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Volumn 130, Issue 41, 2008, Pages 13745-13754

Pd-catalyzed enantioselective aerobic oxidation of secondary alcohols: Applications to the total synthesis of alkaloids

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL OXYGEN DEMAND; COMPLEXATION; OXIDATION; PALLADIUM;

EID: 53849126527     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja804738b     Document Type: Article
Times cited : (142)

References (113)
  • 1
    • 37349027263 scopus 로고    scopus 로고
    • For recent reviews on the enantioselective synthesis of amines, see: a
    • For recent reviews on the enantioselective synthesis of amines, see: (a) Moody, C. J. Angew. Chem., Int. Ed. 2007, 46, 9148.
    • (2007) Angew. Chem., Int. Ed , vol.46 , pp. 9148
    • Moody, C.J.1
  • 11
    • 1442349810 scopus 로고    scopus 로고
    • For selected examples of synthesis of amines directly from alcohols, their corresponding esters, carbonates, sulfonate esters, or alkyl halides, see: a
    • For selected examples of synthesis of amines directly from alcohols, their corresponding esters, carbonates, sulfonate esters, or alkyl halides, see: (a) Kan, T.; Fukuyama, T. Chem. Commun. 2004, 353.
    • (2004) Chem. Commun , pp. 353
    • Kan, T.1    Fukuyama, T.2
  • 24
    • 38049036289 scopus 로고    scopus 로고
    • For recent reviews of asymmetric desymmetrization, see: a
    • For recent reviews of asymmetric desymmetrization, see: (a) Rendler, S.; Ostreich, M. Angew. Chem., Int. Ed. 2008, 47, 248.
    • (2008) Angew. Chem., Int. Ed , vol.47 , pp. 248
    • Rendler, S.1    Ostreich, M.2
  • 25
    • 84889419927 scopus 로고    scopus 로고
    • Recent Advances in Catalytic Asymmetric Desymmetrization Reactions
    • Mikami, K, Lautens, M, Eds, John Wiley & Sons, Inc, Hoboken, NJ
    • (b) Rovis, T. Recent Advances in Catalytic Asymmetric Desymmetrization Reactions. In New Frontiers in Asymmetric Catalysis; Mikami, K., Lautens, M., Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, 2007; pp 275-311.
    • (2007) New Frontiers in Asymmetric Catalysis , pp. 275-311
    • Rovis, T.1
  • 31
    • 1842789167 scopus 로고    scopus 로고
    • For an experimentally derived model for stereoselectivity in the oxidative kinetic resolution of benzylic alcohols catalyzed by Pd-(sparteine)Cl2, see: Trend, R. M, Stoltz, B. M J. Am. Chem. Soc. 2004, 126, 4482
    • 2, see: Trend, R. M.; Stoltz, B. M J. Am. Chem. Soc. 2004, 126, 4482.
  • 37
    • 40749112373 scopus 로고    scopus 로고
    • For total syntheses of aurantioclavine, see: a
    • For total syntheses of aurantioclavine, see: (a) Somei, M.; Yamada, F. Heterocycles 2007, 74, 943.
    • (2007) Heterocycles , vol.74 , pp. 943
    • Somei, M.1    Yamada, F.2
  • 44
    • 4243882699 scopus 로고
    • PCT Int. Appl. 106019w, 1991
    • For discussions of the biological activity of the isopavine alkaloids, see: a
    • For discussions of the biological activity of the isopavine alkaloids, see: (a) Weber, E.; Keana, J.; Barmettler, P. PCT Int. Appl. 106019w, 1991; Chem. Abstr. 1991, 115, 106019w.
    • (1991) Chem. Abstr , vol.115
    • Weber, E.1    Keana, J.2    Barmettler, P.3
  • 45
    • 53849102787 scopus 로고    scopus 로고
    • Childers, W. E.; Abou-Gharbia, M. A. U.S. Patent 4,940,789, 1990; Chem. Abstr. 1990, 113, 191190w.
    • (b) Childers, W. E.; Abou-Gharbia, M. A. U.S. Patent 4,940,789, 1990; Chem. Abstr. 1990, 113, 191190w.
  • 46
    • 0001528330 scopus 로고
    • Pavine and Isopavine Alkaloids
    • For selected syntheses of isopavine alkaloids, see: a, Brossi, A, Ed, Academic Press: New York
    • For selected syntheses of isopavine alkaloids, see: (a) Gözler, B. Pavine and Isopavine Alkaloids. In The Alkaloids; Brossi, A., Ed.; Academic Press: New York, 1987; Vol. 31, pp 343-356.
    • (1987) The Alkaloids , vol.31 , pp. 343-356
    • Gözler, B.1
  • 53
    • 33748480130 scopus 로고    scopus 로고
    • For our preliminary communication of the enantioselective synthesis of, -amurensinine, see
    • For our preliminary communication of the enantioselective synthesis of (+)-amurensinine, see: Tambar, U. K.; Ebner, D. C.; Stoltz, B. M. J. Am. Chem. Soc. 2006, 128, 11752.
    • (2006) J. Am. Chem. Soc , vol.128 , pp. 11752
    • Tambar, U.K.1    Ebner, D.C.2    Stoltz, B.M.3
  • 54
    • 4644296823 scopus 로고    scopus 로고
    • For a review of chemistry and biology of the Lobelia alkaloids, see: Felpin, F.-X.; Lebreton, J. Tetrahedron 2004, 60, 10127.
    • For a review of chemistry and biology of the Lobelia alkaloids, see: Felpin, F.-X.; Lebreton, J. Tetrahedron 2004, 60, 10127.
  • 55
    • 84882395728 scopus 로고
    • For syntheses of racemic (±)-lobeline, see: a
    • For syntheses of racemic (±)-lobeline, see: (a) Wieland, H.; Drishaus, I. Annalen 1929, 473, 102.
    • (1929) Annalen , vol.473 , pp. 102
    • Wieland, H.1    Drishaus, I.2
  • 60
    • 53849104944 scopus 로고    scopus 로고
    • For an X-ray crystallography study of (-)-lobeline salts, see: Glaser, R.; Hug, P.; Drouin, M.; Michael, A. J. Chem. Soc., Perkin Trans. 2 1992, 1071.
    • (f) For an X-ray crystallography study of (-)-lobeline salts, see: Glaser, R.; Hug, P.; Drouin, M.; Michael, A. J. Chem. Soc., Perkin Trans. 2 1992, 1071.
  • 61
    • 4644271993 scopus 로고
    • For a study of the biosynthesis of, -lobeline, see
    • (g) For a study of the biosynthesis of (-)-lobeline, see: Keogh, M. F.; O'Donovan, D. G. J. Chem. Soc. 1970, 2470.
    • (1970) J. Chem. Soc , pp. 2470
    • Keogh, M.F.1    O'Donovan, D.G.2
  • 66
    • 53849110459 scopus 로고    scopus 로고
    • The epimerization at C(3) is believed to be a base-catalyzed equilibration via transient retro-conjugate addition intermediate 19. See also refs 19a, 19b, and 19d. (Chemical Equation Presented)
    • The epimerization at C(3) is believed to be a base-catalyzed equilibration via transient retro-conjugate addition intermediate 19. See also refs 19a, 19b, and 19d. (Chemical Equation Presented)
  • 67
    • 0242705214 scopus 로고    scopus 로고
    • For enantioselective syntheses of, )-lobeline, see: a
    • For enantioselective syntheses of (-)-lobeline, see: (a) Compere, D.; Marazano, C.; Das, B. C. J. Org. Chem. 1999, 64, 4528.
    • (1999) J. Org. Chem , vol.64 , pp. 4528
    • Compere, D.1    Marazano, C.2    Das, B.C.3
  • 69
    • 53849146918 scopus 로고    scopus 로고
    • Klingler, F.-D, Sobotta, R, Boehringer Ingelheim, U.S. Patent 2006014791, 2006
    • (c) Klingler, F.-D.; Sobotta, R. (Boehringer Ingelheim). U.S. Patent 2006014791, 2006.
  • 72
  • 73
    • 53849109010 scopus 로고    scopus 로고
    • Logar, C.; Mesicek, M.; Perpar, M.; Seles, E. Farm. Vestn. 1974, 21; Chem. Abstr. 1975, 82, 81926h.
    • (c) Logar, C.; Mesicek, M.; Perpar, M.; Seles, E. Farm. Vestn. 1974, 21; Chem. Abstr. 1975, 82, 81926h.
  • 74
    • 53849118297 scopus 로고    scopus 로고
    • Krasnov, E. A.; Petrova, L. V.; Bekker, E. F. Khim. Prir. Soedin. 1977, 585; Chem. Abstr. 1977, 87, 164249k.
    • (d) Krasnov, E. A.; Petrova, L. V.; Bekker, E. F. Khim. Prir. Soedin. 1977, 585; Chem. Abstr. 1977, 87, 164249k.
  • 75
    • 85145868659 scopus 로고    scopus 로고
    • For a review of syntheses of the Sedum alkaloids, see: (a) Bates, R. W.; Sa-Ei, K. Tetrahedron 2002, 58, 5957.
    • For a review of syntheses of the Sedum alkaloids, see: (a) Bates, R. W.; Sa-Ei, K. Tetrahedron 2002, 58, 5957.
  • 76
    • 42049097195 scopus 로고    scopus 로고
    • For recent syntheses of either enantiomer of sedamine, see: b
    • For recent syntheses of either enantiomer of sedamine, see: (b) Bates, R. W.; Nemeth, J. A.; Snell, R. H. Synthesis 2008, 1033.
    • (2008) Synthesis , pp. 1033
    • Bates, R.W.1    Nemeth, J.A.2    Snell, R.H.3
  • 86
    • 22544456259 scopus 로고    scopus 로고
    • Others have disclosed similar aryne insertions since our initial report, see: b
    • Others have disclosed similar aryne insertions since our initial report, see: (b) Yoshida, H.; Watanabe, M.; Ohshita, J.; Kunai, A. Chem. Commun. 2005, 3292.
    • (2005) Chem. Commun , pp. 3292
    • Yoshida, H.1    Watanabe, M.2    Ohshita, J.3    Kunai, A.4
  • 90
    • 85050296727 scopus 로고    scopus 로고
    • The selectivity factor, s, for kinetic resolution is defined as the ratio of the rate of reaction of the fast-reacting enantiomer of the racemic substrate, kfast, to the rate of reaction of the slow-reacting enantiomer, kslow, in the same transformation, i.e, s, kfast/kslow, The selectivity factor can be expressed in terms of enantiomeric excess (ee) of the remaining alcohol and the conversion (c) of the alcohol to the corresponding ketone, i.e, s, ln[(1- c)(1-ee)]/ln[(1- c)1 +ee, For s > 10, synthetically useful quantities of enantioenriched alcohol can be accessed. For example, an oxidative kinetic resolution with s, 10 at 62% conversion would afford recovery of alcohol of 90% ee. See also: Kagan, H. B, Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L, Ed, Wiley & Sons: New York, 1988; 18, pp 249-330
    • slow). The selectivity factor can be expressed in terms of enantiomeric excess (ee) of the remaining alcohol and the conversion (c) of the alcohol to the corresponding ketone, i.e., s = ln[(1- c)(1-ee)]/ln[(1- c)(1 +ee)]. For s > 10, synthetically useful quantities of enantioenriched alcohol can be accessed. For example, an oxidative kinetic resolution with s = 10 at 62% conversion would afford recovery of alcohol of 90% ee. See also: Kagan, H. B., Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L., Ed.; Wiley & Sons: New York, 1988; Vol. 18, pp 249-330.
  • 93
    • 84985570392 scopus 로고
    • For reviews of the Stille cross-coupling reaction, see: a
    • For reviews of the Stille cross-coupling reaction, see: (a) Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
    • (1986) Angew. Chem., Int. Ed. Engl , vol.25 , pp. 508
    • Stille, J.K.1
  • 99
    • 53849097889 scopus 로고    scopus 로고
    • See Supporting Information for details
    • See Supporting Information for details.
  • 108
    • 52049096917 scopus 로고    scopus 로고
    • We have recently accomplished a formal synthesis of the naturally occurring enantiomer of amurensinine using a readily accessible diamine ligand that serves as a mimic for, -sparteine in the oxidative kinetic resolution. See: Ebner, D. C, Trend, R. M, Genet, C, McGrath, M. J, O'Brien, P, Stoltz, B. M Angew. Chem, Int. Ed. 2008, 47, 6367-6370
    • We have recently accomplished a formal synthesis of the naturally occurring enantiomer of amurensinine using a readily accessible diamine ligand that serves as a mimic for (+)-sparteine in the oxidative kinetic resolution. See: Ebner, D. C.; Trend, R. M.; Genet, C.; McGrath, M. J.; O'Brien, P.; Stoltz, B. M Angew. Chem., Int. Ed. 2008, 47, 6367-6370.
  • 110
    • 0001412059 scopus 로고    scopus 로고
    • A rationale for the observed selectivity follows from the calculated conformational equilibria of cis,cis-1,4-cyclooctadiene. See: Anet, F. A. L.; Yavari, I. J. Am. Chem. Soc. 1977, 99, 6986. Also see Supporting Information for a stereochemical model.
    • A rationale for the observed selectivity follows from the calculated conformational equilibria of cis,cis-1,4-cyclooctadiene. See: Anet, F. A. L.; Yavari, I. J. Am. Chem. Soc. 1977, 99, 6986. Also see Supporting Information for a stereochemical model.
  • 112
    • 53849116296 scopus 로고    scopus 로고
    • The enantiomeric excess was determined after derivatization of lobeline by the method described in ref 21h. See Supporting Information for details
    • The enantiomeric excess was determined after derivatization of lobeline by the method described in ref 21h. See Supporting Information for details.
  • 113
    • 53849089778 scopus 로고    scopus 로고
    • Crooks and co-workers21h noted the rate of epimerization of diastereomerically pure cis-lobeline to 46:54 cis:trans-lobeline in various deuterated solvents by 1H NMR (CD3OD > CD3CN > CD3COCD3 > CDCl3, In our hands, the epimerization of diastereomerically pure cis-lobeline to 1:1 cis:trans-lobeline was much slower in C6D6 (5 days) as opposed to CDCl3 (2 days) and CD3OD 2 h
    • 3OD (2 h).


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