Acetonitrile Activation: An Effective Two‐Carbon Unit for Cyclization. Issue 13 (18th February 2019)

• Record Type: Journal Article
• Authors: Qin, Qixue; Luo, Xiao; Wei, Jialiang; Zhu, Yuchao; Wen, Xiaojin; Song, Song; Jiao, Ning
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 13(2019)
• Page Start: 4376
• Page End: 4380
• Publication Date: 2019-02-18
• Subjects: C2 cyclization unit -- cyclizations -- cycloaddition -- small-molecule activation -- small-ring compounds; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201900947
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : 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.