Enantioselective Electrophilic Trifluoromethylthiolation of β-Ketoesters: A Case of Reactivity and Selectivity Bias for Organocatalysis†
Xueqiang Wang
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorTao Yang
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorDr. Xiaolin Cheng
Center for Molecular Biophysics, Oak Ridge National Laboratory, 1 Bethel Valley Rd, Oak Ridge, TN 37831 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Qilong Shen
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)===Search for more papers by this authorXueqiang Wang
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorTao Yang
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
These authors contributed equally to this work.
Search for more papers by this authorDr. Xiaolin Cheng
Center for Molecular Biophysics, Oak Ridge National Laboratory, 1 Bethel Valley Rd, Oak Ridge, TN 37831 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Qilong Shen
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China)===Search for more papers by this authorThe authors gratefully acknowledge financial support from the National Basic Research Program of China (2012CB821600), the Key Program of Natural Science Foundation of China (21032006), the National Natural Science Foundation of China (21172245/21172244/B020304), the Shanghai Pujiang Program (11J1412200), and SIOC.
Graphical Abstract
A chiral Lewis base or a phase-transfer catalyst (PTC) can mediate the highly enantioselective trifluoromethylthiolation of β-ketoesters with the previously developed SCF3 reagent (see scheme). Reactions of indanone-derived β-ketoesters occurred with high yield and excellent enantioselectivity with quinine as catalyst. Reactions of tetralone- or 1-benzosuberone-derived β-ketoesters occurred with moderate to good enantioselectivity with a quinine-derived PTC.
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