In:
Angewandte Chemie, Wiley, Vol. 133, No. 4 ( 2021-01-25), p. 1925-1930
Abstract:
(NDI)Ni 2 catalysts (NDI=naphthyridine‐diimine) promote cyclopropanation reactions of 1,3‐dienes using (Me 3 Si)CHN 2 . Mechanistic studies reveal that a metal carbene intermediate is not part of the catalytic cycle. The (NDI)Ni 2 (CHSiMe 3 ) complex was independently synthesized and found to be unreactive toward dienes. Based on DFT models, we propose an alternative mechanism that begins with a Ni 2 ‐mediated coupling of (Me 3 Si)CHN 2 and the diene. N 2 extrusion followed by radical C−C bond formation generates the cyclopropane product. This model reproduces the experimentally observed regioselectivity and diastereoselectivity of the reaction.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202011602
Language:
English
Publisher:
Wiley
Publication Date:
2021
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