Synlett, Inhaltsverzeichnis Synlett 2020; 31(14): 1413-1417DOI: 10.1055/s-0040-1707151 letter © Georg Thieme Verlag Stuttgart · New YorkSulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates Authors Guofu Zhang Lidi Xuan Yiyong Zhao Chengrong Ding ∗ Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Abstract A novel SO2F2-promoted thiocyanation method for the one-step synthesis of thiocyanates through C–O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility. Key words Key wordssulfuryl fluoride catalysis - alcohols - thiocyanation - ammonium thiocyanate - thiocyanates Volltext Referenzen References and Notes 1 Piña IC, Gautschi JT, Wang G.-Y.-S, Sanders ML, Schmitz FJ, France D, Cornell-Kennon S, Sambucetti LC, Remiszewski SW, Perez LB, Bair KW, Crews P. J. Org. Chem. 2003; 68: 3866 2 Elhalem E, Bailey BN, Docampo R, Ujváry I, Szajnman SH, Rodriguez JB. J. Med. Chem. 2002; 45: 3984 3 Capon RJ, Skene C, Liu EH.-T, Lacey E, Gill JH, Heiland K, Friedel T. J. Org. Chem. 2001; 66: 7765 4a Lu X, Wang H, Gao R, Sun D, Bi X. RSC Adv. 2014; 4: 28794 4b Brown SP, Smith AB. III. J. Am. Chem. Soc. 2015; 137: 4034 4c Prabhu KR, Ramesha AR, Chandrasekaran S. J. Org. Chem. 1995; 60: 7142 4d Renard P.-Y, Schwebel H, Vayron P, Josien L, Valleix A, Mioskowski C. Chem. Eur. J. 2002; 8: 2910 4e Bayarmagnai B, Matheis C, Jouvin K, Goossen L.-J. Angew. Chem. Int. Ed. 2015; 54: 5753 5a Goodajdar B.-M, Akbari F, Davarpanah J. Appl. Organomet. 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Chem. 2019; 17: 4087 11 Zhao Y, Mei G, Wang H, Zhang G, Ding C. Synlett 2019; 30: 1484 12 Zhang G, Zhao Y, Xuan L, Ding C. Eur. J. Org. Chem. 2019; 4911 13 Zhao Y.-Y, Zhang G, Ding C. Org. Biomol. Chem. 2019; 17: 7684 14a Wang S.-M, Alharbi NS, Qin H.-L. Synthesis 2019; 51: 3901 14b Schimler SD, Cismesia MA, Hanley PS, Froese RD. J, Jansma MJ, Bland DC, Sanford MS. J. Am. Chem. Soc. 2017; 139: 1452 15 4-Methylbenzyl Thiocyanate (2b); Typical Procedure 4-Methylbenzyl alcohol (1b; 1.0 mmol, 1.0 equiv), NH4SCN (1.0 mmol, 1.0 equiv), Na2CO3 (4.0 mmol, 4.0 equiv), and EtOAc (2.0 mL, 0.5 M) were added sequentially to an oven-dried 30 mL reaction tube equipped with a stirrer bar. The tube was sealed with a plastic stopper and SO2F2 gas was introduced into the stirred mixture by slow bubbling from an SO2F2-filled balloon at r.t. for 5 h. The mixture was then diluted with H2O and extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated to dryness. The residue was purified by chromatography (silica gel, EtOAc–PE) to give a yellow oil; yield: 158 mg (97%). 1H NMR (500 MHz, CDCl3): δ = 7.31–7.21 (m, 2 H), 7.18 (d, J = 7.9 Hz, 2 H), 4.13 (s, 2 H), 2.35 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 138.9, 131.3, 129.8, 128.9, 112.1, 38.3, 21.2. HRMS (EI): m/z [M+] calcd for C9H9NS: 163.0456; found: 163.0458. 16 4-(Thiocyanatomethyl)phenyl Fluoridosulfate (2m) 4-(Hydroxymethyl)phenol (1m; 1.0 mmol, 1.0 equiv), NH4SCN (1.0 mmol, 1.0 equiv), Et3N (4.0 mmol, 4.0 equiv), and EtOAc (2.0 mL, 0.5 M) were added sequentially to an oven-dried 30 mL reaction tube equipped with a stirrer bar. The tube was sealed with a plastic stopper and SO2F2 gas was introduced into the stirred mixture by slow bubbling from an SO2F2-filled balloon at r.t. for 5 h. Workup as described above gave a colorless oil; yield: 193 mg (78%). 1H NMR (500 MHz, CDCl3): δ = 7.50 (d, J = 8.7 Hz, 2 H), 7.38 (d, J = 8.5 Hz, 2 H), 4.16 (s, 2 H). 13C NMR (125 MHz, CDCl3): δ = 150.1, 135.5, 131.1, 121.8, 111.2, 37.1. HRMS (EI): m/z [M+] calcd for C8H6FNO3S2: 246.9773; found: 246.9796. Zusatzmaterial Zusatzmaterial Supporting Information (PDF)
