ACYLPALLADATION OF INTERNAL ALKYNES AND PALLADIUM-CATALYZED CARBONYLATION OF (Z)-BETA-IODOENONES AND RELATED DERIVATIVES PRODUCING GAMMA-LACTONES AND GAMMA-LACTAMS

The reaction of either an internal alkyne-organic halide mixture or (Z)-beta-iodoenones with CO in the presence of a Pd-phosphine catalyst, e.g., Cl2Pd(PPh(3))2, can give one of the three discrete types of compounds as the major products depending on the substrate structure and the reaction conditions. Those substrates which are convertible to (Z)-gamma-oxo-alpha,beta-unsaturated acylpalladium derivatives lacking delta-H atoms are converted to the corresponding 2-butenolides (13) in the presence of water, which serves as a H donor. Carbon monoxide most likely is the source of two electrons. Either in the absence of water (or any other suitable H source) or in the presence of some factors disfavoring the butenolide formation, the same reaction gives the corresponding dimeric product (16). Even in cases where there is an alpha-H atom in the alpha-substitutent, 1,4-elimination products (11), reported to be the major products in a related Pd-catalyzed reaction of terminal alkyne-aryl iodide mixtures with CO, were not detected. In sharp contrast, those substrates which can give rise to (Z)-gamma-oxo-alpha, beta-unsaturated acylpalladium derivatives containing delta-H atoms give, under comparable reaction conditions, enol lactones (12), i.e., (Z)-3-alkylidene-2-butenolides, contaminated with only very minor amounts of 22 even in cases where an excess (4 equiv) of water was present. The required (Z)-beta-iodoenones can be readily prepared in one pot via ZrCp(2)-promoted cyclization of alkynes with nitriles. The ready availability of the starting compounds and the high Z stereoselectivity make the overall sequence an attractive synthetic route to 12. The courses of the Pd-catalyzed carbonylation reactions of (Z)-beta-iodo-alpha,beta-unsaturated imines 23 closely parallel the reactions of enones and produce the corresponding lactams, i.e., 24 and 25.