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Volumn 46, Issue 34, 2007, Pages 6518-6520

Manganese-catalyzed insertion of aldehydes into a C-H bond

Author keywords

Aldehydes; Asymmetric synthesis; C H activation; Manganese; Silyl ethers

Indexed keywords

CATALYST ACTIVITY; CHEMICAL ACTIVATION; CHEMICAL BONDS; ETHERS; MANGANESE COMPOUNDS; SYNTHESIS (CHEMICAL);

EID: 34548356420     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200702256     Document Type: Article
Times cited : (208)

References (27)
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    • For a book of Grignard reactions, see: Grignard Reagents: New Developments (Ed.: H. G. Richey), Wiley, New York, 2000;
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    • Eds, G. S. Silverman, P. E. Rakita, Marcel Dekker, New York
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    • c) G. Dyker, Angew. Chem. 1999, 111, 1808-1822;
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    • Angew. Chem. Int. Ed. 2006, 45, 2766-2768;
    • (2006) Chem. Int. Ed , vol.45 , pp. 2766-2768
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  • 20
    • 0003136878 scopus 로고
    • Nucleophilic addition with fourth-row metal complexes by catalytic C-H activation is still rare. However, there are several examples of the insertion of nonpolar unsaturated molecules initiated by C-H fission with complexes of fourth-row metals, see: a
    • Nucleophilic addition with fourth-row metal complexes by catalytic C-H activation is still rare. However, there are several examples of the insertion of nonpolar unsaturated molecules initiated by C-H fission with complexes of fourth-row metals, see: a) Co: G. Halbritter, F. Knoch, H. Kisch, J. Organomet. Chem. 1995, 492, 87-98;
    • (1995) J. Organomet. Chem , vol.492 , pp. 87-98
    • Co, G.1    Halbritter, F.2
  • 22
    • 34548312812 scopus 로고    scopus 로고
    • Investigation of hydrosilanes: triethylsilane 93%; diethylmethylsilane 59%, dimethylphenylsilane 53%; triphenylsilane 77%. This reaction did not proceed using the following silanes: diphenylsilane, tris(trimethylsilyl)silane, hexamethyldisilane, hexamethyldisilazane.
    • Investigation of hydrosilanes: triethylsilane 93%; diethylmethylsilane 59%, dimethylphenylsilane 53%; triphenylsilane 77%. This reaction did not proceed using the following silanes: diphenylsilane, tris(trimethylsilyl)silane, hexamethyldisilane, hexamethyldisilazane.
  • 23
    • 34548314891 scopus 로고    scopus 로고
    • 4,5-Dihydro-1-methyl-2-phenyl-1H-imidazole 1b also afforded the corresponding silyl ether 6 in 72 % yield. (Chemical Equation Presented)
    • 4,5-Dihydro-1-methyl-2-phenyl-1H-imidazole 1b also afforded the corresponding silyl ether 6 in 72 % yield. (Chemical Equation Presented)
  • 24
    • 34250861182 scopus 로고    scopus 로고
    • For iridium-catalyzed coupling of imidazoles with aldehydes in the presence of a hydrosilane, see
    • For iridium-catalyzed coupling of imidazoles with aldehydes in the presence of a hydrosilane, see: Y. Fukumoto, K. Sawada, M. Hagihara, N. Chatani, S. Murai, Angew. Chem. 2002, 114, 2903-2905;
    • (2002) Angew. Chem , vol.114 , pp. 2903-2905
    • Fukumoto, Y.1    Sawada, K.2    Hagihara, M.3    Chatani, N.4    Murai, S.5
  • 25
    • 0037008168 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2002, 41, 2779-2781.
    • (2002) Chem. Int. Ed , vol.41 , pp. 2779-2781
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  • 26
    • 0040565867 scopus 로고    scopus 로고
    • Another possibility is that the reaction is catalyzed by only a manganese(I) species. There has been a report on the formation of manganese(I) complex 10 by treatment of 1a with [Mn-(CH3)(CO) 5, see: A. Suárez, J. M. Vila, M. T. Pereira, E. Gayoso, M. Gayoso, J. Organomet. Chem. 1987, 335, 359-363. We examined the reaction between 1a, 2a, and 4 using [Mn-(CH 3)(CO)5] as a catalyst. We found that the reaction proceeded, and 5a was obtained in 85% yield. This result indicates that the active species of the reaction would be Mn1. However, in the reaction reported herein, the active species derived from [MnBr(CO)5] will not be the same as that derived from [Mn(CH3)(CO)5, Therefore, it is still not clear whether the real active species is Mn(I) or Mn(III, and further investigation is required, Chemical Equation Presented) Mn(CO)4 10
    • 5]. Therefore, it is still not clear whether the real active species is Mn(I) or Mn(III), and further investigation is required. (Chemical Equation Presented) Mn(CO)4 10
  • 27
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    • For an example of transition-metal-catalyzed enantioselective functionalization via C-H bond activation, see: S. J. O'Malley, K. L. Tan, A. Watzke, R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2005, 127, 13496-13497
    • For an example of transition-metal-catalyzed enantioselective functionalization via C-H bond activation, see: S. J. O'Malley, K. L. Tan, A. Watzke, R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2005, 127, 13496-13497.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.