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Least‐motion stepwise [2 + 2] ketene cycloadition pathways predict the more hindered cis ‐cycloadducts
Author(s) -
Firestone Raymond A.
Publication year - 1994
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560490104
Subject(s) - ketene , cycloaddition , chemistry , product (mathematics) , computational chemistry , motion (physics) , yield (engineering) , rotation (mathematics) , medicinal chemistry , physics , organic chemistry , computer science , thermodynamics , classical mechanics , artificial intelligence , catalysis , mathematics , geometry
Ketene cycloadditions give predominantly the more hindered product. This has been adduced as evidence for concerted antarafacial cycloaddition in accord with the Woodward–Hoffmann rules. However, stepwise mechanisms, heretofore discounted, are now shown to account for the products in a simple least‐motion manner that requires only that rotation in the intermediates be not greatly faster than cyclization. This requirement is amply supported by the literature. © 1994 John Wiley & Sons, Inc.