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Volumn 64, Issue 8, 2008, Pages 1943-1954

Cp*Ir-catalyzed N-alkylation of amines with alcohols. A versatile and atom economical method for the synthesis of amines

Author keywords

Alcohol; Amine; Hydrogen transfer; Iridium catalyst; N Alkylation

Indexed keywords

ALCOHOL DERIVATIVE; AMINE; ANILINE; ANILINE DERIVATIVE; BENZYL ALCOHOL; BENZYLAMINE; BICARBONATE; CYCLOPENTADIENE DERIVATIVE; DIBENZYLAMINE; DIBUTYLAMINE; IRIDIUM; METHYLANILINE; N (2 OCTYL)BENZYLAMINE; N BENZYL(1 PHENYLETHYL)AMINE; N BENZYLANILINE; N BENZYLPHENETHYLAMINE; N CYCLOHEXYLBENZYLAMINE; N CYCLOHEXYLPHENETHYLAMINE; N METHYLBENZYLAMINE; N OCTYLBENZYLAMINE; N OCTYLPHENETHYLAMINE; N,N DIBENZYLETHYLAMINE; N,N DIBENZYLMETHYLAMINE; N,N DIOCTYLBENZYLAMINE; OCTYLAMINE; PENTAMETHYLCYCLOPENTADIENYL; PHENETHYLAMINE; PYRROLIDINE DERIVATIVE; TOLUENE; TRIBENZYLAMINE; UNCLASSIFIED DRUG;

EID: 38349082294     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2007.11.083     Document Type: Article
Times cited : (294)

References (102)
  • 1
    • 38349045476 scopus 로고    scopus 로고
    • For example, see:
  • 45
    • 38349036441 scopus 로고    scopus 로고
    • Heterogeneously catalyzed reactions are also known.
  • 48
    • 38349079069 scopus 로고    scopus 로고
    • Williams et al. reported iridium- and ruthenium-catalyzed N-alkylation reactions of amines with alcohols under mild conditions, which proceed sufficiently with the use of equimolar amounts of starting materials. However, only primary amines and primary alcohols can be used in their catalytic system.
  • 51
    • 38349066458 scopus 로고    scopus 로고
    • Quite recently, Beller et al. reported a new ruthenium-catalyzed system for the N-alkylation of primary amines under mild conditions, in which both primary and secondary alcohols can be used. However, excess amounts (5 equiv) of alcohols have to be employed in these reactions.
  • 62
    • 38349042514 scopus 로고    scopus 로고
    • note
    • 2 as the catalyst. See Ref 16.
  • 63
    • 38349065615 scopus 로고    scopus 로고
    • note
    • When the reaction was carried out at 110 °C, the yield was 63%.
  • 64
    • 38349042515 scopus 로고    scopus 로고
    • note
    • In the case of the reaction with 1-octanol, a better result was obtained at 90 °C than at 110 °C. When the reaction was carried out at 110 °C, formation of a considerable amount of di-alkylated product (N,N-dioctylbenzylamine) was observed.
  • 65
    • 38349027368 scopus 로고    scopus 로고
    • note
    • 3 (1.0 mol %) at 110 °C for 17 h. In this reaction, the selective formation of N-(4-chlorobenzyl)benzylamine was observed without any formation of N-(4-chlorobenzyl)dibenzylamine. This result indicates that the alkylations of primary amines are sufficiently faster than those of secondary amines, which rationalizes the high selectivity for mono-alkylation of primary amines to secondary amines.
  • 66
    • 38349003324 scopus 로고    scopus 로고
    • note
    • (a) The reaction of pyrrolidine (1.0 mmol) with 1-octanol (1.0 mmol) gave 65% of 1-octylpyrrolidine; (b) The reaction of dibutylamine (1.0 mmol) with 1-butanol (1.0 mmol) at 110 °C gave 72% of tributylamine.
  • 67
    • 38349027367 scopus 로고    scopus 로고
    • note
    • 3 (5.0 mol %) at 110 °C for 17 h gave racemic N-benzyl-(1-phenylethyl)amine in 74% isolated yield. The enantiomeric excess of the product was determined to be <1% by chiral HPLC analysis using a Chiralcel OD-H (Daicel) column. This result also supports that the first stage of the catalytic cycle involves the transitory oxidation of alcohols, which causes racemization.
  • 70
    • 38349004949 scopus 로고    scopus 로고
    • *Ir-catalyzed hydrogen transfer reactions, in which catalytic intermediates are trivalent iridium species.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.