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An Interrupted [4+3] Cycloaddition Reaction: A Hydride Shift (Ene Reaction) Intervenes
Author(s) -
Harmata Michael,
Huang Chaofeng,
Rooshenas Parham,
Schreiner Peter R.
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200803487
Subject(s) - cyclopentadiene , hydride , ene reaction , cycloaddition , computer science , process (computing) , chemistry , scheme (mathematics) , medicinal chemistry , mathematics , organic chemistry , programming language , catalysis , hydrogen , mathematical analysis
The road less traveled does indeed make all the difference. The reaction of oxyallylic cations with cyclopentadiene usually yields a [4+3] cycloadduct. Instead, a hydride shift can supersede this cycloadditon process and proceed in synthetically useful yields (see scheme). Computational analyses suggest that substantial electronic effects influence the “road” taken by the oxyallylic cation.