The electrochemical utilization of electron-deficient methylarenes for radical-radical cross-couplings remains very rare.Enabled by an umpolung strategy,the unprecedented electrochemical cross-coupling of electron-def...The electrochemical utilization of electron-deficient methylarenes for radical-radical cross-couplings remains very rare.Enabled by an umpolung strategy,the unprecedented electrochemical cross-coupling of electron-deficient methylarenes with aldehydes was developed.The paired electrolysis simultaneously generated electron-deficient benzylic radicals and ketyl radicals at both electrodes,which then underwent radical recombination,governed by polarity matching and persistent-radical effect(PRE)to afford functionalized alcohols that are not easily accessible by other methods.This protocol features catalystand external redox agent-free conditions and a formal 100%atom economy.Mechanistic studies support the radical-radical cross-coupling pathway.展开更多
The oxidative coupling of methylarenes and N,N-dialkylformamides was developed, and the appropriate reaction conditions were established. By using I2 as the catalyst, and tert-butyl hydroperoxide(TBHP) as the oxidant,...The oxidative coupling of methylarenes and N,N-dialkylformamides was developed, and the appropriate reaction conditions were established. By using I2 as the catalyst, and tert-butyl hydroperoxide(TBHP) as the oxidant, the reaction provided N,N-dialkylamides or N-alkylamides with moderate yields via multiple sp3 C-H bonds activation of methylarenes in aqueous and metal-free conditions.展开更多
A novel copper-catalyzed dual oxidative benzylic C–H aminations of methylarenes with 2-aminobenzoketones in the presence of ammonium acetate was developed. This reaction represents a new avenue for 2-arylquinazolines...A novel copper-catalyzed dual oxidative benzylic C–H aminations of methylarenes with 2-aminobenzoketones in the presence of ammonium acetate was developed. This reaction represents a new avenue for 2-arylquinazolines with good yields. A key intermediate was detected and the kinetics isotope effect（KIE） indicated that C–H bond cleavage was the rate-determining step.展开更多
基金the National Natural Science Foundation of China(grant nos.22271009 and 22171015)Beijing Natural Science Foundation(grant no.2222003)Beijing Municipal Education Committee Project(grant nos.KZ202110005003 and KM202110005006).
文摘The electrochemical utilization of electron-deficient methylarenes for radical-radical cross-couplings remains very rare.Enabled by an umpolung strategy,the unprecedented electrochemical cross-coupling of electron-deficient methylarenes with aldehydes was developed.The paired electrolysis simultaneously generated electron-deficient benzylic radicals and ketyl radicals at both electrodes,which then underwent radical recombination,governed by polarity matching and persistent-radical effect(PRE)to afford functionalized alcohols that are not easily accessible by other methods.This protocol features catalystand external redox agent-free conditions and a formal 100%atom economy.Mechanistic studies support the radical-radical cross-coupling pathway.
基金This work was supported by the National Natural Science Foundation of China(21272117,20972068)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘The oxidative coupling of methylarenes and N,N-dialkylformamides was developed, and the appropriate reaction conditions were established. By using I2 as the catalyst, and tert-butyl hydroperoxide(TBHP) as the oxidant, the reaction provided N,N-dialkylamides or N-alkylamides with moderate yields via multiple sp3 C-H bonds activation of methylarenes in aqueous and metal-free conditions.
基金the National Nature Science Foundation of China (Nos. 2127222, 91213303, 21172205, 21432009, 21472177)
文摘A novel copper-catalyzed dual oxidative benzylic C–H aminations of methylarenes with 2-aminobenzoketones in the presence of ammonium acetate was developed. This reaction represents a new avenue for 2-arylquinazolines with good yields. A key intermediate was detected and the kinetics isotope effect（KIE） indicated that C–H bond cleavage was the rate-determining step.
