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Theory Rules Out a [2 + 2] Addition of Osmium Tetroxide to Olefins as Initial Step of the Dihydroxylation Reaction
Author(s) -
Pidun Ulrich,
Boehme Christian,
Frenking Gernot
Publication year - 1996
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199628171
Subject(s) - dihydroxylation , osmium tetroxide , chemistry , kinetic energy , computational chemistry , ab initio , osmium , ethylene , catalysis , base (topology) , thermodynamics , organic chemistry , mathematics , enantioselective synthesis , physics , mathematical analysis , electron microscope , quantum mechanics , ruthenium , optics
A difference of at least 35 kcalmol −1 between the activation barriers results from ab initio calculations for the competing [2 + 2] and [3 + 2] additions of OsO 4 to ethylene, clearly favoring the latter pathway (the two transition state structures are pictured on the right). The relative barrier heights for the proposed reaction paths hardly change in the presence of NH 3 , used to model the base‐catalyzed reaction. These theoretical findings on asymmetric dihydroxylation contradict the conclusions drawn from kinetic studies by Sharpless et al., but support the recent kinetic investigations by Corey et al.