N-Alkylation of carbamates and amides with alcohols catalyzed by a Cp*Ir complex

被引：69

作者：

Fujita, Ken-ichi ^{[1
,2
]}

Komatsubara, Atsuo ^{[1
]}

Yamaguchi, Ryohei ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Human & Environm Studies, Kyoto 6068501, Japan

[2] Kyoto Univ, Grad Sch Global Environm Studies, Kyoto 6068501, Japan

来源：

TETRAHEDRON | 2009年 / 65卷 / 18期

关键词：

Iridium catalyst; N-Alkylation; Carbamate; Alcohol; DIRECT ALPHA-ALKYLATION; SECONDARY ALCOHOLS; TERTIARY-AMINES; BORROWING HYDROGEN; ORGANIC-SYNTHESIS; RUTHENIUM; EFFICIENT; AMINATION; ACTIVATION; ALDEHYDES;

D O I：

10.1016/j.tet.2009.03.002

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

New atom-economical catalytic systems consisting of [Cp*IrCl2](2)/NaOAc (Cp*=pentamethylcyclopentadienyl) for the N-alkylation of carbamates and amides using alcohols as alkylating agents under solvent-free conditions have been developed. For example, the reaction of n-butyl carbamate with benzyl alcohol in the presence of [Cp*IrCl2](2) (5.0 mol % Ir) and NaOAc (5.0 mol %) at 130 degrees C under the absence of solvent gives n-butyl N-benzylcarbamate in the yield of 94%. The present catalytic system is applicable to not only carbamates but also amides, and only harmless water is produced as co-product. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：3624 / 3628

页数：5

共 54 条

[11] Cyclopentadienyl RuII complexes as highly efficient catalysts for the N-methylation of alkylamines by methanol [J].

Del Zotto, A ;

Baratta, W ;

Sandri, M ;

Verardo, G ;

Rigo, P .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (03) :524-529

[12] Reductive N-alkylation of amides, carbamates and ureas [J].

Dubé, D ;

Scholte, AA .

TETRAHEDRON LETTERS, 1999, 40 (12) :2295-2298

[13] Direct β-alkylation of secondary alcohols with primary alcohols catalyzed by a Cp*lr complex [J].

Fujita, K ;

Asai, C ;

Yamaguchi, T ;

Hanasaka, F ;

Yamaguchi, R .

ORGANIC LETTERS, 2005, 7 (18) :4017-4019

[14] CP*Ir complex-catalyzed hydrogen transfer reactions directed toward environmentally benign organic synthesis [J].

Fujita, K ;

Yamaguchi, R .

SYNLETT, 2005, (04) :560-571

[15] Oxidation of primary and secondary alcohols catalyzed by a pentamethylcyclopentadienyliridium complex [J].

Fujita, K ;

Furukawa, S ;

Yamaguchi, R .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 649 (02) :289-292

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

Fujita, Ken-ichi ;

Enoki, Youichiro ;

Yamaguchi, Ryohei .

TETRAHEDRON, 2008, 64 (08) :1943-1954

[17]

Greene T.W., 1981, PROTECTIVE GROUPS OR

[18] TRANSITION METAL-CATALYZED N-ALKYLATION OF AMINES BY ALCOHOLS [J].

GRIGG, R ;

MITCHELL, TRB ;

SUTTHIVAIYAKIT, S ;

TONGPENYAI, N .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (12) :611-612

[19] Borrowing hydrogen in the activation of alcohols [J].

Hamid, Malai Haniti S. A. ;

Slatford, Paul A. ;

Williams, Jonathan M. J. .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (10) :1555-1575

[20] Ruthenium catalysed N-alkylation of amines with alcohols [J].

Hamid, Malai Haniti S. A. ;

Williams, Jonathan M. J. .

CHEMICAL COMMUNICATIONS, 2007, (07) :725-727

← 1 2 3 4 5 6 →