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Volumn 345, Issue 9-10, 2003, Pages 1159-1171

Theoretical Studies on Diastereo- and Enantioselective Rhodium-Catalyzed Cyclization of Diazo Compound via Intramolecular C-H Bond Insertion

Author keywords

C H activation; Carbene complex; Cyclization; Diazo compounds; Rhodium; Stereoselectivity; Theoretical calculation

Indexed keywords

AMIDE; AZO COMPOUND; CARBON; CARBOXYLIC ACID DERIVATIVE; DIRHODIUM TETRACARBOXYLATE; HETEROCYCLIC COMPOUND; HYDROGEN; RHODIUM; UNCLASSIFIED DRUG;

EID: 0242522913     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/adsc.200303092     Document Type: Article
Times cited : (64)

References (45)
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    • Ed.: L. S. Hegedus, Pergamon Press, New York, Chapters 5.1 and 5.2
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    • b) K. M. Lydon, M. A. McKervey, in Comprehensive Asymmetric Catalysis, Vol. 2 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999, Chapter 16.2;
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    • Ed.: I. Ojima, Wiley-VCH, New York, Chapter 5
    • c) M. P. Doyle, in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), Wiley-VCH, New York, 2000, Chapter 5;
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    • note
    • Merck employs Rh-catalyzed N-H insertion reactions of diazo compounds for the production of carbapenems.
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    • M. S. Gordon, D. R. Gano, J. Am. Chem. Soc. 1984, 106, 5421-5425; R. D. Bach, M-D. Su, E. Aldabbagh, J. L. Andrés, H. B. Schlegel, J. Am. Chem. Soc. 1993, 115, 10237-10246.
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    • note
    • The PM3/B3LYP modeling was also applied to B3LYP-optimized structures themselves to find that the relative stability of the half-chair and boat isomers did not change: TS1a-1 and TS1b-1 were calculated to be more stable than their boat isomers by 3.2 and 5.1 kcal/mol, respectively (1.2 and 5.1 kcal/mol at the B3LYP level).
  • 41
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    • note
    • The cis-trans and cis-cis TSs were also examined, and trans/cis selectivities with respect to the forming C-C bond were calculated to be 98.8:1.2 (entry 1), 98.7:1.3 (entry 2) and 95.3:4.7 (entry 3), which qualitatively reproduced the experimental results.
  • 42
    • 0001595444 scopus 로고
    • In this case, an ethoxycarbonyl group was attached to the reacting carbon atom. Since it destabilizes a neighboring carbocation, the TS of C-H insertion is expected to become later. This would be unfavorable for the trans-TS due to significant steric repulsion between the ester group and the dirhodium carboxylate framework.
    • [10]), Doyle found the cis geometry in a similar system using achiral dirhodium perfluorobutyrate: M. P. Doyle, J. Taunton, H. Q. Pho, Tetrahedron Lett. 1989, 30, 5397-5400. In this case, an ethoxycarbonyl group was attached to the reacting carbon atom. Since it destabilizes a neighboring carbocation, the TS of C-H insertion is expected to become later. This would be unfavorable for the trans-TS due to significant steric repulsion between the ester group and the dirhodium carboxylate framework.
    • (1989) Tetrahedron Lett. , vol.30 , pp. 5397-5400
    • Doyle, M.P.1    Taunton, J.2    Pho, H.Q.3
  • 43
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    • note
    • Steric repulsion may be more significant than electrostatic one since replacement of the methoxy group by phenyl, benzyl, and ethyl groups results in only modest decrease in enantioselectivity. We thank one referee for pointing out this issue.
  • 44
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    • Examples of five-membered ring formation of a disubstituted diazo compound with > 90% ee: a) H. M. L. Davies, M. V. A. Grazini, E. Aouad, Org. Lett. 2001, 3, 1475-1477; b) H. Saito, H. Oishi, S. Kitagaki, S. Nakamura, M. Anada, S. Hashimoto, Org. Lett. 2002, 4, 3887-3890.
    • (2001) Org. Lett. , vol.3 , pp. 1475-1477
    • Davies, H.M.L.1    Grazini, M.V.A.2    Aouad, E.3
  • 45
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    • Examples of five-membered ring formation of a disubstituted diazo compound with > 90% ee: a) H. M. L. Davies, M. V. A. Grazini, E. Aouad, Org. Lett. 2001, 3, 1475-1477; b) H. Saito, H. Oishi, S. Kitagaki, S. Nakamura, M. Anada, S. Hashimoto, Org. Lett. 2002, 4, 3887-3890.
    • (2002) Org. Lett. , vol.4 , pp. 3887-3890
    • Saito, H.1    Oishi, H.2    Kitagaki, S.3    Nakamura, S.4    Anada, M.5    Hashimoto, S.6


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.