In:
Angewandte Chemie, Wiley, Vol. 134, No. 3 ( 2022-01-17)
Abstract:
Polar disconnection of the C(sp 3 )−N bond of N,N‐dialkyl‐substituted tertiary amines via ammonium species conventionally favored the loss of the smaller alkyl group by an S N 2 displacement, while selective C(sp 3 )−N bond cleavage by cutting off the larger alkyl group is still underdeveloped. Herein, we present a novel Pd 0 ‐catalyzed [2+2+1] annulation, proceeding through an alkyne‐directed palladacycle formation and consecutive diamination with a tertiary hydroxylamine by cleaving its N−O bond and one C(sp 3 )−N bond, for the rapid assembly of tricyclic indoles in a single‐step transformation. Noteworthy, experimental results indicated that large tert‐butyl and benzyl groups were selectively cleaved via an S N 1 pathway, in the presence of a smaller alkyl group (Me, Et, i Pr). Under the guidance of this new finding, tricyclic indoles bearing a removable alkyl group could be exclusively obtained by using a (α‐methyl)benzyl/benzyl or tert‐butyl/2‐(methoxycarbonyl)ethyl mixed amino source.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202113820
Language:
English
Publisher:
Wiley
Publication Date:
2022
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