Since the first report of sodium trifluoromethanesulfinate(CF_(3)SO_(2)Na) as an electrophilic trifluoromethylthiolation reagent in 2015,there has been no breakthrough in research in this field.Herein,we disclose an u...Since the first report of sodium trifluoromethanesulfinate(CF_(3)SO_(2)Na) as an electrophilic trifluoromethylthiolation reagent in 2015,there has been no breakthrough in research in this field.Herein,we disclose an unprecedented usage of CF_(3)SO_(2)Na as a radical trifluoromethylthiolation reagent.A photocatalyzed ditrifluoromethylthiolation of alkenes with CF_(3)SO_(2)Na in the presence of PPh_(3) and catalytic copper has been developed.Interestingly,either Ir[(p-Fppy)_(2)(bpy)]PF_6 or Ir(ppy)_(3) could facilitate this transformation.Mechanistic studies indicate that initiation of the radical chain proceeded via two different photocatalytic quenching mechanisms.This protocol provides a practical method for the construction of diverse vicinal ditrifluoromethylthiolated compounds.展开更多
A new,stable and scalable reagent for deuteriodifluoromethylthiolation(deuterated N-difluoromethylthiophthalimide,PhthSCF_(2)D)has been developed.This reagent can be applied for the photocatalytic radical deuteriodifl...A new,stable and scalable reagent for deuteriodifluoromethylthiolation(deuterated N-difluoromethylthiophthalimide,PhthSCF_(2)D)has been developed.This reagent can be applied for the photocatalytic radical deuteriodifluoromethylthiolation of various olefins and aldehydes(30 examples).Meanwhile,it can achieve the electrophilic deuteriodifluoromethylthiolation of a series of electrophilic substrates including electron-rich arenes,aryl/vinylboronicacids,alkynes,amines,thiols andβ-ketoesters(22 examples).Some complex molecules can also be applied in both radical and electrophilic deuteriodifluoromethylthiolation using PhthSCF_(2)D as the reagent.展开更多
基金supported by the National Natural Science Foundation of China (22078161,22108124)the Postdoctoral Science Foundation Funded Project (2019M661848)+1 种基金the Fundamental Research Funds for the Central Universities (30922010403)the Priority Academic Program Development of Jiangsu Higher Education Institutions,the Center for Advanced Materials and Technology in Nanjing University of Science and Technology。
文摘Since the first report of sodium trifluoromethanesulfinate(CF_(3)SO_(2)Na) as an electrophilic trifluoromethylthiolation reagent in 2015,there has been no breakthrough in research in this field.Herein,we disclose an unprecedented usage of CF_(3)SO_(2)Na as a radical trifluoromethylthiolation reagent.A photocatalyzed ditrifluoromethylthiolation of alkenes with CF_(3)SO_(2)Na in the presence of PPh_(3) and catalytic copper has been developed.Interestingly,either Ir[(p-Fppy)_(2)(bpy)]PF_6 or Ir(ppy)_(3) could facilitate this transformation.Mechanistic studies indicate that initiation of the radical chain proceeded via two different photocatalytic quenching mechanisms.This protocol provides a practical method for the construction of diverse vicinal ditrifluoromethylthiolated compounds.
基金the National Natural Science Foundation of China (Nos. 21776138, 22078161)the Fundamental Research Funds for the Central Universities (Nos. 30920021124, 30918011314)+3 种基金the Natural Science Foundation of Jiangsu Province (No. BK20180476)the Postdoctoral Science Foundation Funded Project (No. 2019M661848)the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Center for Advanced Materials and Technology in Nanjing University of Science and Technology for their financial support
文摘A new,stable and scalable reagent for deuteriodifluoromethylthiolation(deuterated N-difluoromethylthiophthalimide,PhthSCF_(2)D)has been developed.This reagent can be applied for the photocatalytic radical deuteriodifluoromethylthiolation of various olefins and aldehydes(30 examples).Meanwhile,it can achieve the electrophilic deuteriodifluoromethylthiolation of a series of electrophilic substrates including electron-rich arenes,aryl/vinylboronicacids,alkynes,amines,thiols andβ-ketoesters(22 examples).Some complex molecules can also be applied in both radical and electrophilic deuteriodifluoromethylthiolation using PhthSCF_(2)D as the reagent.
