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Issue 4, 2012
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Rhodium/diene-catalyzed tandem 1,4-shift/1,4-addition of (E)-1,2-diphenylethenylboronic acid to enones: density functional theory modeling and asymmetric catalysis

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Abstract

The conjugate addition of (E)-1,2-diphenylethenylboronic acid to 2-cyclohexenone in the presence of a diene/rhodium catalyst leads to a rearranged product incorporating a 2-((E)-2-phenylethenyl)phenyl group. The catalytic cycle involves a 1,4-Rh shift from the 1,2-diphenylethenylrhodium intermediate to form a new 2-((E)-2-phenylethenyl)phenylrhodium intermediate. DFT calculations demonstrate that the 1,4-Rh shift occurs via C–H oxidative addition and reductive elimination to/from a distorted square-pyramidal Rh(III)-hydride intermediate. The relative ΔG of the 1,4-shift and carborhodation transition states are in good agreement with the experimentally observed selectivity.

Graphical abstract: Rhodium/diene-catalyzed tandem 1,4-shift/1,4-addition of (E)-1,2-diphenylethenylboronic acid to enones: density functional theory modeling and asymmetric catalysis

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Article information


Submitted
21 Dec 2011
Accepted
16 Jan 2012
First published
17 Jan 2012

Chem. Sci., 2012,3, 1278-1283
Article type
Edge Article

Rhodium/diene-catalyzed tandem 1,4-shift/1,4-addition of (E)-1,2-diphenylethenylboronic acid to enones: density functional theory modeling and asymmetric catalysis

K. Sasaki, T. Nishimura, R. Shintani, E. A. B. Kantchev and T. Hayashi, Chem. Sci., 2012, 3, 1278
DOI: 10.1039/C2SC01093C

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