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Synlett 2020; 31(14): 1413-1417
DOI: 10.1055/s-0040-1707151
DOI: 10.1055/s-0040-1707151
letter
Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates
Authors
We acknowledge financial support from the National Natural Science Foundation of China (20702051) and the Natural Science Foundation of Zhejiang Province (LY13B020017).
Further Information
Publication History
Received: 29 January 2020
Accepted after revision: 28 May 2020
Publication Date:
16 June 2020 (online)
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
sulfuryl fluoride catalysis - alcohols - thiocyanation - ammonium thiocyanate - thiocyanatesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707151.
- Supporting Information (PDF)
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References and Notes
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- 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.
For selected SuFEx chemistry, for see: