The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study.

The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study. Research Abstract Details 

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The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study. Abstract Text:

The rhodium(I) catalyzed [2 + 2 + 1] carbocyclization of tethered diene-enes to afford substituted hexahydropentalenones with high levels of diastereoselectivity was modeled using density functional theory. Previously, this transformation was observed to be facile, whereas the analogous bis-ene substrate could not be cyclized under any reasonable conditions. To establish a conceptual understanding of the carbocyclization mechanism and to identify the functional role of the diene fragment we analyzed the simulated reaction mechanisms using the two parent systems. We discovered a thus far unrecognized, but intuitively plausible, role of the CO ligand for controlling the electron density at the metal center, which affects the feasibility of oxidative addition and reductive elimination steps that are key components of the mechanism. Our calculations suggest that the diene moiety is unique and required because of its ability to undergo a eta(2)-->eta(4) reorganization allowing for the thermoneutral expulsion of one CO ligand, which in turn generates an electron-rich, coordinatively saturated Rh(I) center that can efficiently promote the oxidative addition with a low barrier. A number of functionalization strategies were considered explicitly to derive a rational plan for optimizing the catalysis and to expose the roles of the different components of the reactant-catalyst complex.

The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study. Publishing Authors By Initials

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The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 130

Page Numbers: 5821-30

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 1520-5126

DAY: 2

MONTH: 04

YEAR: 2008

The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study. Information

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LANGUAGE: eng

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Grant and Affiliation Information for The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study.

AFFILIATION: Department of Chemistry and School of Informatics, Indiana University, Bloomington, Indiana 47405, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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