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Volumn , Issue 15, 2008, Pages 2295-2298

Catalytic conjugate addition of cyanide to enones: Cooperative catalysis of Ni(0) and Gd(OTf)

Author keywords

Conjugate addition; Cooperative catalysis; Cyanide; Gadolinium; Nickel

Indexed keywords

CYANIDE; ENONE DERIVATIVE; GADOLINIUM; GADOLINIUM TRIFLATE; KETONE DERIVATIVE; NICKEL; OSELTAMIVIR; UNCLASSIFIED DRUG;

EID: 52949150805     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1078264     Document Type: Article
Times cited : (15)

References (33)
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    • Dauben, W. G, Ed, John Wiley and Sons: New York, and references cited therein
    • Nagata, W.; Yoshioka, M. Organic Reactions, Vol. 25; Dauben, W. G., Ed.; John Wiley and Sons: New York, 1977, 255; and references cited therein.
    • (1977) Organic Reactions , vol.25 , pp. 255
    • Nagata, W.1    Yoshioka, M.2
  • 5
    • 43249105812 scopus 로고    scopus 로고
    • We recently developed the first synthetically useful enantioselective conjugate addition of cyanide to enones using a polymetallic Gd catalyst. See: Tanaka, Y, Kanai, M, Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 6072
    • We recently developed the first synthetically useful enantioselective conjugate addition of cyanide to enones using a polymetallic Gd catalyst. See: Tanaka, Y.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 6072.
  • 6
    • 0037448902 scopus 로고    scopus 로고
    • For catalytic enantioselective conjugate addition of cyanide to α,β-unsaturated carboxylic acid derivatives, see: a
    • For catalytic enantioselective conjugate addition of cyanide to α,β-unsaturated carboxylic acid derivatives, see: (a) Sammis, G. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2003, 125, 4442.
    • (2003) J. Am. Chem. Soc , vol.125 , pp. 4442
    • Sammis, G.M.1    Jacobsen, E.N.2
  • 14
    • 52949092676 scopus 로고    scopus 로고
    • 2).
    • 2).
  • 15
    • 52949107133 scopus 로고    scopus 로고
    • 3 in some cases, leading to diminished yields of the 1,4-products. For example, when 2-cyclohepten-1-one (1c) was used as a substrate, the reaction using TMSCN produced a complex mixture, yielding only 40% of the 1,4-addition product. On the other hand, the reaction using TBSCN was clean, yielding 92% of 3c.
    • 3 in some cases, leading to diminished yields of the 1,4-products. For example, when 2-cyclohepten-1-one (1c) was used as a substrate, the reaction using TMSCN produced a complex mixture, yielding only 40% of the 1,4-addition product. On the other hand, the reaction using TBSCN was clean, yielding 92% of 3c.
  • 16
    • 33847633018 scopus 로고    scopus 로고
    • For previous examples of Ni(0) and Lewis acid catalyzed reactions, see: (a) Nakao, Y.; Yada, A.; Ebata, S.; Hiyama, T. J. Am. Chem. Soc. 2007, 129, 2428.
    • For previous examples of Ni(0) and Lewis acid catalyzed reactions, see: (a) Nakao, Y.; Yada, A.; Ebata, S.; Hiyama, T. J. Am. Chem. Soc. 2007, 129, 2428.
  • 21
    • 52949094929 scopus 로고    scopus 로고
    • In the absence of Gd(OTf)3, TBSCN was not an effective nucleophile; the yield of 3b decreased to as low as 6% using TBSCN in the absence of Gd(OTf)3, whereas the yield was 77% using TMSCN in the absence of Gd(OTf)3 Table 3, entry 3
    • 3 (Table 3, entry 3).
  • 22
    • 52949137810 scopus 로고    scopus 로고
    • General Procedure for Ni/Gd(OTf)3-Catalyzed Conjugate Addition of Cyanide to Enones (Table 2, entry 4) The reaction was performed using degassed solvents under Ar atmosphere. To a solution of Ni(cod) 2 (1.7 mg, 0.006 mmol) in THF (0.2 mL, norbornadiene (1.83 μL, 0.018 mmol) was added. Gadolinium triflate (3.6 mg, 0.006 mmol) was added to the mixture, followed by the addition of 2-cyclohexene-1-one (1b: 29.0 μL, 0.30 mmol, Then, TBSCN (63.6 mg, 0.45 mmol) in THF (0.1 mL) was added to start the reaction. After stirring for 1 h, the reaction mixture was directly loaded on SiO2 column (Caution! Highly toxic HCN is generated in this step. This operation should be conducted in a well-ventilated hood, and purified by flash column chromatography (SiO2, Et2O- hexane, 1:20) to afford 3b (62.6 mg, 0.264 mol) in 89% yield
    • 2O- hexane, 1:20) to afford 3b (62.6 mg, 0.264 mol) in 89% yield.
  • 23
    • 46849088854 scopus 로고    scopus 로고
    • For the latest review of Tamiflu synthesis, see
    • For the latest review of Tamiflu synthesis, see: Shibasaki, M.; Kanai, M. Eur. J. Org. Chem. 2008, 1839.
    • (2008) Eur. J. Org. Chem , pp. 1839
    • Shibasaki, M.1    Kanai, M.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.