Gold-Catalyzed C(sp2)-C(sp) Coupling by Alkynylation through Oxidative Addition of Bromoalkynes

A gold(I)-catalyzed cascade cyclization-alkynylation of allenoates using alkynyl bromide to generate beta-alkynyl-gamma-butenolides was investigated. Whereas alkynyl iodides afforded significant amounts of the homo-coupling of two lactone units, alkynyl bromides led to a selective reaction, and a broad functional group tolerance was observed. Under the optimized reaction conditions, it was possible to directly synthesize a large range of beta-alkynyl-gamma-butenolides in moderate to good yields without the need for any external oxidant.