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
ThesisStudies 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. 1 2 "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. 1 2 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.
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