The Corey–House Reaction: An Early Transition-Metal-Mediated Cross-Coupling

Key words

Corey–House reaction - Gilman cuprates - C–C cross-coupling

Significance

In 1967, Corey and Posner reported a simple method for carbon–carbon cross-coupling using the previously reported Gliman cuprates of type R₂CuLi. In Corey’s original publication Me₂CuLi was generated by adding MeLi to cuprous halides. The resulting dimethylcuprate was used for cross-couplings with alkyl, alkenyl, or aryl bromides and iodides to form the corresponding methylated products. trans-1-Bromo-2-phenylethylene was stereospecifically converted into trans-1-phenylpropene. In a similar fashion formation of cis-1-phenylpropene was observed from cis-1-bromo-2-phenylethylene.

Comment

In 1969 Whitesides, House, and co-workers contributed significantly to the scope of the coupling reaction by using lithium aryl-, sec-­alkyl and tert-alkyl cuprates as coupling partners for the organic halides (G. M. Whitesides, W. F. Fischer Jr., J. San Filippo Jr., R. W. Bashe, H. O. House J. Am. Chem. Soc. 1969, 91, 4871). Thus, the cross-coupling reaction of Gilman cuprates with organyl halides is known as the Corey–House reaction. Variations of the name including Whitesides and Posner are also in use.