Hydrogen-Borrowing Amination of Secondary Alcohols Promoted by a (Cyclopentadienone)iron Complex

Abstract

Thanks to a highly active catalyst, the scope of the (cyclopentadienone)iron complex-promoted ‘hydrogen-borrowing’ (HB) amination has been expanded to secondary alcohols, which had previously been reported to react only in the presence of large amounts of co-catalysts. A range of cyclic and acyclic secondary alcohols were reacted with aromatic and aliphatic amines giving fair to excellent yields of the substitution products. The catalyst was also able to promote the cyclization of diols bearing a secondary alcohol group with primary amines to generate saturated N-heterocycles.

Key words

hydrogen borrowing - iron - amination - alcohols - (cyclopenta­dienone)iron complexes

• References


For the importance of amines as fine chemistry intermediates, see:
• 1a Lawerencem SA. Amine: Synthesis Properties and Applications . Cambridge University Press; Cambridge: 2004
• 1b Brown BR. The Organic Chemistry of Aliphatic Nitrogen Compounds . Cambridge University; Cambridge: 2004
• 2a Valot F, Fache F, Jacquot R, Spagnol M, Lemaire M. Tetrahedron Lett. 1999; 40: 3689
• 2b Narayanan S, Deshpande K. Appl. Catal., A 2000; 199: 1

For reviews, see:
• 3a Corma A, Navas J, Sabater MJ. Chem. Rev. 2018; 118: 1410
• 3b Quintard A, Rodriguez J. ChemSusChem 2016; 9: 28
• 3c Yang Q, Wang Q, Yu Z. Chem. Soc. Rev. 2015; 44: 2305
• 3d Ketcham JM, Shin I, Montgomery TP, Krische MJ. Angew. Chem. Int. Ed. 2014; 53: 9142
• 3e Gunanathan C, Milstein D. Science 2013; 341 (6143): 1229712
• 3f Bähn S, Imm S, Neubert L, Zhang M, Neumann H, Beller M. ChemCatChem 2011; 3: 1853
• 3g Watson AJ. A, Williams JM. J. Science 2010; 329 (5992): 635
• 3h Guillena G, Ramón DJ, Yus M. Chem. Rev. 2010; 110: 1611
• 3i Nixon TD, Whittlesey MK, Williams JM. J. Dalton Trans. 2009; 753
• 3j Hamid MH. S. A, Slatford PA, Williams JM. J. Adv. Synth. Catal. 2007; 349: 1555
• 4a Murahashi S.-I, Kondo K, Hakata T. Tetrahedron Lett. 1982; 23: 229
• 4b Grigg R, Mitchell TR. B, Sutthivaiyakit S, Tongpenyai N. J. Chem. Soc., Chem. Commun. 1981; 611
• 4c Watanabe Y, Tsuji Y, Ohsugi Y. Tetrahedron Lett. 1981; 22: 2667

For ruthenium, see:
• 5a Marichev KO, Takacs JM. ACS Catal. 2016; 6: 2205
• 5b Jumde VR, Gonsalvi L, Guerriero A, Peruzzini M, Taddei M. Eur. J. Org. Chem. 2015; 1829
• 5c Jumde VR, Cini E, Porcheddu A, Taddei M. Eur. J. Org. Chem. 2015; 1068
• 5d Balaraman E, Srimani D, Diskin-Posner Y, Milstein D. Catal. Lett. 2015; 145: 139
• 5e Shan SP, Xiaoke X, Gnanaprakasam B, Dang TT, Ramalingam B, Huynh HV, Seayad AM. RSC Adv. 2015; 5: 4434
• 5f Oldenhuis NJ, Dong VM, Guan Z. J. Am. Chem. Soc. 2014; 136: 12548
• 5g Enyong AB, Moasser B. J. Org. Chem. 2014; 79: 7553
• 5h Chen M, Zhang M, Xie F, Wang X, Jiang H. ChemCatChem 2014; 6: 2993
• 5i Demir S, Coşkun F, Özdemir İ. J. Organomet. Chem. 2014; 755: 134
• 5j Hamid MH. S. A, Allen CL, Lamb GW, Maxwell AC, Maytum HC, Watson AJ. A, Williams JM. J. J. Am. Chem. Soc. 2009; 131: 1766

For iridium, see:
• 6a Wöckel S, Plessow P, Schelwies M, Brinks MK, Rominger F, Hofmann P, Limbach M. ACS Catal. 2014; 4: 152
• 6b Zhang Y, Lim C.-S, Sim DS. B, Pan H.-J, Zhao Y. Angew. Chem. Int. Ed. 2014; 53: 1399
• 6c Ruch S, Irrgang T, Kempe R. Chem. Eur. J. 2014; 20: 13279
• 6d Qu P, Sun C, Ma J, Li F. Adv. Synth. Catal. 2014; 356: 447
• 6e Chang Y.-H, Nakajima Y, Ozawa F. Organometallics 2013; 32: 2210
• 6f Fujita K.-i, Fujii T, Yamaguchi R. Org. Lett. 2004; 6: 3525
• 7a Martínez-Asencio A, Ramón DJ, Yus M. Tetrahedron Lett. 2010; 51: 325
• 7b Shi F, Tse MK, Cui X, Gördes D, Michalik D, Thurow K, Deng Y, Beller M. Angew. Chem. Int. Ed. 2009; 48: 5912
• 8 Rösler S, Ertl M, Irrgang T, Kempe R. Angew. Chem. Int. Ed. 2015; 54: 15046
• 9a Bala M, Verma PK, Sharma U, Kumar N, Singh B. Green Chem. 2013; 15: 1687
• 9b Cui X, Shi F, Zhang Y, Deng Y. Tetrahedron Lett. 2010; 51: 2048
• 9c Jana U, Maiti S, Biswas S. Tetrahedron Lett. 2008; 49: 858
• 10a Yan T, Feringa BL, Barta K. Sci. Adv. 2017; 3: eaao6494
• 10b Yan T, Feringa BL, Barta K. ACS Catal. 2016; 6: 381
• 10c Yan T, Feringa BL, Barta K. Nat. Commun. 2014; 5: 5602

For reviews on catalytic applications of (cyclopentadienone)iron complexes, see:
• 11a Piarulli U, Vailat Facchini S, Pignataro L. Chimia 2017; 71: 580
• 11b Quintard A, Rodriguez J. Angew. Chem. Int. Ed. 2014; 53: 4044
• 12 Lator A, Gaillard S, Poater A, Renaud J.-L. Org. Lett. 2018; 20: 5985

For use of (cyclopentadienone)iron complexes in HB reactions different from alcohol amination, see:
• 13a Polidano K, Allen BD. W, Williams JM. J, Morrill LC. ACS Catal. 2018; 8: 6440
• 13b Seck C, Mbaye MD, Gaillard S, Renaud J.-L. Adv. Synth. Catal. 2018; 360: 4640
• 13c Seck C, Mbaye MD, Coufourier S, Lator A, Lohier J.-F, Poater A, Ward TR, Gaillard S, Renaud J.-L. ChemCatChem 2017; 9: 4410
• 13d Elangovan S, Sortais J.-B, Beller M, Darcel C. Angew. Chem. Int. Ed. 2015; 54: 14483
• 13e Roudier M, Constantieux T, Quintard A, Rodriguez J. Org. Lett. 2014; 16: 2802
• 13f Quintard A, Constantieux T, Rodriguez J. Angew. Chem. Int. Ed. 2013; 52: 12883
• 14a Brown TJ, Cumbes M, Diorazio LJ, Clarkson GJ, Wills M. J. Org. Chem. 2017; 82: 10489
• 14b Rawlings AJ, Diorazio LJ, Wills M. Org. Lett. 2015; 17: 1086
• 15 Pan H.-J, Ng TW, Zhao Y. Chem. Commun. 2015; 51: 11907
• 16a Bai X, Cettolin M, Mazzoccanti G, Pierini M, Piarulli U, Colombo V, Dal Corso A, Pignataro L, Gennari C. Tetrahedron 2019; 75: 1415
• 16b Cettolin M, Bai X, Lübken D, Gatti M, Facchini SV, Piarulli U, Pignataro L, Gennari C. Eur. J. Org. Chem. 2019; 647
• 16c Vailati Facchini S, Cettolin M, Bai X, Casamassima G, Pignataro L, Gennari C, Piarulli U. Adv. Synth. Catal. 2018; 360: 1054
• 16d Vailati Facchini S, Neudörfl J.-M, Pignataro L, Cettolin M, Gennari C, Berkessel A, Piarulli U. ChemCatChem 2017; 9: 1461
• 16e Gajewski P, Gonzalez-de-Castro A, Renom-Carrasco M, Piarulli U, Gennari C, de Vries JG, Lefort L, Pignataro L. ChemCatChem 2016; 8: 3431
• 16f Gajewski P, Renom-Carrasco M, Vailati Facchini S, Pignataro L, Lefort L, de Vries JG, Ferraccioli R, Piarulli U, Gennari C. Eur. J. Org. Chem. 2015; 5526
• 16g Gajewski P, Renom-Carrasco M, Vailati Facchini S, Pignataro L, Lefort L, de Vries JG, Ferraccioli R, Forni A, Piarulli U, Gennari C. Eur. J. Org. Chem. 2015; 1887
• 17 The result by Barta, Feringa et al. using pre-catalyst 1a (5 mol%), Me₃NO (10 mol%), CPME as solvent, 130 °C, 18 h, and 2:1 4a:3a ratio (see Ref. 10c, 69% yield) was reproduced in our laboratory (yield: 70%). We also tested pre-catalyst 1a (5 mol%) under the same conditions reported in Table 1, entry 1 [Me₃NO (10 mol%), toluene as solvent, 130 °C, 24 h and 1.5:1 4a:3a ratio], and obtained product P1 in 82% yield.
• 18a Overman LE, Owen CE, Pavan MM, Richards CJ. Org. Lett. 2003; 5: 1809
• 18b Overman LE. Angew. Chem., Int. Ed. Engl. 1984; 23: 579
• 18c Tamura K, Mizukami H, Maeda K, Watanabe H, Uneyama K. J. Org. Chem. 1993; 58: 32
• 19 The 1,4-reduction product is commonly formed in the hydrogenation of ketones promoted by (cyclopentadienone)iron complexes, and can be selectively obtained under suitable experimental conditions, see: Lator A, Gaillard S, Poater A, Renaud J.-L. Chem. Eur. J. 2018; 24: 5770
• 20 Cyclization of primary amines with secondary diols to yield unsaturated heterocycles (pyrroles) has been recently achieved using a Mn catalyst, see: Borghs JC, Lebedev Y, Rueping M, El-Sepelgy O. Org. Lett. 2019; 21: 70
• 21 Compounds P22 and P23 are new compounds, whereas P20 and P21 had been previously reported, see: Boga C, Manescalchi F, Savoia D. Tetrahedron 1994; 50: 4709
• 22 Still WC, Kahn M, Mitra A. J. Org. Chem. 1978; 43: 2923
• 23 Fisher DJ, Shaum JB, Mills CL, Read De Alaniz J. Org. Lett. 2016; 18: 5074
• 24 Renzi P, Hioe J, Gschwind RM. J. Am. Chem. Soc. 2017; 139: 6752
• 25 Lei Q, Wei Y, Talwar D, Wang C, Xue D, Xiao J. Chem. Eur. J. 2013; 19: 4021
• 26 Li J, Wang C, Xue D, Wei Y, Xiao J. Green Chem. 2013; 15: 2685
• 27 Li B, Sortais JB, Darcel C, Dixneuf PH. ChemSusChem 2012; 5: 396
• 28 Gülcemal D, Gülcemal S, Robertson CM, Xiao J. Organometallics 2015; 34: 4394
• 29 Clark JS. K, Lavoie CM, MacQueen PM, Ferguson MJ, Stradiotto M. Organometallics 2016; 35: 3248
• 30 Silva S, Rodrigues P, Bento I, Maycock CD. J. Org. Chem. 2015; 80: 3067
• 31 Liu X, Lin B, Zhang Z, Lei H, Li Y. RSC Adv. 2016; 6: 94399
• 32 Yang J, Wang C, Xie X, Li H, Li Y. Eur. J. Org. Chem. 2010; 4189
• 33 Iwai T, Harada T, Shimada H, Asano K, Sawamura M. ACS Catal. 2017; 7: 1681
• 34 Billman JH, Tai KM. J. Org. Chem. 1958; 23: 535
• 35 Perissutti E, Fiorino F, Renner C, Severino B, Roviezzo F, Sautebin L, Rossi A, Cirino G, Santagada V, Caliendo G. J. Med. Chem. 2006; 49: 7774
• 36 De Lamo Marin L, Martens T, Mioskowski C, Royer J. J. Org. Chem. 2005; 70: 10592
• 37 Kuchuk E, Muratov K, Perekalin DS, Chusov D. Org. Biomol. Chem. 2019; 17: 83
• 38 Otake Y, Williams JD, Rincón JA, de Frutos O, Mateos C, Kappe CO. Org. Biomol. Chem. 2019; 17: 1384
• 39 Prasad RR. R, Dawson DM, Cox PA, Ashbrook SE, Wright PA, Clarke ML. Chem. Eur. J. 2018; 24: 15309
• 40 Sakai N, Takahashi N, Ogiwara Y. Eur. J. Org. Chem. 2014; 5078