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Volumn 47, Issue 32, 2008, Pages 6045-6048

Highly regio- and stereoselective double Michael addition-cyclization of 2,3-allenoates with organozinc compounds: Efficient synthesis of 5-benzylidenecyclohex-2-enones

Author keywords

Allenes; Cyclization; Esters; Michael addition; Organozinc reagents

Indexed keywords

CHEMICAL COMPOUNDS; CHEMICAL REACTIONS; COMPLEXATION; ORGANOMETALLICS; RAW MATERIALS; STEREOSELECTIVITY; UNSATURATED COMPOUNDS;

EID: 51449113436     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200801497     Document Type: Article
Times cited : (24)

References (30)
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    • for the catalytic enantioselective alkylative aldol reaction of allenic esters and ketones with dialkyl zinc reagents towards the synthesis of functionalized δ-lactones, see: h D. Zhao, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 14440
    • for the catalytic enantioselective alkylative aldol reaction of allenic esters and ketones with dialkyl zinc reagents towards the synthesis of functionalized δ-lactones, see: h) D. Zhao, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 14440.
  • 16
    • 53549124804 scopus 로고    scopus 로고
    • Crystal data for 2a: C26H28O3, Mr, 388.51, monoclinic, P121/c1, Mo Kα, final R indices (I > 2σ(I, R1, 0.0491, wR2, 0.1028, a, 10.4687(8, b, 14.8999(10, c, 14.6133(10) Å, α, 90, β, 103.0580(19, γ, 90°, V, 2220.5(3) Å3, Z, 4, number of reflections measured/unique: 5052/1585 (R int, 0.061, number of observations: 5051 (I > 2σ(I, 291 parameters. CCDC 672093 (2a) and CCDC 672094, 4S,6R)-2c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
    • int = 0.061), number of observations: 5051 (I > 2σ(I)), 291 parameters. CCDC 672093 (2a) and CCDC 672094 ((-)-(4S,6R)-2c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 18
    • 53549104592 scopus 로고    scopus 로고
    • Crystal data for, 4S,6R)-2c: C 26H26Br2O3, Mr, 546.30, monoclinic, P1211, MoKα, final R indices (I > 2σ(I, R1, 0.0635, wR2, 0.1966, a =7.3758(4, b, 24.7978(13, c, 14.0258(7) Å, α, 90, β, 90.2228(14, γ, 90°, V, 2565.4(2) Å3, Z, 4, number of reflections measured/unique: 5956/3461 (Rint, 0.073, number of observations: 5956 (I > 2σI, 561 parameters
    • int = 0.073), number of observations: 5956 (I > 2σ(I)), 561 parameters.
  • 19
    • 34548428596 scopus 로고    scopus 로고
    • For a monograph on carbozincation, see: a, Eds, Z. Rappoport, I. Marek, Wiley, Chichester
    • For a monograph on carbozincation, see: a) E. Lorthiois, C. Meyer, The Chemistry of Organozinc Compounds (Eds.: Z. Rappoport, I. Marek), Wiley, Chichester, 2006, pp. 863-977;
    • (2006) The Chemistry of Organozinc Compounds , pp. 863-977
    • Lorthiois, E.1    Meyer, C.2
  • 20
    • 0008086878 scopus 로고    scopus 로고
    • 2Zn to conjugated alkynes, see: b J. Auger, G. Courtois, L. Miginiac, J. Organomet. Chem. 1977, 133, 285;
    • 2Zn to conjugated alkynes, see: b) J. Auger, G. Courtois, L. Miginiac, J. Organomet. Chem. 1977, 133, 285;
  • 23
    • 84906287738 scopus 로고    scopus 로고
    • for the anti addition of nucleophiles to allenoates, see: e Y. Naruse, S. Kakita, A. Tsunekawa, Synlett 1995, 711.
    • for the anti addition of nucleophiles to allenoates, see: e) Y. Naruse, S. Kakita, A. Tsunekawa, Synlett 1995, 711.
  • 24
    • 0000373915 scopus 로고    scopus 로고
    • In the reported crystal structure of the Reformatsky reagent (BrZnCH 2COOtBu·THF)2, the C-Zn bond was clearly visible: a) J. Dekker, P. H. M. Budzelaar, J. Boersma, G. J. M. van der Kerk, A. L. Spek, Organometallics 1984, 3, 1403;
    • 2, the C-Zn bond was clearly visible: a) J. Dekker, P. H. M. Budzelaar, J. Boersma, G. J. M. van der Kerk, A. L. Spek, Organometallics 1984, 3, 1403;
  • 26
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    • for the configurational stability of organozinc reagents, see
    • for the configurational stability of organozinc reagents, see: S. Klein, I. Marek, J. F. Normant, J. Org. Chem. 1994, 59, 2925.
    • (1994) J. Org. Chem , vol.59 , pp. 2925
    • Klein, S.1    Marek, I.2    Normant, J.F.3
  • 27
    • 53549122600 scopus 로고    scopus 로고
    • We thank one of the referees for suggesting this mechanistic possibility
    • We thank one of the referees for suggesting this mechanistic possibility.
  • 28
    • 53549127419 scopus 로고    scopus 로고
    • The fact that we did not observe the formation of the six-membered product 2 during the studies described in ref. [3] indicates the lower reactivity of magnesium 1,3-dienolates towards 2,3-allenoates.
    • The fact that we did not observe the formation of the six-membered product 2 during the studies described in ref. [3] indicates the lower reactivity of magnesium 1,3-dienolates towards 2,3-allenoates.
  • 29
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    • The reaction of optically active (-)-(R)-2a with RMgBr provided the racemic products of conjugate addition.
    • The reaction of optically active (-)-(R)-2a with RMgBr provided the racemic products of conjugate addition.
  • 30
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    • For an uncatalyzed addition of a dialkyl zinc reagent to 2-alkenoates with a radical mechanism, see
    • For an uncatalyzed addition of a dialkyl zinc reagent to 2-alkenoates with a radical mechanism, see: F. Denes, S. Cutri, A. Perez-Luna, F. Chemla, Chem. Eur. J. 2006, 12, 6506.
    • (2006) Chem. Eur. J , vol.12 , pp. 6506
    • Denes, F.1    Cutri, S.2    Perez-Luna, A.3    Chemla, F.4


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