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Volumn 130, Issue 48, 2008, Pages 16146-16147

Asymmetric reductive Mannich reaction to ketimines catalyzed by a Cu(I) complex

Author keywords

[No Author keywords available]

Indexed keywords

BETA AMINO ACID; COPPER COMPLEX; IMINE; KETIMINE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 57149101142     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8069727     Document Type: Article
Times cited : (116)

References (36)
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    • (a) A general diastereoselective enolate addition to chiral sulfinyl imines: Tang, T. P.; Ellman, J. A. J. Org. Chem. 2002, 67, 7819.
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    • An asymmetric Mannich-type reaction to ketone-derived N-acyl hydrazones using a stoichiometric chiral promoter: Notte, G. T, Leighton, J. L. J. Am. Chem. Soc. 2008, 130, 6676
    • (b) An asymmetric Mannich-type reaction to ketone-derived N-acyl hydrazones using a stoichiometric chiral promoter: Notte, G. T.; Leighton, J. L. J. Am. Chem. Soc. 2008, 130, 6676.
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    • A diastereoselective [3 + 2] cycloaddition to chiral substrates as an alternative method for the Mannich reaction: Fuller, A. A.; Chen, B.; Minter, A. R.; Mapp, A. K. J. Am. Chem. Soc. 2005, 127, 5376.
    • A diastereoselective [3 + 2] cycloaddition to chiral substrates as an alternative method for the Mannich reaction: Fuller, A. A.; Chen, B.; Minter, A. R.; Mapp, A. K. J. Am. Chem. Soc. 2005, 127, 5376.
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    • An organo-catalyzed asymmetric Mannich reaction between special α-ketimino esters (activated ketimines) and aldehydes; Zhuang, W.; Saaby, S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2004, 43, 4476.
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    • CuOAr-catalyzed direct asymmetric Mannich reaction of ketimines was recently reported: (a) Yazaki, R.; Nitabaru, T.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 14477.
    • CuOAr-catalyzed direct asymmetric Mannich reaction of ketimines was recently reported: (a) Yazaki, R.; Nitabaru, T.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 14477.
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    • For pioneering studies on transmetalation from a silyl enolate to a copper enolate, see: Pagenkopf, B. L.; Krüger, J.; Stojanovic, A.; Carreira, E. M. Angew. Chem., Int. Ed. 1998, 37, 3124.
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    • Transmetalation from silicon enolate to copper enolate is the rate-determining step in the Cu-catalyzed aldol reaction to ketones, and therefore not very efficient: Oisaki, K, Suto, Y, Kanai, M, Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 5644
    • Transmetalation from silicon enolate to copper enolate is the rate-determining step in the Cu-catalyzed aldol reaction to ketones, and therefore not very efficient: Oisaki, K.; Suto, Y.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 5644.
  • 15
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    • This type of copper enolate formation was applied to catalytic asymmetric reductive or alkylative aldol reactions of ketones. For selected examples, see: (a) Lam, H. W, Joensuu, P. M. Org. Lett. 2005, 7, 4225
    • This type of copper enolate formation was applied to catalytic asymmetric reductive or alkylative aldol reactions of ketones. For selected examples, see: (a) Lam, H. W.; Joensuu, P. M. Org. Lett. 2005, 7, 4225.
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    • Reductive Mannich reactions of aldimines: (a) Nishiyama, H.; Ishikawa, J.; Shiomi, T. Tetrahedron Lett. 2007, 48, 7841.
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    • Extension to the catalytic asymmetric version has not been reported
    • (e) Muraoka, T.; Kamiya, S.; Matsuda, I.; Itoh, K. Chem. Commun. 2002, 1284. Extension to the catalytic asymmetric version has not been reported.
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    • For the initial stage optimization, see Table S-1 in Supporting Information (SI). N-Phosphinoyl ketimines produced more promising results than N-benzyl and N-toluenesulfonyl ketimines.
    • For the initial stage optimization, see Table S-1 in Supporting Information (SI). N-Phosphinoyl ketimines produced more promising results than N-benzyl and N-toluenesulfonyl ketimines.
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    • For determination of the relative and absolute configuration of the products, see SI
    • For determination of the relative and absolute configuration of the products, see SI.
  • 30
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    • There was no simple and general catalytic method for diastereoselective synthesis of β2,3,3-amino acid derivatives, even in a racemic system
    • 2,3,3-amino acid derivatives, even in a racemic system.
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    • 3SiH (0°C). This sharp difference might be due to switching of the reactive nucleophile (achiral boron enolate vs. chiral copper enolate) depending on the reducing reagents (see SI). The fact that enantiomeric excess of 3ba improved to 56% ee in the presence of pyridine (1.8 equiv: possible deactivator of boron enolate) using PinBH supports this consideration.
    • 3SiH (0°C). This sharp difference might be due to switching of the reactive nucleophile (achiral boron enolate vs. chiral copper enolate) depending on the reducing reagents (see SI). The fact that enantiomeric excess of 3ba improved to 56% ee in the presence of pyridine (1.8 equiv: possible deactivator of boron enolate) using PinBH supports this consideration.
  • 33
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    • In Table 2, entries 6 and 7, no cyclized products such as 4bd were observed.
    • In Table 2, entries 6 and 7, no cyclized products such as 4bd were observed.
  • 34
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    • See SI for more examples of product conversion
    • See SI for more examples of product conversion.
  • 35
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    • Reviews of Cu-catalyzed asymmetric tetrasubstituted carbon construction, see: a
    • Reviews of Cu-catalyzed asymmetric tetrasubstituted carbon construction, see: (a) Shibasaki, M.; Kanai, M. Chem. Rev. 2008, 108, 2853.
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    • Shibasaki, M.1    Kanai, M.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.