Synlett, Table of Contents Synlett 2018; 29(17): 2321-2325DOI: 10.1055/s-0037-1610265 letter © Georg Thieme Verlag Stuttgart · New York Na2CO3-Catalyzed O-Acylation of Phenols for the Synthesis of Aryl Carboxylates with Use of Alkenyl Carboxylates Xiao-Yu Zhou* School of Chemistry and Materials Engineering, Liupanshui Normal University, Liupanshui, 553004, P. R. of China Email: zhouxiaoyu20062006@126.com , Xia Chen* School of Chemistry and Materials Engineering, Liupanshui Normal University, Liupanshui, 553004, P. R. of China Email: zhouxiaoyu20062006@126.com › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract Inorganic base-catalyzed O-acylation of phenol and its derivatives has been developed. The procedure provides an efficient catalysis system for the preparation of aryl carboxylates with alkenyl carboxylates as acyl reagents. The reaction proceeded smoothly by using Na2CO3 as the catalyst in MeCN to produce the corresponding aryl carboxylates in good to excellent yields. Key words Key wordsacylation - phenols - aryl carboxlates - alkenyl carboxylates - catalysis Full Text References References and Notes 1a Wuts PG. M. Greene TW. Protection for the Hydroxyl Group Including 1,2- and 1,3-Diols. In Greene’s Protective Groups in Organic Synthesis. John Wiley & Sons; New York: 2006. 4th ed 1b Pearson AL. Roush WJ. Handbook of Reagents for Organic Synthesis: Activating Agents and Protecting Groups . John Wiley & Sons; Chichester: 1999 1c Sartori G. Ballini R. Bigi F. Bosica G. Maggic R. Righi P. Chem. Rev. 2004; 104: 199 2 Thasana N. Worayuthakarn R. Kradanrat P. Hohn E. Young L. Ruchirawat S. J. Org. Chem. 2007; 72: 9379 3 Watson DA. Fan X. Buchwald SL. J. Org. Chem. 2008; 73: 7096 4 Ye Z. Wang W. Luo F. Zhang S. Cheng J. Org. Lett. 2009; 11: 3974 5a Wang W. Luo F. Zhang S. Cheng J. J. Org. Chem. 2010; 75: 2415 5b Zhang L. Zhang G. Zhang M. Cheng J. J. Org. Chem. 2010; 75: 7472 5c Luo F. Pan C. Qian P. Cheng J. Synthesis 2010; 2005 6a Magens S. Plietker B. J. Org. Chem. 2010; 75: 3715 6b Weng S.-S. Ke C.-S. Chen F.-K. Lyu Y.-F. Lin G.-Y. Tetrahedron 2011; 67: 1640 7 Grasa GA. Kissling RM. Nolan SP. Org. Lett. 2002; 4: 3583 8a Barry J. Bram G. Petit A. Tetrahedron Lett. 1988; 29: 4567 8b Takeno M. Kawasaki Y. Muromachi Y. Nishiyama Y. Sakaguchi S. Ishii Y. J. Org. Chem. 1996; 61: 3088 8c Tashiro D. Kawasaki Y. Sakaguchi S. Ishii Y. J. Org. Chem. 1997; 62: 8141 8d Yang Y.-C. Leung DY. C. Toy PH. Synlett 2013; 24: 1870 9 Sarkar SD. Grimme S. Studer A. J. Am. Chem. Soc. 2010; 132: 1190 10 Petersen TB. Khan R. Olofsson B. Org. Lett. 2011; 13: 3462 11 Liu H.-X. Dang Y.-Q. Yuan Y.-F. Xu Z.-F. Qiu S.-X. Tan H.-B. Org. Lett. 2016; 18: 5584 12 Gálvez AO. Schaack CP. Noda H. Bode JW. J. Am. Chem. Soc. 2017; 139: 1826 13 General Procedure for the Synthesis of Aryl Carboxylates A mixture of phenol 1 (0.50 mmol), Na2CO3 (10.6 mg, 0.10 mmol, 20 mol%), and alkenyl carboxylate (2.0 mmol, 4.0 equiv) in MeCN (3 mL) was added to a Schlenk flask (25 mL) and stirred at r.t. The mixture was stirred at 120 °C until the reaction was finished. Then, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (petroleum ether/ethyl acetate 20:1 to 10:1) to afford the product 3. Naphthalen-2-yl Acetate (3aa) Yield: 99%, 92.8 mg, white solid, mp 70–72 °C. 1H NMR (400 MHz, CDCl3): δ = 7.81–7.72 (m, 3 H), 7.50 (d, J = 2.2 Hz, 1 H), 7.45–7.37 (m, 2 H), 7.19–7.15 (m, 1 H), 2.29 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 169.7, 148.3, 133.7, 131.4, 129.4, 127.8, 127.6, 126.6, 125.7, 121.1, 118.5, 21.2 ppm. HRMS: m/z calcd for C12H10O2Na [M + Na]+: 209.0578; found: 209.0582. Supplementary Material Supplementary Material Supporting Information
