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Volumn 48, Issue 3, 2009, Pages 559-563

Catalyzed dehydrogenative coupling of primary alcohols with water, methanol, or amines

Author keywords

Alcohols; Amines; Density functional calculations; Homogeneous catalysis; Rhodium

Indexed keywords

AMIDES; AMINATION; AMINES; CARBOXYLATION; CARBOXYLIC ACIDS; CATALYSIS; CHEMICAL REACTIONS; HYDROGEN; METAL WORKING; METHANOL; ORGANIC ACIDS; ORGANIC COMPOUNDS; REACTION KINETICS; RHODIUM;

EID: 58249100147     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200804757     Document Type: Article
Times cited : (465)

References (31)
  • 1
    • 58249111511 scopus 로고    scopus 로고
    • K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 4th compl. rev.ed., Wiley-VCH, Weinheim, 2003.
    • K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 4th compl. rev.ed., Wiley-VCH, Weinheim, 2003.
  • 7
    • 0344893535 scopus 로고    scopus 로고
    • for catalytic systems capable of dehydrogenating alcohols to symmetrical esters in the presence of a suitable hydrogen acceptor, see: c Y. Blum, Y. Shvo, J. Organomet. Chem. 1985, 282, C7;
    • for catalytic systems capable of dehydrogenating alcohols to symmetrical esters in the presence of a suitable hydrogen acceptor, see: c) Y. Blum, Y. Shvo, J. Organomet. Chem. 1985, 282, C7;
  • 13
    • 54949099698 scopus 로고    scopus 로고
    • for a recent example with oxygen as the hydrogen acceptor, see i
    • for a recent example with oxygen as the hydrogen acceptor, see i) S. Arita, T. Koike, Y. Kayaki, T. Ikariya, Chem. Asian. J. 2008, 3, 1479.
    • (2008) Chem. Asian. J , vol.3 , pp. 1479
    • Arita, S.1    Koike, T.2    Kayaki, Y.3    Ikariya, T.4
  • 21
    • 0000787564 scopus 로고    scopus 로고
    • Oxidation potentials of aldehydes and ketones: a H. Adkins, R. M. Elofson, A. G. Rossow, C. C. Robinson, J. Am. Chem. Soc. 1949, 71, 3622;
    • Oxidation potentials of aldehydes and ketones: a) H. Adkins, R. M. Elofson, A. G. Rossow, C. C. Robinson, J. Am. Chem. Soc. 1949, 71, 3622;
  • 22
    • 28244483158 scopus 로고    scopus 로고
    • for other successful applications of cyclohexanone as hydrogen acceptor, see: b
    • for other successful applications of cyclohexanone as hydrogen acceptor, see: b) G. R. A. Adair, J. M. J. Williams, Chem. Commun. 2005, 5578;
    • (2005) Chem. Commun , pp. 5578
    • Adair, G.R.A.1    Williams, J.M.J.2
  • 24
    • 33846125646 scopus 로고    scopus 로고
    • We refined the protocol given by H. Rohit Ingle, N. K. Kala Raj, P. Manikandan, J. Mol. Catal. A 2007, 262, 52 and obtained excellent yields (see the Supporting Information for details).
    • We refined the protocol given by H. Rohit Ingle, N. K. Kala Raj, P. Manikandan, J. Mol. Catal. A 2007, 262, 52 and obtained excellent yields (see the Supporting Information for details).
  • 25
    • 58249112204 scopus 로고    scopus 로고
    • The dehydrogenation of primary alcohols to methyl esters under harsh reaction conditions using crotonitrile was described: N. A. Owston, A. J. Parker, J. M. J. Williams, Chem. Commun. 2008, 624
    • The dehydrogenation of primary alcohols to methyl esters under harsh reaction conditions using crotonitrile was described: N. A. Owston, A. J. Parker, J. M. J. Williams, Chem. Commun. 2008, 624.
  • 27
    • 58249121658 scopus 로고    scopus 로고
    • This coupling reaction proceeds with high efficiency because catalyst 2 converts methanol very slowly into methylformate. The initial step, the dehydrogenation of MeOH into formaldehyde, is significantly thermodynamically less favorable than the dehydrogenation of higher alcohols (RCH2OH, to their corresponding aldehydes see also reference [7
    • 2OH), to their corresponding aldehydes (see also reference [7]).
  • 28
    • 58249106813 scopus 로고    scopus 로고
    • R. D. Gaussian 03, M. J. Frisch et al., see the Supporting Information.
    • R. D. Gaussian 03, M. J. Frisch et al., see the Supporting Information.
  • 30
    • 58249124427 scopus 로고    scopus 로고
    • The mechanism of the reaction between the amino hydride e and hydrogen acceptor A is simply given by the counter-clockwise reading of the catalytic cycle, that is, e→d→c→b→a in Scheme 3.
    • The mechanism of the reaction between the amino hydride e and hydrogen acceptor A is simply given by the counter-clockwise reading of the catalytic cycle, that is, e→d→c→b→a in Scheme 3.
  • 31
    • 58249100009 scopus 로고    scopus 로고
    • 3 (1 mol%) and is complete in 10 minutes at room temperature. Benzaldehyde (3 M) in MeOH was used. One equivalent of benzaldehyde served as the hydrogen acceptor.
    • 3 (1 mol%) and is complete in 10 minutes at room temperature. Benzaldehyde (3 M) in MeOH was used. One equivalent of benzaldehyde served as the hydrogen acceptor.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.