메뉴 건너뛰기




Volumn 48, Issue 3, 2009, Pages 547-550

Catalytic enantioselective silylation of acyclic and cyclic triols: Application to total syntheses of cleroindicins D, F, and C

Author keywords

Enantioselectivity; Homogeneous catalysis; Natural products; Silanes; Total synthesis

Indexed keywords

CATALYSIS; CHEMICAL REACTIONS; ELECTRON TRANSITIONS; ENANTIOSELECTIVITY; ETHERS; REACTION KINETICS; SILANES;

EID: 58249117807     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200805338     Document Type: Article
Times cited : (87)

References (26)
  • 1
    • 53549101406 scopus 로고    scopus 로고
    • For an application of enantioselective catalysis to site- and enantioselective synthesis, see
    • For an application of enantioselective catalysis to site- and enantioselective synthesis, see: C. A. Lewis, S. J. Miller, Angew. Chem. 2006, 118, 5744-5747;
    • (2006) Angew. Chem , vol.118 , pp. 5744-5747
    • Lewis, C.A.1    Miller, S.J.2
  • 2
    • 33748581386 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 5616-5619.
    • (2006) Angew. Chem. Int. Ed , vol.45 , pp. 5616-5619
  • 3
    • 53849095853 scopus 로고    scopus 로고
    • For copper-catalyzed enantioselective benzoylation reactions of 1,2,3-triols, see: a
    • For copper-catalyzed enantioselective benzoylation reactions of 1,2,3-triols, see: a) B. Jung, M. S. Hong, S. H. Kang, Angew. Chem. 2007, 119, 2670-2672;
    • (2007) Angew. Chem , vol.119 , pp. 2670-2672
    • Jung, B.1    Hong, M.S.2    Kang, S.H.3
  • 4
    • 34250886944 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2007, 46, 2616-2618;
    • (2007) Angew. Chem. Int. Ed , vol.46 , pp. 2616-2618
  • 6
    • 33748413162 scopus 로고    scopus 로고
    • For previous reports regarding catalytic enantioselective silylation reactions, see: a
    • For previous reports regarding catalytic enantioselective silylation reactions, see: a) Y. Zhao, J. Rodrigo, A. H. Hoveyda, M. L. Snapper, Nature 2006, 443, 67-70;
    • (2006) Nature , vol.443 , pp. 67-70
    • Zhao, Y.1    Rodrigo, J.2    Hoveyda, A.H.3    Snapper, M.L.4
  • 8
    • 36148978554 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2007, 46, 8471-8474.
    • (2007) Angew. Chem. Int. Ed , vol.46 , pp. 8471-8474
  • 9
    • 57649166595 scopus 로고    scopus 로고
    • For an overview of enantioselective silylation processes, see
    • For an overview of enantioselective silylation processes, see: S. Rendler, M. Oestreich, Angew. Chem. 2008, 120, 254-257;
    • (2008) Angew. Chem , vol.120 , pp. 254-257
    • Rendler, S.1    Oestreich, M.2
  • 10
    • 38049036289 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 248-250.
    • (2008) Angew. Chem. Int. Ed , vol.47 , pp. 248-250
  • 11
    • 4444276636 scopus 로고    scopus 로고
    • Catalytic enantioselective dihydroxylations of cyclic allylic alcohols afford the derived anti diastereomers. See: H. C. Kolb, M. S. VanNieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483-2547.
    • Catalytic enantioselective dihydroxylations of cyclic allylic alcohols afford the derived anti diastereomers. See: H. C. Kolb, M. S. VanNieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483-2547.
  • 12
    • 0037111592 scopus 로고    scopus 로고
    • Hydroxy-directed dihydroxylation reactions of cyclic allylic alcohols afford meso triols diastereoselectively. See: T. J. Donohoe, K. Blades, P. R. Moore, M. J. Waring, J. J. G. Winter, M. Helliwell, N. J. Newcombe, G. Stemp, J. Org. Chem. 2002, 67, 7946-7956.
    • Hydroxy-directed dihydroxylation reactions of cyclic allylic alcohols afford meso triols diastereoselectively. See: T. J. Donohoe, K. Blades, P. R. Moore, M. J. Waring, J. J. G. Winter, M. Helliwell, N. J. Newcombe, G. Stemp, J. Org. Chem. 2002, 67, 7946-7956.
  • 14
    • 36849014341 scopus 로고    scopus 로고
    • For a total synthesis of rac-cleroindicin D, culminating in a structural revision of the natural product, see: S. Barradas, M. C. Carreño, M. González-López, A. Latorre, A. Urbano, Org. Lett. 2007, 9, 5019-5022.
    • For a total synthesis of rac-cleroindicin D, culminating in a structural revision of the natural product, see: S. Barradas, M. C. Carreño, M. González-López, A. Latorre, A. Urbano, Org. Lett. 2007, 9, 5019-5022.
  • 15
    • 58249116514 scopus 로고    scopus 로고
    • For details regarding preparation of triol substrates, see the Supporting Information
    • For details regarding preparation of triol substrates, see the Supporting Information.
  • 16
    • 58249117603 scopus 로고    scopus 로고
    • Varying amounts of bis-silylation products are formed in reactions involving substrates that bear a smaller substituent at the central carbinol unit. For example, 8, 32, and 36% bissilyl product is isolated from the transformations shown in entries 3, 7, and 8 of Table 1, respectively. Such bis-silylations increase the enantiomeric purity of the chiral monosilyl products
    • Varying amounts of bis-silylation products are formed in reactions involving substrates that bear a smaller substituent at the central carbinol unit. For example, 8%, 32%, and 36% bissilyl product is isolated from the transformations shown in entries 3, 7, and 8 of Table 1, respectively. Such bis-silylations increase the enantiomeric purity of the chiral monosilyl products.
  • 17
    • 0034805351 scopus 로고    scopus 로고
    • For enantioselective syntheses of a related cyclohexane-based triols by enzymatic resolution of meso-2-(2-propynyl)cyclohexane-1,2,3-triol, see: T. Matsumoto, T. Konegawa, H. Yamaguchi, T. Nakamura, T. Sugai, K. Suzuki, Synlett 2001, 1650-1652.
    • For enantioselective syntheses of a related cyclohexane-based triols by enzymatic resolution of meso-2-(2-propynyl)cyclohexane-1,2,3-triol, see: T. Matsumoto, T. Konegawa, H. Yamaguchi, T. Nakamura, T. Sugai, K. Suzuki, Synlett 2001, 1650-1652.
  • 18
    • 58249117693 scopus 로고    scopus 로고
    • It should be noted that 15% of bis-silylated product is also obtained in the enantioselective silylation of 1,2,3-triol 16; this byproduct is easily removed by using silica gel chromatography. Such a process serves as a correcting mechanism in the catalytic process to remove the minor product enantiomer
    • It should be noted that 15% of bis-silylated product is also obtained in the enantioselective silylation of 1,2,3-triol 16; this byproduct is easily removed by using silica gel chromatography. Such a process serves as a "correcting" mechanism in the catalytic process to remove the minor product enantiomer.
  • 19
    • 0007673575 scopus 로고
    • For enantioselective syntheses of cyclohexane-1,2,3-triols through enzymatic kinetic resolution, see
    • For enantioselective syntheses of cyclohexane-1,2,3-triols through enzymatic kinetic resolution, see: L. Dumortier, J. Van der Eycken, M. Vandewalle, Tetrahedron Lett. 1989, 30, 3201-3204.
    • (1989) Tetrahedron Lett , vol.30 , pp. 3201-3204
    • Dumortier, L.1    Van der Eycken, J.2    Vandewalle, M.3
  • 22
    • 58249109408 scopus 로고    scopus 로고
    • In the presence of 30 mol% 1 (0 8C) and after 72 h of reaction time, silyl ether 19 is isolated in 32% yield and 98.5:1.5 e.r, 97% ee
    • In the presence of 30 mol% 1 (0 8C) and after 72 h of reaction time, silyl ether 19 is isolated in 32% yield and 98.5:1.5 e.r. (97% ee).
  • 25
    • 0000458209 scopus 로고
    • For a review of hydroxyl-directed epoxidations, see:b
    • For a review of hydroxyl-directed epoxidations, see:b) A. H. Hoveyda, D. A. Evans, G. C. Fu, Chem. Rev. 1993, 93, 1307-1370.
    • (1993) Chem. Rev , vol.93 , pp. 1307-1370
    • Hoveyda, A.H.1    Evans, D.A.2    Fu, G.C.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.