Ground-State Distortion in N‑Acyl-tert-butyl-carbamates (Boc) and N‑Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N–C Cross-Coupling

Amide N–C­(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*CO resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the develop...

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Bibliographic Details
Published in:Journal of organic chemistry 2016-09, Vol.81 (17), p.8091-8094
Main Authors: Szostak, Roman, Shi, Shicheng, Meng, Guangrong, Lalancette, Roger, Szostak, Michal
Format: Article
Language:English
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Summary:Amide N–C­(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*CO resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N–C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N–C­(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N–C­(O) amide bond cleavage as a key step.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b01560