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Advanced Synthesis and Catalysis
Volumn 353, Issue 7, 2011, Pages 1161-1168
N-alkylation of amines with alcohols catalyzed by a water-soluble cp*iridium complex: An efficient method for the synthesis of amines in aqueous media
Author keywords

alcohols; alkylation; amines; iridium; water soluble catalyst
Indexed keywords

EID: 79955923751     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201000962     Document Type: Article
Times cited : (219)
References (90)
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    • in:, (Eds.: L.A. Oro, C. Claver), Wiley-VCH, Weinheim, Germany, Chapter, pp
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    • Fujita, K.1    Yamaguchi, R.2
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    • For recent reviews on organic reactions in aqueous media, see A. Chanda, V. V. Fokin, Chem. Rev. 2009, 109, 725-748
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    • Chanda, A.1    Fokin, V.V.2
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    • [10a,10b]). The alkylation of primary amines with primary alcohols in water has been achieved in good to high yields, while the scope of the catalytic system seems to be rather limited, and the alkylation of secondary amines in water resulted in lower yields.
    • [10a,10b]). The alkylation of primary amines with primary alcohols in water has been achieved in good to high yields, while the scope of the catalytic system seems to be rather limited, and the alkylation of secondary amines in water resulted in lower yields.
  • 70
    • 79955910966 scopus 로고    scopus 로고
    • -) as a counteranion among the catalysts 1 - 3 could be attributed to the differences of activities for the transfer hydrogenation of the iminic intermediate (see the plausible mechanism shown in Scheme2). There have been many examples that iodide exhibits a positive effect in the transition metal-catalyzed hydrogenation of imines
    • -) as a counteranion among the catalysts 1-3 could be attributed to the differences of activities for the transfer hydrogenation of the iminic intermediate (see the plausible mechanism shown in Scheme2). There have been many examples that iodide exhibits a positive effect in the transition metal-catalyzed hydrogenation of imines
  • 74
  • 77
  • 82
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    • A similar amide-alkoxide exchange reaction for Cp Ir complexes has been reported by Bergman.
    • A similar amide-alkoxide exchange reaction for Cp*Ir complexes has been reported by Bergman:, D. S. Glueck, L. J. N. Winslow, R. G. Bergman, Organometallics 1991, 10, 1462-1479.
    • (1991) Organometallics , vol.10 , pp. 1462-1479
    • Glueck, D.S.1    Winslow, L.J.N.2    Bergman, R.G.3
  • 83
    • 79955920834 scopus 로고    scopus 로고
    • In the present reaction, the catalytic intermediates would be Ir(III) species. There are many examples of Cp Ir-catalyzed hydrogen transfer reactions in which catalytic intermediates are trivalent iridium species
    • In the present reaction, the catalytic intermediates would be Ir(III) species. There are many examples of Cp*Ir-catalyzed hydrogen transfer reactions in which catalytic intermediates are trivalent iridium species
  • 88
    • 79955907144 scopus 로고    scopus 로고
    • We also carried out the reaction of benzylamine (4h) with a chiral secondary alcohol: the reaction of 4h (2.0mmol) with (S)-1-phenylethanol (2.0mmol) in the presence of 3 (3.0mol%) in water under reflux for 14h gave racemic N-benzyl-1-phenylethylamine (<1% ee) in 70% isolated yield. This result obviously indicates that the first stage of the catalytic cycle involves the dehydrogenative oxidation of an alcohol giving transiently an achiral carbonyl compound, which causes racemization.
    • We also carried out the reaction of benzylamine (4h) with a chiral secondary alcohol: the reaction of 4h (2.0mmol) with (S)-1-phenylethanol (2.0mmol) in the presence of 3 (3.0mol%) in water under reflux for 14h gave racemic N-benzyl-1-phenylethylamine (<1% ee) in 70% isolated yield. This result obviously indicates that the first stage of the catalytic cycle involves the dehydrogenative oxidation of an alcohol giving transiently an achiral carbonyl compound, which causes racemization.
  • 89
    • 79955896808 scopus 로고    scopus 로고
    • 1HNMR revealed the formation of the reaction intermediates; benzaldehyde (9%), N-benzylideneaniline (6%), and the product N-benzylaniline (8%) along with a hydrido-iridium complex (δ=-13.15), supporting the proposed mechanism shown in Scheme2.
    • 1HNMR revealed the formation of the reaction intermediates; benzaldehyde (9%), N-benzylideneaniline (6%), and the product N-benzylaniline (8%) along with a hydrido-iridium complex (δ=-13.15), supporting the proposed mechanism shown in Scheme2.

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