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Volumn 127, Issue 46, 2005, Pages 16255-16262

Regiospecific and stereoselective syntheses of (±)-reserpine and (-)-reserpine

Author keywords

[No Author keywords available]

Indexed keywords

REGIOSPECIFIC SYNTHESIS; RESERPINE; STEREOSELECTIVE SYNTHESIS;

EID: 28044452880     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055744x     Document Type: Article
Times cited : (72)

References (86)
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    • Heterocycles 1987, 25, 263.
    • (1987) Heterocycles , vol.25 , pp. 263
  • 19
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    • Many routes to reserpine. although abandoned for one reason or another, deserve attention. Cf., inter alia, Isobe, M.; Fukami, N.; Nishikawa, T.; Goto, T. Heterocycles 1987, 25, 521.
    • (1987) Heterocycles , vol.25 , pp. 521
    • Isobe, M.1    Fukami, N.2    Nishikawa, T.3    Goto, T.4
  • 20
    • 0042426388 scopus 로고
    • The original Woodward synthesis of reserpine goes through the initial formation of isoreserpine, its C-3 epimer, via a borohydride reduction in methanol which presumably involves axial addition of hydride to a pre chair iminium intermediate. A variety of modified reduction conditions of an iminium intermediate have been explored in the hope of producing reserpine directly, rather than via its C-3 epimer. Catalytic hydrogenation (cf. Gottfredsen, W. O.; Vangedal, S. Acta Chem. Scand. 1956, 10, 1414) also gives isoreserpine. but zinc-aqueous acid processes have been reported to yield reserpine selectively,
    • (1956) Acta Chem. Scand. , vol.10 , pp. 1414
    • Gottfredsen, W.O.1    Vangedal, S.2
  • 21
    • 0041424004 scopus 로고
    • (a) For instance, Weisenborn et al. (Weisenborn, F. L.; Diassi, P. A. J. Am. Chem. Soc. 1956, 78, 2022) reported the formation of reserpine, in unspecified yield, by zinc-aqueous acetic acid reduction.
    • (1956) J. Am. Chem. Soc. , vol.78 , pp. 2022
    • Weisenborn, F.L.1    Diassi, P.A.2
  • 24
    • 0023231077 scopus 로고
    • Martin (J. Am. Chem. Soc: 1987, 109, 6124) reports, however, that his group's attempts to duplicate the favorable results reported earlier for these zinc-acid reductions gave, by contrast, ratios of 1:1.7-2.0 in favor of isoreserpine.
    • (1987) J. Am. Chem. Soc , vol.109 , pp. 6124
  • 43
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    • Ph.D. Thesis. Columbia University
    • Livingston, D. A. Ph.D. Thesis. Columbia University; Diss. Abstr. Int. B 1982, 43 (5), 1496.
    • (1982) Diss. Abstr. Int. B , vol.43 , Issue.5 , pp. 1496
    • Livingston, D.A.1
  • 45
    • 84942709251 scopus 로고
    • For discussions of the deconjugation of some αβ-unsaturated esters, see: (a) Krebs, E.-P. Helv. Chim. Acta 1981, 64, 1023.
    • (1981) Helv. Chim. Acta , vol.64 , pp. 1023
    • Krebs, E.-P.1
  • 51
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    • For a discussion of the factors affecting the ratio of E to Z isomers from deprotonation-silylation of unconjugated esters, see: Ireland, R. E.; Wipf, P.: Armstrong, J. D., III. J. Org. Chem. 1991, 56, 650.
    • (1991) J. Org. Chem. , vol.56 , pp. 650
    • Ireland, R.E.1    Wipf, P.2    Armstrong III, J.D.3
  • 54
    • 28044435882 scopus 로고
    • Wender et al. (Wender, P. A.; Schaus. J. M.; White, A. W. Heterocycles 1987, 25, 263) have described direct reduction of a closely related α-methoxycyclohexanone to the epimer trans to the vicinal methoxy group, in the presence of ceric chloride
    • (1987) Heterocycles , vol.25 , pp. 263
    • Wender, P.A.1    Schaus, J.M.2    White, A.W.3
  • 55
  • 56
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    • The considerably more reactive cyclopentadiene has been successfully added to methyl 3-methoxyacrylate under Lewis acid catalysis: Baldwin, S. W.; Tomesch, J. C. J. Org. Chem. 1974, 39, 2382.
    • (1974) J. Org. Chem. , vol.39 , pp. 2382
    • Baldwin, S.W.1    Tomesch, J.C.2
  • 59
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    • note
    • A similar problem has been encountered with a 3-chloroacrylate: see ref 22b.
  • 62
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    • The selection of a 2-furyl substituent on silicon was made in the expectation that it would facilitate later exchange for fluorine. Cf. Simas, A. B. C.; Stork, G. J. Braz. Chem. Soc. 1996, 7, 265.
    • (1996) J. Braz. Chem. Soc. , vol.7 , pp. 265
    • Simas, A.B.C.1    Stork, G.2
  • 71
  • 73
    • 84984087516 scopus 로고
    • The first published reference to the reduction of a lactone (five-membered) to a lactol by DibalH seems to be the following: Schmidlin, J.; Wettstein, A. Helv. Chim. Acta 1963, 46, 2799.
    • (1963) Helv. Chim. Acta , vol.46 , pp. 2799
    • Schmidlin, J.1    Wettstein, A.2
  • 77
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    • See also footnote 33 of Martin's 1987 paper
    • Stork, G.; Guthikonda. R. J. Am. Chem. Soc. 1972, 94, 5109. See also footnote 33 of Martin's 1987 paper.
    • (1972) J. Am. Chem. Soc. , vol.94 , pp. 5109
    • Stork, G.1    Guthikonda, R.2
  • 80
    • 28044433704 scopus 로고    scopus 로고
    • note
    • The assignment of axial stereochemistry to the cyano group in 40 was supported by NMR data and by an X-ray structure determination of a related cyanopiperidine.
  • 81
    • 0026681079 scopus 로고
    • - in acetonitrile), so that kinetic arguments relating to the angle of initial entry (perpendicular chair) into the iminium ion intermediate may not be relevant to this case. Thermodynamic equilibrium is, in any case, also in favor of an axial cyano group in 2-cyanopiperidines, possibly because of an endo anomeric effect: cf. Booth. H.: Dixon, J. M.; Khedhair, K. A. Tetrahedron 1992, 48, 6161.
    • (1992) Tetrahedron , vol.48 , pp. 6161
    • Booth, H.1    Dixon, J.M.2    Khedhair, K.A.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.