Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
Abstract: Alcohol amination is a green and environmentally friendly process with a high atomic utilization rate.Catalyst is an important factor affecting the results of alcohol amination.The main characteristics and research progress of ruthenium and iridium catalysts among homogeneous catalysts are introduced,and the research direction for industrial application of homogeneous catalysts is summarized.
[1] Bähn S,Imm S,Neubert L,et al.The catalytic amination of alcohols[J].Chemcatchem,2011,3(12):1853-1864. [2] Grigg R,Mitchell T R B,Sutthivaiyakit S,et al.Transition metal-catalysed N-alkylation of amines by alcohols[J].Journal of the Chemical Society Chemical Communications,1981,12(12):611-612. [3] Watanabe Y,Tsuji Y,Ohsugi Y.The ruthenium catalyzed N-alkylation and N-heterocyclization of aniline using alcohols and aldehydes[J].Tetrahedron Letters,1981,22(28):2667-2670. [4] Arcelli A,Bui-The-Khai,Porzi G.Selective conversion of primary amines into N,N-dimethylalkyl-or N,N-dialkylmethyl-amines with methanol and RuCl2(Ph3P)3[J].Journal of Organometallic Chemistry,1982,235(1):93-96. [5] Ganguly S,Roundhill D M.Conversion of long-chain terminal alcohols and secondary amines into tertiary amines using ruthenium(Ⅱ) tertiary phosphine complexes as homogeneous catalysts[J].Polyhedron,1990,9(20):2517-2526. [6] Sakano T,Ishii H,Yamaguchi I,et al.Preparation and characterization of various N-substituted-2-aza- [3] -ferrocenophanes and its chemical and electrochemical properties[J].Inorganica Chimica Acta,1999,296(1):176-182. [7] Marsella J A.Ruthenium catalyzed reactions of ethylene glycol with primary amines:Steric factors and selectivity control[J].Journal of Organometallic Chemistry,1991,407(1):97-105. [8] Tsuji Y,Huh K T,Ohsugi Y,et al.Ruthenium complex catalyzed N-heterocyclization.Syntheses of N-substituted piperidines,morpholines,and piperazines from amines and 1,5-diols[J].Journal of Organometallic Chemistry,1985,50(9):1365-1370. [9] Felföldi K,Klyavlin M S,Bartók M.Transformation of organic compounds in the presence of metal complexes Ⅴ.Cyclization of aminoalcohols on a ruthenium complex[J].Journal of Organometallic Chemistry,1989,362(1):193-195. [10] Tsuji Y,Yokoyama Y,Huh K T,et al.Ruthenium complex-catalyzed N-heterocyclization.Syntheses of N-substituted pyrroles and pyrrolidines from 1,4-diols and primary amines[J].Bulletin of the Chemical Society of Japan,1987,60(9):3456-3458. [11] Watanabe Y,Ohta T,Tsuji Y.The ruthenium catalyzed N-alkylation of amides with alcohols[J].Bulletin of the Chemical Society of Japan,1983,56(9):2647-2651. [12] Alessandro D Z,Baratta W,Sandri M,et al.Cyclopentadienyl RuⅡ complexes as highly efficient catalysts for the N-methylation of alkylamines by methanol[J].European Journal of Inorganic Chemistry,2004,2004(3):524-529. [13] Naskar S,Bhattacharjee M.Selective N-monoalkylation of anilines catalyzed by a cationic ruthenium(Ⅱ) compound[J].Tetrahedron Letters,2007,48(19):3367-3370. [14] Tillack A,Hollmann D,Michalik D,et al.A novel ruthenium-catalyzed amination of primary and secondary alcohols[J].Tetrahedron Letters,2006,47(50):8881-8885. [15] Hollmann D,Tillack A,Michalik D,et al.An improved ruthenium catalyst for the environmentally benign amination of primary and secondary alcohols[J].Chemistry-An Asian Journal,2007,2(3):403-410. [16] Tillack A,Hollmann D,Mevius K,et al.Salt-free synthesis of tertiary amines by ruthenium-catalyzed amination of alcohols[J].European Journal of Organic Chemistry,2008,28:4745-4750. [17] Bähn S,Tillack A,Imm S,et al.Ruthenium-catalyzed selective monoamination of vicinal diols[J].Chemsuschem,2009,2(6):551-557. [18] Hamid M H S A,Williams J M J.Ruthenium catalysed N-alkylation of amines with alcohols[J].Chemical Communications,2007,7:725-727. [19] Hamid M H S A,Williams J M J.Ruthenium-catalysed synthesis of tertiary amines from alcohols[J].Tetrahedron Letters,2007,48(47):8263-8265. [20] Hamid M H,Allen C L,Lamb G W,et al.Ruthenium-catalyzed N-alkylation of amines and sulfonamides using borrowing hydrogen methodology[J].Journal of the American Chemical Society,2010,40(24):1766-1774. [21] Luo J Y,Wu M Y,Xiao F H,et al.Ruthenium-catalyzed direct amination of alcohols with tertiary amines[J].Tetrahedron Letters,2011,52(21):2706-2709. [22] Bähn S,Imm S,Mevius K,et al.Selective ruthenium-catalyzed N-alkylation of indoles by using alcohols[J].Chemistry-A European Journal,2010,16:3590-3593. [23] Enyong A B,Moasser B.Ruthenium-catalyzed N-alkylation of amines with alcohols under mild conditions using the borrowing hydrogen methodology[J].Journal of Organometallic Chemistry,2014,79(16):7553-7563. [24] Jumde V R,Gonsalvi L,Guerriero A,et al.A ruthenium-based catalytic system for a mild borrowing-hydrogen process[J].European Journal of Organic Chemistry,2015,2015(8):5-7. [25] Marichev K O,Takacs J M.Ruthenium-catalyzed amination of secondary alcohols using borrowing hydrogen methodology[J].ACS Catalysis,2016,6(4):2205-2210. [26] Gunanathan C,Milstein D.Selective synthesis of primary amines directly from alcohols and ammonia[J].Angewandte Chemie International Edition,2009,47(45):8661-8664. [27] Imm S,Bähn S,Neubert L,et al.An efficient and general synthesis of primary amines by ruthenium-catalyzed amination of secondary alcohols with ammonia[J].Angewandte Chemie International Edition,2010,49(44):8126-8129. [28] Imm S,Bähn S,Zhang M,et al.Improved ruthenium-catalyzed amination of alcohols with ammonia:Synthesis of diamines and amino esters[J].Angewandte Chemie,2011,50(33):7599-7603. [29] Pingen D,Müller D,Vogt D.Direct amination of secondary alcohols using ammonia[J].Angewandte Chemie,2010,49(44):8130-8133. [30] Nakagawa N,Derrah E J,Schelwies M,et al.Triphos derivatives and diphosphines as ligands in the ruthenium-catalysed alcohol amination with NH3[J].Dalton Transactions,2016,45(16):6856-6865. [31] Fujita K I,Yamamoto K,Yamaguchi R.Oxidative cyclization of amino alcohols catalyzed by a Cp*Ir complex.Synthesis of indoles,1,2,3,4-tetrahydroquinolines,and 2,3,4,5-tetrahydro-1-benzazepine[J].Organic Letters,2002,4(16):2691-2694. [32] Fujita K I,Yamaguchi R.Cp*Ir complex-catalyzed hydrogen transfer reactions directed toward environmentally benign organic synthesis[J].Synlett,2005,(4):560-571. [33] Fujita K I,Fujii T,Yamaguchi R.Cp*Ir complex-catalyzed N-heterocyclization of primary amines with diols:A new catalytic system for environmentally benign synthesis of cyclic amines[J].Organic Letters,2004,6(20):3525-3528. [34] Fujita K I,Li Z,Ozeki N,et al.N-alkylation of amines with alcohols catalyzed by a Cp*Ir complex[J].Tetrahedron Letters,2003,44(13):2687-2690. [35] Fujita K I,Enoki Y,Yamaguchi R.Cp*Ir-catalyzed N-alkylation of amines with alcohols.A versatile and atom economical method for the synthesis of amines[J].Tetrahedron,2008,64(8):1943-1954. [36] Saidi O,Blacker A J,Farah M M,et al.Iridium-catalysed amine alkylation with alcohols in water[J].Chemical Communications,2010,46:1541-1543. [37] Saidi O,Blacker A J,Lamb G W,et al.Borrowing hydrogen in water and ionic liquids:Iridium-catalyzed alkylation of amines with alcohols[J].Organic Process Research & Development,2010,14(4):1046-1049. [38] Kawahara R,Fujita K I,Yamaguchi R.Multialkylation of aqueous ammonia with alcohols catalyzed by water-soluble Cp*Ir-ammine complexes[J].Journal of the American Chemical Society,2010,132(43):15108-15111. [39] Prades A,Corberán R,Poyatos M,et al.[IrCl2Cp*(NHC)] complexes as highly versatile efficient catalysts for the cross-coupling of alcohols and amines[J].Chemistry-A European Journal,2008,14(36):11474-11479. [40] Bartoszewicz A,Marcos R,Sahoo S,et al.A highly active bifunctional iridium complex with an alcohol/alkoxide-tethered N-heterocyclic carbene for alkylation of amines with alcohols[J].Chemistry-A European Journal,2012,18(45):14510-14519. [41] Blank B,Madalska M,Kempe R.An efficient method for the selective iridium-catalyzed monoalkylation of (hetero)aromatic amines with primary alcohols[J].Advanced Synthesis & Catalysis,2008,350(5):749-758. [42] Blank B,Michlik S,Kempe R.Synthesis of selectively mono-N-arylated aliphatic diamines via iridium-catalyzed amine alkylation[J].Advanced Synthesis & Catalysis,2009,351(17):2903-2911. [43] Michlik S,Hille T,Kempe R.The iridium-catalyzed synthesis of symmetrically and unsymmetrically alkylated diamines under mild reaction conditions[J].Advanced Synthesis & Catalysis,2012,354(5):847-862. [44] Andrushko N,Andrushko V,Roose P,et al.Amination of aliphatic alcohols and diols with an iridium pincer catalyst[J].Chemcatchem,2010,2(6):640-643. [45] Li F,Xie J J,Shan H X,et al.General and efficient method for direct N-monomethylation of aromatic primary amines with methanol[J].RSC Advances,2012,2(23):8645-8652. [46] Li J Q,Andersson P G.Room temperature and solvent-free iridium-catalyzed selective alkylation of anilines with alcohols[J].Chemical Communications,2013,49:6131-6133. [47] Ruch S,Irrgang T,Kempe R.New iridium catalysts for the selective alkylation of amines by alcohols under mild conditions and for the synthesis of quinolines by acceptor-less dehydrogenative condensation[J].Chemistry-A European Journal,2014,20(41):13279-13285. [48] Wetzel A,Wöckel S,Schelwies M,et al.Selective alkylation of amines with alcohols by Cp*-iridium(Ⅲ) half-sandwich complexes[J].Organic Letters,2013,15(2):266-269. [49] Campos J,Sharninghausen L S,Manas M G,et al.Methanol dehydrogenation by iridium N-heterocyclic carbene complexes[J].Inorganic Chemistry,2015,54(11):5079-5084. [50] Yamashita Y,Gopalarathnam A,Hartwig J F.Iridium-catalyzed,asymmetric amination of allylic alcohols activated by lewis acids[J].Journal of the American Chemical Society,2007,129(24):7508-7509. [51] Roggen M,Carreira E M.Stereospecific substitution of allylic alcohols to give optically active primary allylic amines:Unique reactivity of a (P,alkene)Ir complex modulated by iodide[J].Journal of the American Chemical Society,2010,132(34):11917-11919. [52] Bandini M.Allylic alcohols:Sustainable sources for catalytic enantioselective alkylation reactions[J].Angewandte Chemie International Edition,2011,50(5):994-995. [53] Lafrance M,Roggen M,Carreira E M.Direct,enantioselective iridium-catalyzed allylic amination of racemic allylic alcohols[J].Angewandte Chemie International Edition,2012,51(14):3470-3473. [54] Bandini M,Cera G,Chiarucci M.Catalytic enantioselective alkylations with allylic alcohols[J].Synthesis,2012,4:504-512.