Fluoroolefins-Mediated Deoxygenative Substitution of Alcohols: Chemo- and Enantiospecific Construction of C-S, C-N, C-O, and C-Se Bonds
Hengyuan Li, Linqian Qin, Jia Nie, Huanfeng Jiang and Chuanle Zhu*
*School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China,
Email: cechlzhu
scut.edu.cn
H. Li, L. Qin, J. Nie, H. Jiang, C. Zhu, Org. Lett., 2023, 25, 5431-5436.
DOI: 10.1021/acs.orglett.3c01713
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Abstract
A fluoroolefin-mediated deoxygenative substitution of nonactivated and activated alcohols with diverse acidic nucleophiles enables a chemo- and enantiospecific construction of C-S, C-N, C-O, and C-Se bonds with clear inversion of the configuration.
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General Procedure
A 25 mL oven-dried Schlenk tube equipped with a magnetic stirring bar, t-BuOLi (0.8 mmol, 4 equiv), alcohol (0.3 mmol, 1.5 equiv), DMSO (2 mL) and fluoroolefin activator (0.32 mmol, 1.6 equiv) was vigorously stirred at 60 °C for 12 h. After 12 hours, nucleophile (0.2 mmol, 1 equiv) was added, the mixture was stirred at 100°C for 24 hours under N2 atmosphere. Then the mixture was stopped stirring, added water (15 mL), extracted with EtOAc (15 mL ×3). The combined organic phases were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. Further purification by flash column chromatography on silica gel (eluting with petroleum ether/ethyl acetate) provided the product.
Key Words
sulfides, nucleophilic substitution
ID: J54-Y2023
