Silver-Mediated Oxidative Aliphatic CH Trifluoromethylthiolation

• Published in: Angewandte Chemie International Edition Vol. 54; no. 13; pp. 4065 - 4069
• Main Authors: Guo, Shuo, Zhang, Xiaofei, Tang, Pingping
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 23.03.2015; WILEY‐VCH Verlag; Wiley
• Subjects: Aliphatic compounds; Amino Acids - chemistry; Biological Products - chemistry; Chemistry; Chemistry, Multidisciplinary; Compatibility; CH activation; Derivatives; fluorine; Hydrocarbons, Fluorinated - chemical synthesis; Indicators and Reagents; Models, Molecular; Molecular Conformation; Natural products; Oxidation-Reduction; Physical Sciences; radicals; Science & Technology; Silver Compounds - chemistry; Sulfates - chemistry; Sulfhydryl Compounds - chemical synthesis; Synthesis; synthetic methods; trifluoromethylthiolation; radicals; trifluoromethylthiolation; UNACTIVATED ALKENES; AQUEOUS-SOLUTION; ELEMENTAL SULFUR; C-H activation; ARYL BORONIC ACIDS; HYPERVALENT IODINE REAGENT; ALPHA-FLUORINATED ETHERS; COPPER-CATALYZED TRIFLUOROMETHYLTHIOLATION; ELECTROPHILIC TRIFLUOROMETHANESULFANYLATION; SELECTIVE TRIFLUOROMETHYLTHIOLATION; synthetic methods; fluorine; CARBOXYLIC-ACIDS; CH activation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201411807

The first example of a practical and direct trifluoromethylthiolation reaction of unactivated aliphatic CH bonds employs a silver‐based reagent. The reaction is operationally simple, scalable, and proceeds under aqueous conditions in air. Furthermore, its broad scope and good functional‐group compatibility were demonstrated by applying this method to the selective trifluoromethylthiolation of natural products and natural‐product derivatives. The silver‐mediated trifluoromethylthiolation of unactivated aliphatic CH bonds is reported. The reaction is operationally simple, amenable to gram‐scale synthesis, and can be employed for the late‐stage trifluoromethylthiolation of complex small molecules.