Jirō Tsuji

Jiro Tsuji
BornMay 11, 1927
Shiga Prefecture, Japan
DiedApril 1, 2022
Kamakura, Japan
NationalityJapanese
Alma materKyoto University B.S. (1951)

Baylor University M.S. (1957)

Columbia University Ph.D. (1960)
Known forTsuji-Trost reaction, Tsuji–Wilkinson decarbonylation reaction
Scientific career
FieldsOrganic Chemistry, Organometallic Chemistry
InstitutionsTokyo Institute of Technology
Thesis Studies Toward the Total Synthesis of Vitamin D. Synthetic Studies Related to the aconite-arrya Alkaloids
Doctoral advisorGilbert Stork

Jiro Tsuji (May 11, 1927 – April 1, 2022)[1] was a Japanese chemist, notable for his discovery of organometallic reactions, including the Tsuji-Trost reaction, the Tsuji-Wilkinson decarbonylation, and the Tsuji-Wacker reaction.

Early life and education

Tsuji was born in Japan in 1927.[1]

After attending Kyoto University, Tsuji began his doctoral research at Columbia University under Gilbert Stork[2] studying natural product synthesis, and making contributions to research on the dissolving metal reduction of enones.[3][4]

Independent career

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.

Tsuji's first report of rhodium-mediated decarbonylation.[9]

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.[12]

Tsuji's first report of palladium-mediated allylation.[13]

Later research hinged on the discovery that allyl acetoacetates decarboxylate and regioselectively alpha-allylate in the presence of catalytic Pd(OAc)2 and PPh3 via the intermediacy of an allylpalladium enolate[14] - 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.[15] This transformation was applied by Tsuji to the racemic synthesis of methyl jasmonate.[16] Tsuji also found that the palladium enolate could be engaged in intramolecular aldol reactions.[17]

Awards

  • 1980 - Chemical Society of Japan Award, for "research on new organic synthesis processes using transition metal compounds"
  • 1994 - Purple ribbon medal of honor
  • 2004 - Japan Academy Prize, for "research on new organic synthesis reactions using palladium catalysts"[18]
  • 2014 - Tetrahedron Prize

References

  1. ^ a b "Obituary: Jiro Tsuji". cen.acs.org. August 8, 2022. Archived from the original on June 9, 2023. Retrieved 2023-06-09.
  2. ^ Yamamoto, Y. (March 1999). "A profile of Professor Jiro Tsuji". Journal of Organometallic Chemistry. 576 (1–2): xi–xiii. doi:10.1016/S0022-328X(98)01135-8.
  3. ^ Stork, Gilbert; Tsuji, Jiro (June 1961). "LITHIUM-AMMONIA REDUCTION OF α,β-UNSATURATED KETONES. II. FORMATION AND ALKYLATION OF A β-CARBANION INTERMEDIATE". Journal of the American Chemical Society. 83 (12): 2783–2784. doi:10.1021/ja01473a053. ISSN 0002-7863.
  4. ^ Stork, Gilbert; Rosen, P.; Goldman, N.; Coombs, R. V.; Tsuji, J. (January 1965). "Alkylation and Carbonation of Ketones by Trapping the Enolates from the Reduction of α,β-Unsaturated Ketones". Journal of the American Chemical Society. 87 (2): 275–286. doi:10.1021/ja01080a025. ISSN 0002-7863.
  5. ^ Tsuji, Jiro.; Kiji, Jitsuo.; Imamura, Shinzo.; Morikawa, Masanobu. (October 1964). "Organic Syntheses by Means of Noble Metal Compounds. VIII. 1 Catalytic Carbonylation of Allylic Compounds with Palladium Chloride". Journal of the American Chemical Society. 86 (20): 4350–4353. doi:10.1021/ja01074a023. ISSN 0002-7863.
  6. ^ Tsuji, J.; Morikawa, M.; Kiji, J. (January 1963). "Reaction of olefin-palladium chloride complex with carbon monoxide". Tetrahedron Letters. 4 (16): 1061–1064. doi:10.1016/S0040-4039(01)90774-9.
  7. ^ Tsuji, Jiro; Kiji, Jitsuo; Morikawa, Masanobu (January 1963). "Organic syntheses by means of noble metal compounds III. Reaction of π -allylpalladium chloride complex with carbon monoxide". Tetrahedron Letters. 4 (26): 1811–1813. doi:10.1016/S0040-4039(01)90920-7.
  8. ^ Tsuji, Jiro; Ohno, Kiyotaka; Kajimoto, Tsunesuke (January 1965). "Organic syntheses by means of noble metal compounds XX. Decarbonylation of acyl chloride and aldehyde catalyzed by palladium and its relationship with the rosenmund reduction". Tetrahedron Letters. 6 (50): 4565–4568. doi:10.1016/S0040-4039(01)89065-1.
  9. ^ a b Tsuji, Jiro; Ohno, Kiyotaka (1965-01-01). "Organic syntheses by means of noble metal compounds XXI. Decarbonylation of aldehydes using rhodium complex". Tetrahedron Letters. 6 (44): 3969–3971. doi:10.1016/S0040-4039(01)89127-9. ISSN 0040-4039.
  10. ^ Tsuji, Jiro; Takahashi, Hidetaka; Morikawa, Masanobu (1965). "Organic syntheses by means of noble metal compounds XVII. Reaction of π-allylpalladium chloride with nucleophiles". Tetrahedron Letters. 6 (49): 4387–4388. doi:10.1016/S0040-4039(00)71674-1.
  11. ^ Trost, Barry M.; Fullerton, Terry J. (January 1973). "New synthetic reactions. Allylic alkylation". Journal of the American Chemical Society. 95 (1): 292–294. doi:10.1021/ja00782a080. ISSN 0002-7863.
  12. ^ Tsuji, Jiro; Shimizu, Isao; Yamamoto, Keiji (August 1976). "Convenient general synthetic method for 1,4- and 1,5-diketones by palladium catalyzed oxidation of α-allyl and α-3-butenyl ketones". Tetrahedron Letters. 17 (34): 2975–2976. doi:10.1016/S0040-4039(01)85504-0.
  13. ^ Tsuji, Jiro; Takahashi, Hidetaka; Morikawa, Masanobu (1965-01-01). "Organic syntheses by means of noble metal compounds XVII. Reaction of π-allylpalladium chloride with nucleophiles". Tetrahedron Letters. 6 (49): 4387–4388. doi:10.1016/S0040-4039(00)71674-1. ISSN 0040-4039.
  14. ^ Shimizu, Isao; Yamada, Toshiro; Tsuji, Jiro (January 1980). "Palladium-catalyzed rearrangement of allylic esters of acetoacetic acid to give γ,δ-unsaturated methyl ketones". Tetrahedron Letters. 21 (33): 3199–3202. doi:10.1016/S0040-4039(00)77444-2.
  15. ^ Shimizu, Isao; Tsuji, Jiro (October 1982). "Palladium-catalyzed decarboxylation-dehydrogenation of allyl .beta.-oxo carboxylates and allyl enol carbonates as a novel synthetic method for .alpha.-substituted .alpha.,.beta.-unsaturated ketones". Journal of the American Chemical Society. 104 (21): 5844–5846. doi:10.1021/ja00385a075. ISSN 0002-7863.
  16. ^ Kataoka, Hideaki; Yamada, Toshiro; Goto, Kuniaki; Tsuji, Jiro (1987-01-01). "An efficiemt synthetic method of methyl (±)-jasmonate". Tetrahedron. 43 (18): 4107–4112. doi:10.1016/S0040-4020(01)83449-9. ISSN 0040-4020.
  17. ^ Nokami, Junzo; Mandai, Tadakatsu; Watanabe, Hisayuki; Ohyama, Hiroshi; Tsuji, Jiro (May 1989). "The palladium-catalyzed directed aldol reaction of aldehydes with ketone enolates generated by the decarboxylation of allyl .beta.-keto carboxylates under neutral conditions". Journal of the American Chemical Society. 111 (11): 4126–4127. doi:10.1021/ja00193a069. ISSN 0002-7863.
  18. ^ "Prof. Jiro Tsuji and Prof. Akira Suzuki received the Japan Academy Prize". Journal of Synthetic Organic Chemistry, Japan. 62 (5): 410. 2004. doi:10.5059/yukigoseikyokaishi.62.410. ISSN 0037-9980. Archived from the original on June 9, 2023. Retrieved June 9, 2023.{{cite journal}}: CS1 maint: bot: original URL status unknown (link)