Mild Copper-Catalyzed Addition of Arylboronic Esters to Di-tert-butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates

Abstract

An efficient copper-catalyzed addition of arylboronic esters to (Boc)₂O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition–elimination mechanism.

Key words

copper catalysis - arylboronic esters - addition - carboxylation - methyl arylcarboxylates

Publication History

Received: 29 December 2020

Accepted after revision: 29 January 2021

Accepted Manuscript online:
29 January 2021

Article published online:
17 February 2021

• References and Notes

• 1a Cherney AH, Kadunce NT, Reisman SE. Chem. Rev. 2015; 115: 9587
• 1b Breit B, Schmidt Y. Chem. Rev. 2008; 108: 2928
• 1c Yoshikai N, Nakamura E. Chem. Rev. 2012; 112: 2339
• 2a Burns DH, Miller JD, Chan H.-K, Delaney MO. J. Am. Chem. Soc. 1997; 119: 2125
• 2b Bertz SH, Eriksson M, Miao G, Snyder JP. J. Am. Chem. Soc. 1996; 118: 10906
• 2c Genna DT, Posner GH. Org. Lett. 2011; 13: 5358
• 2d Lipshutz BH, Kozlowski JA, Wilhelm RS. J. Org. Chem. 1983; 48: 546
• 2e Pan J.-L, Chen T, Zhang Z.-Q, Li Y.-F, Zhang X.-M, Zhang F.-M. Chem. Commun. 2016; 52: 2382

For selected examples, see:
• 3a Johnson DA, Jennings MP. Org. Lett. 2018; 20: 6099
• 3b Guo Y, Harutyunyan SR. Angew. Chem. Int. Ed. 2019; 58: 12950
• 3c Cahiez G, Gager O, Buendia J. Angew. Chem. Int. Ed. 2010; 49: 1278
• 3d Xiao B, Gong T.-J, Liu Z.-J, Liu J.-H, Luo D.-F, Xu J, Liu L. J. Am. Chem. Soc. 2011; 133: 9250
• 3e Liu J.-H, Yang C.-T, Lu X.-Y, Zhang Z.-Q, Xu L, Cui M, Lu X, Xiao B, Fu Y, Liu L. Chem. Eur. J. 2014; 20: 15334
• 3f Ren P, Stern L.-A, Hu X. Angew. Chem. Int. Ed. 2012; 51: 9110
• 4a Hall DG. In Boronic Acids: Preparation and Applications in Organic Synthesis and Medicine. Hall DG. Wiley-VCH; Weinheim: 2005. 1
• 4b Fyfe JW. B, Watson AJ. B. Chem 2017; 3: 31
• 5a Akgun B, Hall DG. Angew. Chem. Int. Ed. 2018; 57: 13028
• 5b Lennox AJ. J, Lloyd-Jones GC. Angew. Chem. Int. Ed. 2013; 52: 7362
• 5c Lennox AJ. J, Lloyd-Jones GC. Chem. Soc. Rev. 2014; 43: 412
• 5d Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457

For selected examples of couplings with aryl halides or pseudohalides, see:
• 6a Thathagar MB, Beckers J, Rothenberg G. J. Am. Chem. Soc. 2002; 124: 11858
• 6b Bergmann AM, Oldham AM, You W, Brown MK. Chem. Commun. 2018; 54: 5381
• 6c Zhou Y, You W, Smith KB, Brown MK. Angew. Chem. Int. Ed. 2014; 53: 3475
• 6d Gurung SK, Thapa S, Shrestha B, Giri R. Org. Chem. Front. 2015; 2: 649
• 6e Gurung SK, Thapa S, Kafle A, Dickie DA, Giri R. Org. Lett. 2014; 16: 1264
• 6f Tailor SB, Manzotti M, Asghar S, Rowsell BJ. S, Luckham SL. J, Sparkes HA, Bedford RB. Organometallics 2019; 38: 1770
• 6g Budiman YP, Friedrich A, Radius U, Marder TB. ChemCatChem 2019; 11: 5387
• 6h Mao J, Guo J, Fang F, Ji S.-J. Tetrahedron 2008; 64: 3905
• 6i Li J.-H, Li J.-L, Xie Y.-X. Synthesis 2007; 984

Selected examples on coupling with alkyl halides or pseudohalides:
• 7a Yang C.-T, Zhang Z.-Q, Liu Y.-C, Liu L. Angew. Chem. Int. Ed. 2011; 50: 3904
• 7b Shintani R, Takatsu K, Takeda M, Hayashi T. Angew. Chem. Int. Ed. 2011; 50: 8656
• 7c Sun Y.-Y, Yi J, Lu X, Zhang Z.-Q, Xiao B, Fu Y. Chem. Commun. 2014; 50: 11060
• 7d Zhu Z, Liu J, Dong S, Chen B, Wang Z, Tang R, Li Z. Asian J. Org. Chem. 2020; 9: 631
• 7e Jiang S, Dong X.-Y, Gu Q.-S, Ye L, Li Z.-L, Liu X.-Y. J. Am. Chem. Soc. 2020; 142: 19652
• 7f Takeda M, Takatsu K, Shintani R, Hayashi T. J. Org. Chem. 2014; 79: 2354

For selected examples of couplings with alkynyl halides or pseudohalides, see:
• 8a Yu C.-M, Kweon J.-H, Ho P.-S, Kang S.-C, Lee GY. Synlett 2005; 2631
• 8b Wang S, Wang M, Wang L, Wang B, Li P, Wang J. Tetrahedron 2011; 67: 4800
• 8c Babu SA, Saranya S, Rohit KR, Anilkumar J. ChemistrySelect 2019; 4: 1019
• 9a Takatsu K, Shintani R, Hayashi T. Angew. Chem. Int. Ed. 2011; 50: 5548
• 9b Wu C, Yue G, Nielsen CD.-T, Xu K, Hirao H, Zhou J. J. Am. Chem. Soc. 2016; 138: 742
• 10a Lu X.-Y, Yang C.-T, Liu J.-H, Zhang Z.-Q, Lu X, Lou X, Xiao B, Fu Y. Chem. Commun. 2015; 51: 2388
• 10b Lu X.-Y, Li J.-S, Wang J.-Y, Wang S.-Q, Li Y.-M, Zhu Y.-J, Zhou R, Ma W.-J. RSC Adv. 2018; 8: 41561
• 11a Shintani R, Takatsu K, Hayashi T. Chem. Commun. 2010; 46: 6822
• 11b Ni C, Gao J, Fang X. Chem. Commun. 2020; 56: 2654
• 11c Liao Y.-Y, Hu Q.-S. J. Org. Chem. 2011; 76: 7602
• 11d Zheng H, Zhang Q, Chen J, Liu M, Cheng S, Ding J, Wu H, Su W. J. Org. Chem. 2009; 74: 943
• 11e Tomita D, Yamatsugu K, Kanai M, Shibasaki M. J. Am. Chem. Soc. 2009; 131: 6946
• 12a Ohishi T, Nishiura M, Hou Z. Angew. Chem. Int. Ed. 2008; 47: 5792
• 12b Riss PJ, Lu S, Telu S, Aigbirhio FI, Pike VW. Angew. Chem. Int. Ed. 2012; 51: 2698
• 12c Takaya J, Tadami S, Ukai K, Iwasawa N. Org. Lett. 2008; 10: 2697
• 12d Ohmiya H, Tanabe M, Sawamura M. Org. Lett. 2011; 13: 1086
• 12e Wang W, Zhang G, Lang R, Xia C, Li F. Green Chem. 2013; 15: 635
• 12f Nayal OS, Hong J, Yang Y, Mo F. Org. Chem. Front. 2019; 6: 3673
• 12g Duong HA, Nguyen TM, Rosman NZ. B, Tan LJ. L. Synthesis 2014; 46: 1881
• 12h Zheng R, Zhou Q, Gu H, Jiang H, Wu J, Jin Z, Han D, Dai G, Chen R. Tetrahedron Lett. 2014; 55: 5671
• 13 Saito Y, Ouchi H, Takahata H. Tetrahedron 2006; 62: 11599
• 14a Sämann C, Haag B, Knochel P. Chem. Eur. J. 2012; 18: 16145
• 14b Degennaro L, Maggiulli D, Carlucci C, Fanelli F, Romanazzi G, Luisi R. Chem. Commun. 2016; 52: 9554
• 14c Huck L, de la Hoz A, Díaz-Ortiz A, Alcazar J. Org. Lett. 2017; 19: 3747
• 14d Kogami M, Watanabe N. Synth. Commun. 2013; 43: 681
• 15 Methyl (Het)arylcarboxylates 3a–y, 5a–e; General Procedure A 15 mL Schlenk tube equipped with a stirrer bar was charged with CuCl (10 mol%), L7 (13 mol%), LiOMe (2.5 equiv), and the appropriate boronic ester 1 or 4 (0.375 mmol). The vessel was then evacuated and filled with Ar (three cycles). DMA (0.5 mL) and (Boc)₂O (0.25 mmol) were added sequentially under Ar, and the mixture was stirred at 30 ℃ for 6 h. MeI (5 equiv) was then added in air, and the mixture was stirred at 30 ℃ for additional 2 h. The mixture was finally diluted with EtOAc and washed with sat. aq NaCl (20 mL). The aqueous phase was further extracted with EtOAc (3 × 20 mL), and the combined organic phases were dried (Na₂SO₄) and concentrated. The residue was purified by column chromatography [silica gel EtOAc–hexane (1:100 to 1:50)]. Methyl 2-Naphthoate (3b) Prepared by following the general procedure as a white solid; yield: 91% (by HPLC). ¹H NMR (400 MHz, CDCl₃): δ = 8.62 (s, 1 H), 8.08–8.05 (m, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.88 (d, J = 8.7 Hz, 2 H), 7.63–7.49 (m, 2 H), 3.98 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 167.29, 135.53, 132.51, 131.09, 129.37, 128.25, 128.17, 127.78, 127.41, 126.66, 125.24, 52.26. The NMR spectral data agreed with the reported values.¹⁶
• 16 Tobisu M, Yamakawa K, Shimasaki T, Chatani N. Chem. Commun. 2011; 47: 2946