PALLADIUM-CATALYZED CROSS COUPLING OF ALLYL HALIDES WITH ORGANOTIN REAGENTS: A METHOD OF JOINING HIGHLY FUNCTIONALIZED PARTNERS REGIOSELECTIVELY AND STEREOSPECIFICALLY.

Article abstract of DOI:10.1021/ja00329a032

The palladium-catalyzed reaction of allyl halides with aryl- and vinyltin reagents gives high yields of cross-coupled products. In the presence of 1-3 atm of carbon monoxide, ketones are obtained, resulting from cross coupling accompanied by carbon monoxide insertion. The reaction is mild and tolerant of a wide variety of functionalities (OH, OR, CN, CO//2R, CHO) on either the allyl chloride or the tin reagent. Coupling at the allyl halide partner proceeds with inversion of configuration at the carbon bearing the halide, with retention of geometry at the allylic double bond, and with a regioselectivity for the least-substituted carbon in the allylic framework. Retention of double-bond geometry is observed in the vinyltin partner.