Re₂O₇-Catalyzed Approach to Spirocyclic Ether Formation from Acyclic Precursors: Observation of Remote Stereoinduction.

ABSTRACT: Ketones that are flanked by an allylic alcohol and an alkene isomerize to spirocyclic ethers in the presence of Re₂O₇ through allylic alcohol transposition, oxocarbenium ion formation, and Prins cyclization. These processes provide significant increases in molecular complexity, with multiple stereocenters being set relative to a stereocenter in the substrate. Stereoselectivity arises from the initial reversible steps being more rapid than the final step, thereby allowing for thermodynamically controlled stereochemical equilibration prior to product formation.

SUBMITTER: Afeke C 

PROVIDER: S-EPMC7720882 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature