Intramolecular oxyalkylation of unactivated alkenes

Zhi Xu, Yougant Airan, Martin Tomanik, Andrew T. Yang, Natalie Bhak, Seth B. Herzon

Research output: Contribution to journalArticlepeer-review


The synthesis of cyclopropanes by the cyclization of allylic diazoesters is well-known. In prior studies toward the sesquiterpenoid euonyminol, we attempted to carry out an intramolecular cyclopropanation of an allylic diazoester containing an electronically-unbiased alkene embedded in a 6-oxa-bicyclo[3.2.1]-oct-3-ene skeleton. We obtained exclusively a product arising from 1,2-addition of oxygen and carbon (oxyalkylation) to the alkene. While oxyalkylation products have been reported when electron-rich alkenes (e.g. enol ethers) are employed, oxyalkylation products derived from electronically-unbiased alkenes are rare. Here, we establish that the oxyalkylation is general for a range of 6-oxa-bicyclo[3.2.1]-oct-3-ene substrates and show that these products form competitively in the cyclization of simpler α-diazo-β-ketoesters. Our data suggest increasing charge separation in the transition state for the addition promotes the oxyalkylation pathway.

Original languageEnglish (US)
Article number134070
StatePublished - Jul 17 2024


  • Cyclopropanation
  • Diazoester
  • Oxyalkylation
  • Unactivated alkene

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry


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