Synlett, Table of Contents Synlett 2021; 32(08): 833-837DOI: 10.1055/a-1377-7369 letter Mild Copper-Catalyzed Addition of Arylboronic Esters to Di-tert-butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates Authors Jin-Di Xu Xiao-Bo Su Cai Wang Li-Wei Yao Jing-Hui Liu∗ Guo-Qin Hu∗ Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) 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 Key wordscopper catalysis - arylboronic esters - addition - carboxylation - methyl arylcarboxylates Full Text References 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. 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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 Supplementary Material Supplementary Material Supporting Information (PDF)
