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Updated: Jul 1, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Copper/Chiral Phosphoric-Acid-Catalyzed Intramolecular Reductive Isocyanide-Alkene (1 + 2) Cycloaddition:
Sidi Cheng1,2, Ting Yu1,2, Jing Li1,2
1State Key Laboratory of Respiratory Disease, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530, China.
Abstract:
Enantioenriched 2-azabicyclo[3.1.0]hexanes are accessed from readily available allyl substituted α-isocyanoesters by intramolecular (1 + 2) cycloaddition with the olefinic moiety and isocyano carbon as the respective C2 and C1 units. Cyclopropanation is initiated by 1,1-hydrocupration of isocyanide followed by formimidoylcopper to copper α-aminocarbenoid equilibration and subsequent (1 + 2) cycloaddition. The unprecedented copper/chiral phosphoric acid (CPA) catalytic system can be operated in the presence of water under air, delivering a variety of 2-azabicyclo[3.1.0]hexanes containing an angular all-carbon quaternary stereocenter in good to excellent yields and enantioselectivity.
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