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The reaction of arylstannanes ArSnR 3 with unfunctionalised alkynes was found to proceed in the presence of a rhodium catalyst and a catalytic amount of zinc chloride to give ortho -alkenylarylstannanes with high selectivity in high yields. The catalytic cycle is very unique, consisting of three transmetalation steps, from Sn to Rh, Rh to Zn, and Zn to Sn, in addition to arylrhodation of alkyne followed by 1,4-migration of Rh from 2-arylalkenyl carbon to ortho -alkenylaryl carbon.

Addition of arylstannanes to alkynes giving ortho-alkenylarylstannanes catalysed cooperatively by a rhodium complex and zinc chloride