Jirō Tsuji

[3][4] His independent career began at Toyo Rayon (now Toray Industries) studying the stoichiometric, and later catalytic[5] carbonylation of PdII-alkene complexes with carbon monoxide.

[6][7] His preliminary results showed that acyl halides and aldehydes could be decarbonylated by Pd0 at high temperatures (200 °C) yielding alkenes;[8] further investigation revealed that stoichiometric quantities of Wilkinson's catalyst was able to affect the same reaction at lower temperatures,[9] now known as the Tsuji-Wilkinson decarbonylation.

His pioneering work resulting in the development of the Tsuji-Trost reaction was the discovery that allyl-PdII complexes react with malonates, acetoacetates, and enamines yielding alpha-allylated carbonyl compounds,[10] which was later generalized and rendered asymmetric by Barry Trost.

[11] Tsuji additionally noted the utility of these alpha-allylated ketones and esters in preparing 1,4-dicarbonyl compounds using the Wacker oxidation.

Following work revealed that replacement of PPh3 in the reaction mixture with the bidentate ligand dppe could favor beta-hydride elimination of the palladium enolate, yielding enones.