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The thermal C 2 –C 6 (Schmittel)/ene cyclization of enyne–allenes – crossing the boundary between classical and nonstatistical kinetics
Author(s) -
Schmittel Michael,
Vavilala Chandrasekhar,
Cinar Mehmet Emin
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1887
Subject(s) - enyne , chemistry , allene , diradical , ene reaction , computational chemistry , kinetics , stereochemistry , catalysis , organic chemistry , nuclear physics , physics , quantum mechanics , singlet state , excited state
The thermal C 2 –C 6 /ene cyclization of enyne–allenes has become an exciting venue for both mechanistic and synthetic studies. While at first most efforts were aimed at establishing the diradical nature of the thermal process and to derive therefrom efficient protocols for synthetic schemes, recent evidence has disclosed the C 2 –C 6 cyclization as a unique reaction heavily influenced by nonstatistical dynamic effects. Depending on the substituents at the enyne–allene, one can readily identify transitions between classical and nonstatistical behaviors on the basis of experimental data. Copyright © 2011 John Wiley & Sons, Ltd.