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1
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38349045476
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6
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Beller M., Trauthwein H., Eichberger M., Breindl C., Herwig J., Müller T.E., and Thiel O.R. Chem.-Eur. J. 5 (1999) 1306
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Müller, T.E.6
Thiel, O.R.7
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11
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2942585374
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Tillack A., Jiao H., Castro I.G., Hartung C.G., and Beller M. Chem.-Eur. J. 10 (2004) 2409
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Tillack, A.1
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20
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0034712156
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Wolfe J.P., Tomori H., Sadighi J.P., Yin J., and Buchwald S.L. J. Org. Chem. 65 (2000) 1158
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45
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38349036441
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Heterogeneously catalyzed reactions are also known.
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46
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0033532101
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Valot F., Fache F., Jacquot R., Spagnol M., and Lemaire M. Tetrahedron Lett. 40 (1999) 3689
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48
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38349079069
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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.
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51
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38349066458
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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.
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53
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34248151386
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Hollmann D., Tillack A., Michalik D., Jackstell R., and Beller M. Chem. Asian J. 2 (2007) 403
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61
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For a preliminary report, see:
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For a preliminary report, see:. Fujita K., Li Z., Ozeki N., and Yamaguchi R. Tetrahedron Lett. 44 (2003) 2687
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62
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38349042514
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note
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2 as the catalyst. See Ref 16.
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63
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38349065615
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note
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When the reaction was carried out at 110 °C, the yield was 63%.
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64
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38349042515
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note
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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.
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65
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38349027368
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note
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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.
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66
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38349003324
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note
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(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.
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67
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38349027367
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note
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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.
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70
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38349004949
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*Ir-catalyzed hydrogen transfer reactions, in which catalytic intermediates are trivalent iridium species.
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75
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20444432759
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80
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33646096265
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Zhang Z., Mao J., Zhu D., Wu F., Chen H., and Wan B. Tetrahedron 62 (2006) 4435
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