Rogue Scholar

MetalReaction MechanismSimulationTutorial MaterialChemical Sciences

Secrets revealed for conjugate addition to cyclohexenone using a Cu-alkyl reagent.

https://doi.org/10.59350/xmq7a-3hj74

Published November 4, 2012 in Henry Rzepa's Blog

Author Henry Rzepa

The text books say that cyclohexenone A will react with a Grignard reagent by delivery of an alkyl (anion) to the carbon of the carbonyl ( 1,2-addition ) but if dimethyl lithium cuprate is used, a conjugate 1,4-addition proceeds, to give the product B shown below.

References

Colloid and Surface ChemistryBiochemistryGeneral ChemistryCatalysis

Rapid-Injection NMR Study of Iodo- and Cyano-Gilman Reagents with 2-Cyclohexenone: Observation of π-Complexes and Their Rates of Formation

https://doi.org/10.1021/ja027744s

Published October 29, 2002 in Journal of the American Chemical Society

Authors Steven H. Bertz, Clifford M. Carlin, Daniel A. Deadwyler, Michael D. Murphy, Craig A. Ogle, Paul H. Seagle

Colloid and Surface ChemistryBiochemistryGeneral ChemistryCatalysis

Rapid Injection NMR in Mechanistic Organocopper Chemistry. Preparation of the Elusive Copper(III) Intermediate

https://doi.org/10.1021/ja067533d

Published May 17, 2007 in Journal of the American Chemical Society

Authors Steven H. Bertz, Stephen Cope, Michael Murphy, Craig A. Ogle, Brad J. Taylor

Colloid and Surface ChemistryBiochemistryGeneral ChemistryCatalysis

Organocuprate Conjugate Addition: The Square-Planar “Cu^III” Intermediate

https://doi.org/10.1021/ja0675346

Published May 17, 2007 in Journal of the American Chemical Society

Authors Haipeng Hu, James P. Snyder

Structural Reassignment of Obtusallenes V, VI, and VII by GIAO-Based Density Functional Prediction

https://doi.org/10.1021/np0705918

Published February 23, 2008 in Journal of Natural Products

Authors D. Christopher Braddock, Henry S. Rzepa