Open AccessRe2O7-Catalyzed Approach to Spirocyclic Ether Formation from Acyclic Precursors: Observation of Remote Stereoinduction
Author(s) -
Cephas Afeke,
Youwei Xie,
Paul E. Floreancig
Publication year - 2019
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.9b01660
Subject(s) - stereocenter , chemistry , oxocarbenium , stereoselectivity , alkene , allylic rearrangement , stereochemistry , catalysis , ether , enantioselective synthesis , organic chemistry , nucleophile
Ketones that are flanked by an allylic alcohol and an alkene isomerize to spirocyclic ethers in the presence of Re 2 O 7 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.