PALLADIUM-CATALYZED HYDROGENOLYSIS OF ALLYLIC COMPOUNDS WITH FORMIC-ACID - ITS APPLICATION TO ORGANIC-SYNTHESIS

Hydrogenolysis of various allylic compounds with formic acid is carried out under mild conditions in the presences of a palladium catalyst. 1-Olefins are obtained selectively by the hydrogenolysis of terminal allylic compounds. Protection of amines is carried out by converting to allyl carbamates, which are deprotected to regenerate amines by the palladium-catalyzed hydrogenolysis. Allyl ethers of oximes used for the protection of ketones are similarly deprotected. Decarboxylation of allylic esters of beta-keto esters, alpha-oxal carboxylates, and malonates proceeds smoothly to afford ketones, alpha-keto acids, and carboxylic acids. Regio- and stereoselective ring opening of alkenyl oxiranes is carried out, and successfully applied to the syntheses of (S, S)-Hydroxymethylheptanol, Serricornin, and Nupharamine.