Issue 4, 2012

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Dec 2011
Accepted
16 Jan 2012
First published
17 Jan 2012

Chem. Sci., 2012,3, 1278-1283

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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