In:
Chemistry – A European Journal, Wiley, Vol. 22, No. 41 ( 2016-10-04), p. 14494-14498
Abstract:
Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N−C activation/cross‐coupling reactions are highly twisted around the N−C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N ‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The 15 N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N−C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201603543
Language:
English
Publisher:
Wiley
Publication Date:
2016
detail.hit.zdb_id:
1478547-X
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