Jirō Tsuji


Jiro Tsuji was a Japanese chemist, notable for his discovery of organometallic reactions, including the Tsuji–Trost reaction, the Tsuji–Wilkinson decarbonylation reaction, and the Tsuji–Wacker reaction.

Early life and education

Tsuji was born in Japan in 1927.
After attending Kyoto University, Tsuji began his doctoral research at Columbia University under Gilbert Stork studying natural product synthesis, and making contributions to research on the dissolving metal reduction of enones.

Independent career

His independent career began at Toyo Rayon studying the stoichiometric, and later catalytic carbonylation of PdII-alkene complexes with carbon monoxide. His preliminary results showed that acyl halides and aldehydes could be decarbonylated by Pd0 at high temperatures yielding alkenes; further investigation revealed that stoichiometric quantities of Wilkinson's catalyst was able to affect the same reaction at lower temperatures, now known as the Tsuji–Wilkinson decarbonylation reaction.
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, which was later generalized and rendered asymmetric by Barry Trost. Tsuji additionally noted the utility of these alpha-allylated ketones and esters in preparing 1,4-dicarbonyl compounds using the Wacker oxidation.
Later research hinged on the discovery that allyl acetoacetates decarboxylate and regioselectively alpha-allylate in the presence of catalytic Pd2 and PPh3 via the intermediacy of an allylpalladium enolate - a catalytic Carroll rearrangement. 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. This transformation was applied by Tsuji to the racemic synthesis of methyl jasmonate. Tsuji also found that the palladium enolate could be engaged in intramolecular aldol reactions.

Awards