.nlm.nih.gov/pubmed/28989678
http://dx.doi.org/10.1039/c7sc02692g
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