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Updated: May 17, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Synthesis of bridged polycyclic ring systems via carbene cascades terminating in C-H bond insertion
Santa Jansone-Popova1, Jeremy A May
1Department of Chemistry, University of Houston, 136 Fleming Building, Houston, Texas 77204-5003, USA.
Abstract:
A carbene cascade reaction that constructs functionalized bridged bicyclic systems from alkynyl diazoesters is presented. The cascade proceeds through diazo decomposition, carbene/alkyne metathesis, and C-H bond insertion. The diazoesters are easily synthesized from cyclic ketones. Substrate ring size and substitution patterns control the connectivity and diastereomeric preference found in the products.
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Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.