[3+2] versus [2+2] Addition of Metal Oxides Across CC Bonds. Reconciliation of Experiment and Theory
- 21 May 2003
- journal article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 36 (9) , 645-651
- https://doi.org/10.1021/ar020268q
Abstract
The reaction of a metal oxide with a double bond is the initial step in the osmium-catalyzed cis-dihydroxylation of olefins. The mechanism of the addition of osmium tetraoxide and rhenium(VII) oxides across CC bonds was controversial. Early work indicated a [3+2] addition, and later kinetic studies suggested an initial [2+2] addition, whereas recent quantum-chemical calculations showed the [3+2] addition to be favored. Experiment and theory have now become reconciled. In this Account, we discuss recent contributions to the mechanistic debate as well as future challenges.Keywords
This publication has 47 references indexed in Scilit:
- Transition States for the [2 + 2] Addition of CH2CH2, CH2O, and [M]O across the CC Double Bond of Ketene: Electronic Structure and Energy DecompositionThe Journal of Physical Chemistry A, 2001
- Osmium-Catalyzed Asymmetric Dihydroxylation of Olefins by H2O2 Using a Biomimetic Flavin-Based Coupled Catalytic SystemJournal of the American Chemical Society, 2001
- Efficient Catalytic Deoxygenation of Epoxides Using [Tris(3,5-dimethylpyrazolyl)hydridoborato]rhenium OxidesOrganometallics, 2000
- Are There Metal Oxides That Prefer a [2 + 2] Addition over a [3 + 2] Addition to Olefins? Theoretical Study of the Reaction Mechanism of LReO3 Addition (L = O-, Cl, Cp) to Ethylene1Journal of the American Chemical Society, 1999
- Theoretical Study on the Origin of Enantioselectivity in the Bis(dihydroquinidine)-3,6-pyridazine·Osmium Tetroxide-Catalyzed Dihydroxylation of StyreneJournal of the American Chemical Society, 1999
- LReO3 Epoxidizes, cis-Dihydroxylates, and Cleaves Alkenes as Well as Alkenylates Aldehydes: Toward an Understanding of WhyOrganometallics, 1998
- Organorhenium OxidesAccounts of Chemical Research, 1997
- Theory Rules Out a [2 + 2] Addition of Osmium Tetroxide to Olefins as Initial Step of the Dihydroxylation ReactionAngewandte Chemie International Edition in English, 1996
- Reversible oxidation of a strained alkene by Cp*ReO3Journal of the American Chemical Society, 1993
- Note sur les Produits de Condensation Cycliques de L'acétone avec les Diols 1.3Recueil des Travaux Chimiques des Pays-Bas, 1922