The mechanism of the carbonylation of alkynes promoted by the Pd(OAc)2/2-pyridyldiphenylphosphine/methanesulfonic acid catalytic system has been studied. The carbonylation of 2-butyne in the presence of methanol affords stereospecifically the methyl ester of (E)-2-methyl-2-butenoic acid, indicating that the addition of H and COOCH3 moieties proceeds with cis stereochemistry. Experiments carried out using 1-alkynes and CH3OD reveal that the catalyst also promotes the exchange of the terminal hydrogen of the alkyne with the deuterium of the alcohol. 1H NMR experiments show that upon addition of phenylacetylene to a CD2Cl2 solution containing the catalyst and CH3OH a palladium complex having a 2-styryl group bound to the metal center, Pd−C(C6H5)CH2, is formed. This species can be invoked as an intermediate to account for both the H/D exchange and the carbonylation reaction. Carbonylation of 2-butyne in the presence of a 1/1 mixture of CH3OH and CH3OD indicates that a fairly large isotope effect (k H/k D = 6.4) is operative. All these results suggest that the carbonylation of alkynes proceeds via the protonation of a Pd(0)−alkyne species to give a Pd−vinyl complex, followed by CO insertion and alcoholysis.

The coupling of arylboronic acids with electron‐rich allylic bromides is accomplished in the absence of any transition‐metal catalyst through conventional heating. The reaction is completely regioselective, affording only the α‐coupled product, and can be carried out under mild aerobic conditions in an organic solvent; the presence of a base is required.

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Abstract-The iminophosphine-palladium(0) complex [Pd(dmfu)(P-N)] [dmfu ¼ dimethyl fumarate; P-N ¼ 2-(PPh 2 )C 6 H 4 -1-CH@NC 6 H 4 -4-OMe] is a very efficient catalyst for the Suzuki coupling. In the reaction of aryl bromides with phenylboronic acid, turnover numbers up to ca. 200,000 are obtained at 110°C in 2 h. Good rates are obtained also with the sterically hindered and electronically deactivated 2-bromo-1,3,5-trimethylbenzene. The complex is able to catalyze the exhaustive arylation of 2, 3,7,8,12,13,17,10, to yield the corresponding undecaaryl substituted derivative.