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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Titanium-Mediated Synthesis of Spirocyclic NH-Azetidines from Oxime Ethers
Nicole Erin Behnke1, Kaitlyn Lovato1, Muhammed Yousufuddin2
1Department of Chemistry, Rice University, 6500 Main Street, Houston, TX, 77030, USA.
Abstract:
The TiIV -mediated synthesis of spirocyclic NH-azetidines from oxime ethers using either an alkyl Grignard reagent or terminal olefin ligand exchange coupling partner is described. Through a proposed Kulinkovich-type mechanism, a titanacyclopropane intermediate forms and serves as a 1,2-aliphatic dianion equivalent, inserting into the 1,2-dielectrophilc oxime ether to ultimately give rise to the desired N-heterocyclic four-membered ring. This transformation proceeds in moderate yield to furnish previously unreported and structurally diverse NH-azetidines in a single step.
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