Corey-House synthesis

Two alkyl groups can be coupled by indirectly reacting two molecules of RX, or RX with R X, to give R—R or R—R. respectively. The preferred method is the Corey-House synthesis, which uses the organometallic lithium dialkylcuprates, RXuLi, as intermediates. 

Pioneering work on the desulphonylation of jS-ketosulphones was carried out by Corey and Chaykovsky - . This reaction was part of a sequence which could be used in the synthesis of ketones, as shown in equation (53). The main thrust of this work was in the use of sulphoxides, but Corey did stress the merits of both sulphones and sulphonamides for different applications of this type of reaction. The method soon found application by Stetter and Hesse for the synthesis of 3-methyl-2,4-dioxa-adamantane , and by House and Larson in an ingenious synthesis of intermediates directed towards the gibberellin skeleton, and also for more standard applications . Other applications of the method have also been madealthough it does suffer from certain limitations in that further alkylation of an a-alkyl- -ketosulphone is a very sluggish, inefficient process. Kurth and O Brien have proposed an alternative, one-pot sequence of reactions (equation 54), carried out at — 78 to — 50°, with yields better than 50%. The major difference between the two routes is that the one-pot process uses the desulphonylation step to generate the enolate anion, whereas in the Corey-House procedure, the desulphonylation with aluminium amalgam is a separate, non-productive step. 

Lithium Dialkylcuperates The Corey-Posner, Whitesides-House Synthesis... 

E COREY-POSNER, WHITESIDE-HOUSE SYNTHESIS (SECTION 12.9)... 

A highly versatile method for the synthesis of alkanes and other hydrocarbons from organic halides has been developed by E. J. Corey (Harvard University, Nobel Prize for Chemistry in 1990), G. H. Posner (The Johns Hopkins University), and by G. M. Whitesides (Harvard University) and H. O. House (Georgia Institute of Technology). 

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