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Volumn , Issue 1, 2007, Pages 75-78

A convenient synthesis of z-allylsilanes with good stereoselectivity promoted by samarium diiodide

Author keywords

Allylsilanes; Diastereoselectivity; Eliminations; Samarium

Indexed keywords

2 CHLOROALDEHYDE DERIVATIVE; ALCOHOL DERIVATIVE; ALDEHYDE DERIVATIVE; SAMARIUM DIIODIDE; SILANE DERIVATIVE; UNCLASSIFIED DRUG; Z ALLYLSILANE DERIVATIVE;

EID: 33846451052     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-958436     Document Type: Article
Times cited : (11)

References (49)
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    • (j) Fleming, I. In Comprehensive Organic Synthesis, Vol. 2; Trost, B. M.; Fleming, I.; Paquette, L. A., Eds.; Pergamon: Oxford, 1991, 563.
    • (1991) Comprehensive Organic Synthesis , vol.2 , pp. 563
    • Fleming, I.1
  • 14
    • 0025029262 scopus 로고
    • For reviews concerning the synthesis of allylsilanes, see
    • (a) For reviews concerning the synthesis of allylsilanes, see: Sarkar, T. K. Synthesis 1990, 969.
    • (1990) Synthesis , pp. 969
    • Sarkar, T.K.1
  • 16
    • 0343011976 scopus 로고    scopus 로고
    • To see some examples of the synthesis of E-allylsilanes: Tanigawa, Y.; Fuse, Y.; Murahashi, S.-I. Tetrahedron Lett. 1982, 23, 557.
    • To see some examples of the synthesis of E-allylsilanes: Tanigawa, Y.; Fuse, Y.; Murahashi, S.-I. Tetrahedron Lett. 1982, 23, 557.
  • 32
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    • α-Chloroaldehydes can be easily obtained, see: Halland, N.; Braunton, A.; Bachmann, S.; Marigo, M.; Jørgensen, K. A. J. Am. Chem. Soc. 2004, 126, 4790.
    • (a) α-Chloroaldehydes can be easily obtained, see: Halland, N.; Braunton, A.; Bachmann, S.; Marigo, M.; Jørgensen, K. A. J. Am. Chem. Soc. 2004, 126, 4790.
  • 33
    • 0000921726 scopus 로고    scopus 로고
    • α-Chlorination of α-alkylated aldehydes was carried out using sulfuryl chloride: Stevens, C. L.; Farkas, E.; Gillis, B. J. Am. Chem. Soc. 1954, 76, 2695.
    • (b) α-Chlorination of α-alkylated aldehydes was carried out using sulfuryl chloride: Stevens, C. L.; Farkas, E.; Gillis, B. J. Am. Chem. Soc. 1954, 76, 2695.
  • 34
    • 33846445199 scopus 로고    scopus 로고
    • General Procedure for the Synthesis of Compounds 3. Trimethylsilylmethyllithium (12 mL, 1.0 M solution in pentane) was added at -85 °C to a solution of the corresponding α-chloroaldehyde 1(10 mmol) in THF (10 mL, After stirring for 2 h, the reaction mixture was quenched by addition of sat. aq NH4Cl (10 mL, Standard work-up provided crude 3-chloro-1-(trimethylsilyl)alkan-2-ols 2. The O-acetylation reaction was carried out by treatment of the corresponding crude 3-chloro-1-(trimethylsilyl) alkan-2-ols 2 (1 mmol) with Et3N (10 mL, Ac2O (10 mL) and a catalytic amount of DMAP (5 mg, The reaction mixture was stirred for 12 h at r.t, then the reaction was quenched with ice-cold H2O 30 mL, The organic material was extracted with CH2Cl2. The combined extracts were dried over Na2SO4 and the solvent was removed under reduced pressure affording compounds 3 which were utiliz
    • 4 and the solvent was removed under reduced pressure affording compounds 3 which were utilized without further purification. Compounds 3 were obtained as a mixture of diastereoisomers (roughly 1:1), after column chromatography (hexane-EtOAc, 5:1).
  • 35
    • 0038561088 scopus 로고    scopus 로고
    • 2 in THF was rapidly obtained by reaction of diiodomethane with samarium powder in the presence of sonic waves: Concellón, J. M.; Rodríguez-Solla, H.; Bardales, E.; Huerta, M. Eur. J. Org. Chem. 2003, 1775.
    • 2 in THF was rapidly obtained by reaction of diiodomethane with samarium powder in the presence of sonic waves: Concellón, J. M.; Rodríguez-Solla, H.; Bardales, E.; Huerta, M. Eur. J. Org. Chem. 2003, 1775.
  • 36
    • 33846453490 scopus 로고    scopus 로고
    • General Procedure for the Synthesis of Allylsilanes 4. A solution of SmI2 (1.2 mmol) in THF (12 mL) was added dropwise, under a nitrogen atmosphere, to a stirred solution of the corresponding starting material 3 (0.4 mmol) at r.t. The reaction mixture was then refluxed for 8 h. After this time, it was quenched with aq HCl (0.1 M, 10 mL, The organic material was extracted with Et2O. The combined extracts were dried over Na2SO4 and the solvent was removed under reduced pressure affording crude compounds 4 which were purified by short-column chromatography (silica gel, pentane as eluent, Spectroscopical data for the compounds 4 which are not described in the literature are given here, Z)-Dodeca-2,11-dienyltrimethylsilane (4d, Rf= 0.83 (pentane, 1H NMR (300 MHz, CDCl3, δ, 5.80 (ddt, J, 17.0, 10.2, 6.7 Hz, 1 H, 5.40-5.32 (m, 1 H, 5.28-5.21 (m, 1 H, 4.98 dd
    • -1.
  • 39
    • 33845281959 scopus 로고    scopus 로고
    • Other six-membered-ring transition-state models have been proposed to explain the selectivity in other reactions of SmI2: (a) Molander, G. A, Etter, J. B, Zinke, P. W. J. Am. Chem. Soc. 1987, 109, 453
    • 2: (a) Molander, G. A.; Etter, J. B.; Zinke, P. W. J. Am. Chem. Soc. 1987, 109, 453.
  • 44
    • 0002068159 scopus 로고
    • To see previous works about the γ-effect of the silicon atom, see: a
    • To see previous works about the γ-effect of the silicon atom, see: (a) Sommer, L. H.; Dorfman, E.; Goldberg, G. M.; Whitmore, F. C. J. Am. Chem. Soc. 1946, 68, 488.
    • (1946) J. Am. Chem. Soc , vol.68 , pp. 488
    • Sommer, L.H.1    Dorfman, E.2    Goldberg, G.M.3    Whitmore, F.C.4
  • 47
    • 33846447358 scopus 로고    scopus 로고
    • This is consistent with other previously reported SmI2- mediated β-elimination methodologies with Z-selectivity see ref. 7-9, So, when aryl-substituted olefins were obtained an enhancement of the E-stereoisomer was observed
    • 2- mediated β-elimination methodologies with Z-selectivity (see ref. 7-9). So, when aryl-substituted olefins were obtained an enhancement of the E-stereoisomer was observed.
  • 48
    • 33846443914 scopus 로고    scopus 로고
    • An isomerization process of the Z-phenyl alkene to the more stable E-isomer cannot be discarded under this reaction conditions
    • An isomerization process of the Z-phenyl alkene to the more stable E-isomer cannot be discarded under this reaction conditions.
  • 49
    • 18444385349 scopus 로고    scopus 로고
    • 2-promoted processes when benzylic radicals are generated: Davies, S. G.; Rodríguez-Solla, H.; Tamayo, J. A.; Cowley, A. R.; Concellón, C.; Garner, A. C.; Parkes, A. L.; Smith, A. D. Org. Biomol. Chem. 2005, 3, 1435.
    • 2-promoted processes when benzylic radicals are generated: Davies, S. G.; Rodríguez-Solla, H.; Tamayo, J. A.; Cowley, A. R.; Concellón, C.; Garner, A. C.; Parkes, A. L.; Smith, A. D. Org. Biomol. Chem. 2005, 3, 1435.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.