No abstract

Benzyl esters of propiolic and beta-keto acids undergo catalytic decarboxylative coupling when treated with appropriate palladium catalysts. Such decarboxylative couplings allow the benzylation of alkynes without the use of strong bases and/or organometallics. This allows the synthesis of sensitive benzylic alkynes that are prone to undergo isomerizations under basic conditions. Additionally, decarboxylation facilitates the site-specific benzylation of diketones and ketoesters under mild, base-free conditions. Ultimately, the methodology described expands our ability to cross-couple medicinally relevant heterocycles.

No abstract

Palladium nanoparticles, generated in situ from the reaction of palladium(II) chloride, have been demonstrated to be an efficient catalyst for C-N bond formation. A variety of aliphatic and aromatic amines have been allylated by substituted and unsubstituted allyl acetates in high yields by using palladium nanoparticles in the presence of a base without any ligand. The allylations are highly regio- and stereoselective.

Palladium(0) nanoparticle has been used as an efficient catalyst for the allylation of active methylene compounds. Very efficient bisallylation is achieved for a variety of active methylene compounds by allyl acetate and its derivatives in one stroke in THF solvent. The reaction in water provides monoallylated product selectively by allyl acetate only. The recovered Pd(0) nanoparticle is recycled. A probable mechanism is suggested.