Fluorinated heterocycles play a vital role in pharmaceutical and agrochemical industries.Hence,rapid and efficient construction of fluorinated heterocycles remains highly demanded.Herein,a difluoroalkylative carbonyla...Fluorinated heterocycles play a vital role in pharmaceutical and agrochemical industries.Hence,rapid and efficient construction of fluorinated heterocycles remains highly demanded.Herein,a difluoroalkylative carbonylative cyclization of unactivated alkenes and ethylene gas enabled by palladium catalysis has been developed for the first time toward the synthesis ofα-carbonyl difluoro-modified glutarimides.This procedure can also be applied to the synthesis of Ge Migliptin which is a medicine approved for the treatment of type 2 diabetes mellitus.展开更多
Visible-light-mediated para-C-H difluoroalkylation of anilides via combination of steric effects and Lewis acid activation strategies has been developed. The addition of(C_6H_5O)_(2)P(O)OH and Ag_(2)CO_(3) properly tu...Visible-light-mediated para-C-H difluoroalkylation of anilides via combination of steric effects and Lewis acid activation strategies has been developed. The addition of(C_6H_5O)_(2)P(O)OH and Ag_(2)CO_(3) properly tune the redox potential of ruthenium catalyst and leads to mild reaction conditions. The protocol exhibits broad functional group tolerance and allows the late-stage functionalization of complex bioactive molecules.展开更多
A Ru(Ⅱ)-catalyzed para-difluoroalkylation of aro matic alde hydes and ketones with a tra nsient directing group has been developed.It utilizes less expensive ruthenium catalysts and allows facile access to challengin...A Ru(Ⅱ)-catalyzed para-difluoroalkylation of aro matic alde hydes and ketones with a tra nsient directing group has been developed.It utilizes less expensive ruthenium catalysts and allows facile access to challenging difluoroalkylated aldehydes.The mechanism studies suggest that the distinct coordination mode of ruthenium complex with imine moieties is responsible for para-selectivity.展开更多
An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The re...An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The reaction does not need any catalyst and tolerates a wide scope of substrates,which affords the(β-chlorodifluoroethyl)phosphonate products in good to excellent yields.This reaction represents the first example of the halogenation of difluoroalkyl diazo compounds,and also provides an easy way for the synthesis of difluoromethylenephosphonate-containing compounds.展开更多
以硫化镉量子点为催化剂,在光照条件下以二氟溴乙酸乙酯为二氟烷基化试剂,高效地实现肉桂酸脱羧二氟烷基化反应,共合成了18个含有烯丙基二氟模块的化合物(3a^3r),收率53%~80%,其结构经1 H NMR,13 C NMR和19 F NMR确证。该反应条件温和,...以硫化镉量子点为催化剂,在光照条件下以二氟溴乙酸乙酯为二氟烷基化试剂,高效地实现肉桂酸脱羧二氟烷基化反应,共合成了18个含有烯丙基二氟模块的化合物(3a^3r),收率53%~80%,其结构经1 H NMR,13 C NMR和19 F NMR确证。该反应条件温和,底物适用范围广,官能团耐受性好。自由基抑制实验结果表明:反应经过自由基途径。展开更多
基金supported by the DICP and K.C.Wong Education Foundation(GJTD-2020-08)。
文摘Fluorinated heterocycles play a vital role in pharmaceutical and agrochemical industries.Hence,rapid and efficient construction of fluorinated heterocycles remains highly demanded.Herein,a difluoroalkylative carbonylative cyclization of unactivated alkenes and ethylene gas enabled by palladium catalysis has been developed for the first time toward the synthesis ofα-carbonyl difluoro-modified glutarimides.This procedure can also be applied to the synthesis of Ge Migliptin which is a medicine approved for the treatment of type 2 diabetes mellitus.
基金support from the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2017124)。
文摘Visible-light-mediated para-C-H difluoroalkylation of anilides via combination of steric effects and Lewis acid activation strategies has been developed. The addition of(C_6H_5O)_(2)P(O)OH and Ag_(2)CO_(3) properly tune the redox potential of ruthenium catalyst and leads to mild reaction conditions. The protocol exhibits broad functional group tolerance and allows the late-stage functionalization of complex bioactive molecules.
基金support from the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2017124)。
文摘A Ru(Ⅱ)-catalyzed para-difluoroalkylation of aro matic alde hydes and ketones with a tra nsient directing group has been developed.It utilizes less expensive ruthenium catalysts and allows facile access to challenging difluoroalkylated aldehydes.The mechanism studies suggest that the distinct coordination mode of ruthenium complex with imine moieties is responsible for para-selectivity.
基金supports from the National Natural Science Foundation of China (No. 21761132021)German Research Foundation (No. RO362/74–1)Qin Lan project from Jiangsu Province for JLH is also acknowledged
文摘An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The reaction does not need any catalyst and tolerates a wide scope of substrates,which affords the(β-chlorodifluoroethyl)phosphonate products in good to excellent yields.This reaction represents the first example of the halogenation of difluoroalkyl diazo compounds,and also provides an easy way for the synthesis of difluoromethylenephosphonate-containing compounds.
文摘以硫化镉量子点为催化剂,在光照条件下以二氟溴乙酸乙酯为二氟烷基化试剂,高效地实现肉桂酸脱羧二氟烷基化反应,共合成了18个含有烯丙基二氟模块的化合物(3a^3r),收率53%~80%,其结构经1 H NMR,13 C NMR和19 F NMR确证。该反应条件温和,底物适用范围广,官能团耐受性好。自由基抑制实验结果表明:反应经过自由基途径。
