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Volumn 48, Issue 39, 2009, Pages 7221-7223

Enantioselective synthesis of (-)-β-Santalol by a copper-catalyzed enynol cyclization-fragmentation reaction

Author keywords

Copper; Cyclopropanes; Enantioselectivity; Fragrances; Rearrangement

Indexed keywords

CYCLOPROPANE RING; CYCLOPROPANES; ENANTIOSELECTIVE SYNTHESIS; FRAGMENTATION REACTIONS; PLATINUM CATALYSTS; REARRANGEMENT;

EID: 70349915725     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200903449     Document Type: Article
Times cited : (43)

References (77)
  • 1
    • 84988122577 scopus 로고
    • For the synthesis of (-)-β-santalol (very strong sandalwood odor) and (+)-β-santalol (odorless) through the use of chiral auxiliaries see
    • a) For the synthesis of (-)-β-santalol (very strong sandalwood odor) and (+)-β-santalol (odorless) through the use of chiral auxiliaries see: A. Krotz, G. Helmchen, Liebigs Ann. Chem. 1994, 601;
    • (1994) Liebigs Ann. Chem , pp. 601
    • Krotz, A.1    Helmchen, G.2
  • 5
    • 0001545486 scopus 로고
    • for the synthesis of (±)-β-santalol, see
    • b) for the synthesis of (±)-β-santalol, see: D. Solas, J. Wolinsky, J. Org. Chem. 1983, 48, 1988;
    • (1983) J. Org. Chem , vol.48 , pp. 1988
    • Solas, D.1    Wolinsky, J.2
  • 10
    • 70349959599 scopus 로고    scopus 로고
    • The wood of Santalum album L. has been overharvested, and the Indian government now bans exportation of this threatened species (2004 IUCN Red List).
    • The wood of Santalum album L. has been overharvested, and the Indian government now bans exportation of this threatened species (2004 IUCN Red List).
  • 14
    • 46749159211 scopus 로고    scopus 로고
    • For reviews on enyne cycloisomerization reactions, see
    • For reviews on enyne cycloisomerization reactions, see: H. C. Shen, Tetrahedron 2008, 64, 7847;
    • (2008) Tetrahedron , vol.64 , pp. 7847
    • Shen, H.C.1
  • 53
  • 56
    • 70349964243 scopus 로고    scopus 로고
    • The copper reagent possibly produces an intermediate of type B with more-localized charges and thus favors the fragmentation pathway. As B and C are two extreme representations of the same intermediate, the ease of fragmentation may also be related to the unlikelihood that a 1,2-R shift would take place in this system (owing to the electrophilicity of the carbenoid).
    • The copper reagent possibly produces an intermediate of type B with more-localized charges and thus favors the fragmentation pathway. As B and C are two extreme representations of the same intermediate, the ease of fragmentation may also be related to the unlikelihood that a 1,2-R shift would take place in this system (owing to the electrophilicity of the carbenoid).
  • 66
    • 70349959583 scopus 로고    scopus 로고
    • 2O) according to
    • 2O) according to:
  • 68
    • 70349950412 scopus 로고    scopus 로고
    • We chose to prepare compounds 8 and 9 by this method based on a known procedure
    • We chose to prepare compounds 8 and 9 by this method based on a known procedure
  • 69
    • 70349937757 scopus 로고
    • G Joachimsmann-Dufresne, as the conditions are neutral (in contrast to acetate pyrolysis), industrially sound (as opposed to mesylate elimination), and high-yielding.
    • (G Joachimsmann-Dufresne, M. Blanchard, Bull. Soc. Chim. Fr. 1968, 385) , as the conditions are neutral (in contrast to acetate pyrolysis), industrially sound (as opposed to mesylate elimination), and high-yielding.
    • (1968) Bull. Soc. Chim. Fr , vol.385
    • Joachimsmann-Dufresne, G.1    Blanchard, M.2
  • 70
    • 70349957850 scopus 로고    scopus 로고
    • Surprisingly, the ee values of 8 and, to a larger extent, 9 were lower than those of 6 and 7, although the diastereomeric ratio remained the same. Compounds 8 and 9 possibly undergo a thermal 1,2-H shift.
    • Surprisingly, the ee values of 8 and, to a larger extent, 9 were lower than those of 6 and 7, although the diastereomeric ratio remained the same. Compounds 8 and 9 possibly undergo a thermal 1,2-H shift.
  • 73
    • 70349941012 scopus 로고    scopus 로고
    • For a long synthesis of (±)-3 of unspecified configuration (8 steps, 13% yield), see
    • For a long synthesis of (±)-3 of unspecified configuration (8 steps, 13% yield), see:
  • 75
    • 70349948698 scopus 로고    scopus 로고
    • 4 in toluene (70°C, 1 h) led to completely selective cyclization-fragmentation; however, the yield was inferior (55%).
    • 4 in toluene (70°C, 1 h) led to completely selective cyclization-fragmentation; however, the yield was inferior (55%).
  • 77
    • 70349957849 scopus 로고    scopus 로고
    • We are presently tackling the longstanding problem that no more general alternative exists for the synthesis of Z trisubstituted allylic alcohols.
    • We are presently tackling the longstanding problem that no more general alternative exists for the synthesis of Z trisubstituted allylic alcohols.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.