Nickel-Catalyzed Transesterification of Methyl Esters

Dedicated to the late Prof. Keith Fagnou on the 20^th anniversary of the start of his academic career.

Abstract

A transesterification of methyl esters with aliphatic alcohols was developed using Ni/dcype catalysis. This reaction features the cleavage of the strong C(acyl)–OMe bond in the absence of acidic or basic additives, providing volatile methanol as the only stoichiometric waste product. A wide range of (hetero)aromatic and aliphatic methyl esters can be converted into the corresponding functionalized esters in good to excellent yields with high efficiency. Compared with traditional transesterifications, this cross-coupling approach offers new opportunities for efficient and chemoselective synthesis.

Key words

nickel - transesterification - methyl esters - aliphatic alcohols - cross-coupling

Publication History

Received: 02 June 2023

Accepted after revision: 10 July 2023

Article published online:
04 September 2023

• References and Notes

• 1a Suzuki A. Angew. Chem. Int. Ed. 2011; 50: 6722
• 1b Johansson SeechurnC. C. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
• 1c Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
• 1d Ruiz-Castillo PBuchwald S. L. Chem. Rev. 2016; 116: 12564
• 2a Liu J, Ye Y, Sessler JL, Gong H. Acc. Chem. Res. 2020; 53: 1833
• 2b Weix DJ. Acc. Chem. Res. 2015; 48: 1767
• 2c Pang X, Su P.-F, Shu X.-Z. Acc. Chem. Res. 2022; 55: 2491
• 3a Douglas JJ, Sevrin MJ, Stephenson CR. Org. Process Res. Dev. 2016; 20: 1134
• 3b Twilton J, Le C, Zhang P, Shaw MH, Evans RW, MacMillan DW. C. Nat. Rev. Chem. 2017; 1: 0052
• 3c Wiles RJ, Molander GA. Isr. J. Chem. 2020; 60: 281
• 4a Zhu C, Ang NW. J, Meyer TH, Qiu Y, Ackermann L. ACS Cent. Sci. 2021; 7: 415
• 4b Novaes LF. T, Liu J, Shen Y, Lu L, Meinhardt JM, Lin S. Chem. Soc. Rev. 2021; 50: 7941
• 4c Yan M, Kawamata Y, Baran PS. Chem. Rev. 2017; 117: 13230
• 5 Boit TB, Bulger AS, Dander JE, Garg NK. ACS Catal. 2020; 10: 12109
• 6a Basch CH, Liao J, Xu J, Piane JJ, Watson MP. J. Am. Chem. Soc. 2017; 139: 5313
• 6b Twitty JC, Hong Y, Garcia B, Tsang S, Liao J, Schultz DM, Hanisak J, Zultanski SL, Dion A, Kalyani D, Watson MP. J. Am. Chem. Soc. 2023; 145: 5684
• 7a Dander JE, Garg NK. ACS Catal. 2017; 7: 1413
• 7b Liu C, Szostak M. Chem. Eur. J. 2017; 23: 7157
• 7c Chaudhari MB, Gnanaprakasam B. Chem. Asian J. 2019; 14: 76
• 8a Takise R, Muto K, Yamaguchi J. Chem. Soc. Rev. 2017; 46: 5864
• 8b Guo L, Rueping M. Acc. Chem. Res. 2018; 51: 1185
• 9 Zheng Y.-L, Newman SG. Chem. Commun. 2021; 57: 2591
• 10a Ben HalimaT, Zhang W, Yalaoui I, Hong X, Yang YF, Houk KN, Newman SG. J. Am. Chem. Soc. 2017; 139: 1311
• 10b Ben HalimaT, Vandavasi JK, Shkoor M, Newman SG. ACS Catal. 2017; 7: 2176
• 10c Masson-Makdissi J, Vandavasi JK, Newman SG. Org. Lett. 2018; 20: 4094
• 11 Hie L, Fine NathelN. F, Hong X, Yang YF, Houk KN, Garg NK. Angew. Chem. Int. Ed. 2016; 55: 2810
• 12 Ben HalimaT, Masson-Makdissi J, Newman SG. Angew. Chem. Int. Ed. 2018; 57: 12925
• 13 Zheng Y.-L, Newman SG. ACS Catal. 2019; 9: 4426
• 14 Zheng Y.-L, Newman SG. Angew. Chem. Int. Ed. 2019; 58: 18159
• 15 Cook A, Prakash S, Zheng Y.-L, Newman SG. J. Am. Chem. Soc. 2020; 142: 8109

For related examples of nickel-catalyzed reductions of C–O and C–N bond-containing molecules, see:
• 16a Alvarez-Bercedo P, Martin R. J. Am. Chem. Soc. 2010; 132: 17352
• 16b Tobisu M, Yamakawa K, Shimasaki T, Chatani N. Chem. Commun. 2011; 47: 2946
• 16c Yue H, Guo L, Lee S.-C, Liu X, Rueping M. Angew. Chem. Int. Ed. 2017; 56: 3972
• 16d Simmons BJ, Hoffmann M, Hwang J, Jackl MK, Garg NK. Org. Lett. 2017; 19: 1910
• 17 Zheng Y.-L, Xie P.-P, Daneshfar O, Houk KN, Hong X, Newman SG. Angew. Chem. Int. Ed. 2021; 60: 13476

For other key examples of Ni-catalyzed functionalization of methyl esters, see:
• 18a Walker JA, Vickerman KL, Humke JN, Stanley LM. J. Am. Chem. Soc. 2017; 139: 10228
• 18b Yue H, Zhu C, Rueping M. Org. Lett. 2018; 20: 385
• 18c Okita T, Muto K, Yamaguchi J. Org. Lett. 2018; 20: 3132
• 18d Iyori Y, Takahashi K, Yamazaki K, Ano Y, Chatani N. Chem. Commun. 2019; 55: 13610
• 19 Esterification Methods, Reactions, and Applications. Otera J, Nishikido J. Wiley-VCH; Weinheim: 2010
• 20a Hie L, Fine NathelN. F, Shah TK, Baker EL, Hong X, Yang Y.-F, Liu P, Houk KN, Garg NK. Nature 2015; 524: 79
• 20b Hie L, Baker EL, Anthony SM, Garg NK. Angew. Chem. Int. Ed. 2016; 55: 15129
• 20c Weires NA, Caspi DD, Garg NK. ACS Catal. 2017; 7: 4381
• 20d Dander JE, Weires NA, Garg NK. Org. Lett. 2016; 18: 3934
• 21 Bourne-Branchu Y, Gosmini C, Danoun G. Chem. Eur. J. 2017; 23: 10043
• 22a Isbrandt ES, Sullivan RJ, Newman SG. Angew. Chem. Int. Ed. 2019; 58: 7180
• 22b Kashani SK, Jessiman JE, Newman SG. Org. Process Res. Dev. 2020; 24: 1948
• 23 Newton JJ, Britton R, Friesen CM. J. Org. Chem. 2018; 83: 12784
• 24 Grasa GA, Kissling RM, Nolan SP. Org. Lett. 2002; 4: 3583
• 25 Typical Experimental Procedure and Characterization Data of 6 In a glovebox, an oven-dried (120 °C) screw-capped vial was charged with a magnetic stir bar, Ni(cod)₂ (3.3 mg, 6 mol%), and dcype (5.9 mg, 7 mol%). Thoroughly degassed toluene (0.4 mL, 0.5 M) obtained from a solvent purification system was then added. Then, methyl 1-methylindole-6-carboxylate (0.2 mmol, 37.8 mg) and cyclopropylmethanol (0.3 mmol, 21.6 mg) were subsequently added. The vial was sealed with a Teflon-lined screw cap and shipped outside of the glovebox. The reaction was stirred in a pre-heated silicone oil bath at 130 °C for 2 h. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and filtered through a plug of silica gel. The crude mixture was concentrated and purified via column chromatography (hexanes/EtOAc = 8:1) to afford 6 as a brown solid (27.5 mg, 60%). ¹H NMR (400 MHz, CDCl₃): δ = 8.13 (s, 1 H), 7.85 (dd, J = 8.4, 1.6 Hz, 1 H), 7.65 (d, J = 8.4 Hz, 1 H), 7.20 (d, J = 3.2 Hz, 1 H), 6.53 (d, J = 2.8 Hz, 1 H), 4.20 (d, J = 7.2 Hz, 2 H), 3.86 (s, 3 H), 1.38–1.26 (m, 1 H), 0.70–0.59 (m, 2 H), 0.47–0.36 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.9, 136.1, 132.02, 131.95, 123.5, 120.4, 120.3, 111.7, 101.3, 69.4, 33.0, 10.0, 3.3. Accurate mass (EI): m/z calcd for C₁₄H₁₅NO₂: 229.1097; found: 229.1062; spectral accuracy = 98.2%.
• 26a Amaike K, Muto K, Yamaguchi J, Itami K. J. Am. Chem. Soc. 2012; 134: 13573
• 26b Meng L, Kamada Y, Muto K, Yamaguchi J, Itami K. Angew. Chem. Int. Ed. 2013; 52: 10048
• 26c Muto K, Yamaguchi J, Musaev DG, Itami K. Nat. Commun. 2015; 6: 7508
• 26d Liu X, Jia J, Rueping M. ACS Catal. 2017; 7: 4491
• 26e Chatupheeraphat A, Liao HH, Srimontree W, Guo L, Minenkov Y, Poater A, Cavallo L, Rueping M. J. Am. Chem. Soc. 2018; 140: 3724
• 26f Guo L, Chatupheeraphat A, Rueping M. Angew. Chem. Int. Ed. 2016; 55: 11810
• 26g Chatupheeraphat A, Liao HH, Lee SC, Rueping M. Org. Lett. 2017; 19: 4255
• 26h Yue H, Guo L, Liao HH, Cai Y, Zhu C, Rueping M. Angew. Chem. Int. Ed. 2017; 56: 4282
• 26i Pu X, Hu J, Zhao Y, Shi Z. ACS Catal. 2016; 6: 6692
• 26j Takise R, Isshiki R, Muto K, Itami K, Yamaguchi J. J. Am. Chem. Soc. 2017; 139: 3340
• 26k Isshiki R, Kurosawa MB, Muto K, Yamaguchi J. J. Am. Chem. Soc. 2021; 143: 10333
• 26l Matsushita K, Takise R, Muto K, Yamaguchi J. Sci. Adv. 2020; 6: eaba7614
• 26m Iizumi K, Kurosawa MB, Isshiki R, Muto K, Yamaguchi J. Synlett 2021; 32: 1555
• 26n Ji C.-L, Xie P.-P, Hong X. Molecules 2018; 23: 2681
• 27 Hong X, Liang Y, Houk KN. J. Am. Chem. Soc. 2014; 136: 2017