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Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups
Author(s) -
Xie Youwei,
Floreancig Paul E.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402010
Subject(s) - chemistry , electrophile , allylic rearrangement , ketone , aldehyde , nucleophile , stereocenter , trapping , oxocarbenium , alcohol , nucleophilic addition , combinatorial chemistry , transposition (logic) , organic chemistry , enantioselective synthesis , catalysis , ecology , linguistics , philosophy , biology
Allylic alcohols undergo transposition reactions in the presence of Re 2 O 7 whereby the equilibrium can be dictated by trapping one isomer with a pendent electrophile. Additional ionization can occur when the trapping group is an aldehyde or ketone, thus leading to cyclic oxocarbenium ion formation. Terminating the process through bimolecular nucleophilic addition into the intermediate provides a versatile method for the synthesis of diverse oxygen‐containing heterocycles. Understanding the relative rates of the steps in the sequence leads to the design of reactions which create multiple stereocenters with good to excellent levels of control.