Acetonitrile Activation: An Effective Two‐Carbon Unit for Cyclization

A novel activation of acetonitrile for the construction of cyclobutenones by [2+2] cyclization was developed. Acetonitrile is utilized for the first time as two‐carbon (C2) cyclization building block. The present protocol successfully inhibits the competitive cycloaddition with the C≡N bond of aceto...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-03, Vol.58 (13), p.4376-4380
Main Authors: Qin, Qixue, Luo, Xiao, Wei, Jialiang, Zhu, Yuchao, Wen, Xiaojin, Song, Song, Jiao, Ning
Format: Article
Language:English
Subjects:
Acetonitrile
Activation
C2 cyclization unit
Carbon
Carbon cycle
Construction
cyclizations
Cycloaddition
Organic chemistry
small-molecule activation
small-ring compounds
Substrates
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Summary:A novel activation of acetonitrile for the construction of cyclobutenones by [2+2] cyclization was developed. Acetonitrile is utilized for the first time as two‐carbon (C2) cyclization building block. The present protocol successfully inhibits the competitive cycloaddition with the C≡N bond of acetonitrile, but enables the in situ formation of an unsaturated carbon–carbon bond and the subsequent cycloaddition as a C2 unit. This chemistry features simple reaction conditions, high chemoselectivities, wide substrate scope, and offers a new and practical approach to cyclobutenones and cyclobuteneimines. A carbon or two: In contrast to the reported cycloaddition reaction with the nitrile group of acetonitrile, this work describes a novel [2+2] cycloaddition reaction for construction of cyclobutenones using acetonitrile as a two‐carbon cyclization unit for the first time. The reaction proceeds under mild reaction conditions.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201900947