α-Diazo-β-ketonitriles: Uniquely Reactive Substrates for Arene and Alkene Cyclopropanation

作者：Roger R. Nani, Sarah E. Reisman · 发表于：Journal of the American Chemical Society · 年份：2013 · DOI：10.1021/ja401610p · 被引用次数：99 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic Alkyne Reactions、Asymmetric Synthesis and Catalysis

An investigation of the intramolecular cyclopropanation reactions of α-diazo-β-ketonitriles is reported. These studies reveal that α-diazo-β-ketonitriles exhibit unique reactivity in their ability to undergo arene cyclopropanation reactions; other similar acceptor-acceptor-substituted diazo substrates instead produce mixtures of C-H insertion and dimerization products. α-Diazo-β-ketonitriles also undergo highly efficient intramolecular cyclopropanation of tri- and tetrasubstituted alkenes. In addition, the α-cyano-α-ketocyclopropane products are demonstrated to serve as substrates for SN2, SN2', and aldehyde cycloaddition reactions.