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Enantioselective Electrophilic Trifluoromethylthiolation of β-Ketoesters: A Case of Reactivity and Selectivity Bias for Organocatalysis

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [2];  [1]
  1. Chinese Academy of Sciences (CAS), Shanghai (China). Shanghai Inst. of Organic Chemistry, Key Lab. of Organofluorine Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Molecular Biophysics
+ Show Author Affiliations

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. In conclusion, reactions of tetralone- or 1-benzosuberone-derived β-ketoesters occurred with moderate to good enantioselectivity with a quinine-derived PTC.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE; National Natural Science Foundation of China; National Basic Research Program of China; Key Program of Natural Science Foundation of China
DOE Contract Number:
AC05-00OR22725
OSTI ID:
1376301
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 52; ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

References (11)

In the Golden Age of Organocatalysis journal October 2004
Enantioselective organocatalyzed Henry reaction with fluoromethyl ketones journal January 2008
Asymmetric Organic Catalysis with Modified Cinchona Alkaloids journal May 2004
New Method for Trifluoromethylation of Enolate Anions and Applications to Regio-, Diastereo- and Enantioselective Trifluoromethylation journal September 1994
Enantioselective Friedel−Crafts Reaction of β-Trifluoromethylated Acrylates with Pyrroles and Its Application to the Synthesis of Trifluorinated Heliotridane journal February 2010
α-Fluorinated Ethers, Thioethers, and Amines:  Anomerically Biased Species journal March 2005
Asymmetric Construction of Stereogenic Carbon Centers Featuring a Trifluoromethyl Group from Prochiral Trifluoromethylated Substrates journal November 2010
Partition coefficients and their uses journal December 1971
Asymmetric Fluorination, Trifluoromethylation, and Perfluoroalkylation Reactions journal December 2004
Cinchona Alkaloids and Their Derivatives: Versatile Catalysts and Ligands in Asymmetric Synthesis journal June 2001
A survey of Hammett substituent constants and resonance and field parameters journal March 1991

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
asymmetric synthesis
fluorine
organocatalysis
quinine
trifluoromethylthiolation