Hydrogen-atom-transfer(HAT)is an efficient way for direct C-H functionalization of inert C-H bonds,therefore it has attracted great interests in recent years.So far,various HAT catalysts have been developed.Among them...Hydrogen-atom-transfer(HAT)is an efficient way for direct C-H functionalization of inert C-H bonds,therefore it has attracted great interests in recent years.So far,various HAT catalysts have been developed.Among them,quinuclidine and its derivatives show different characters toward other HAT catalysts as they tend to abstract electron-rich and hydridic hydrogens in the presence of weak and neutral C-H bonds.These features enable direct C-H functionalization of compounds with various groups which are unable or difficult by other methods.This review summarizes recent advance of photoinduced reactions with quinuclidine and its derivatives as HAT catalysts and exhibits powerful synthetic potential by using quinuclidine and its derivatives as HAT catalysts.展开更多
U.V. irradiation of N-methylphenothiazine 1 in carbon tetrachloride produced 3-(phenothiazin-N-yl-carbonyl)-N-methylphenothiazine 2 together with the radical cation salt 1(+) CCl4- and methyl chloride, presumably via ...U.V. irradiation of N-methylphenothiazine 1 in carbon tetrachloride produced 3-(phenothiazin-N-yl-carbonyl)-N-methylphenothiazine 2 together with the radical cation salt 1(+) CCl4- and methyl chloride, presumably via a photoinduced electron transfer mechanism.展开更多
Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electr...Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to ~3TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.展开更多
Photoinduced charge transfer reaction of benzophenone(BP) with, mine was carried out in the vesicles of dicetyldimethylammonium bromide (DCDAB) over wide ranges of amine concentration (0. 01～4. 0M). Linear plots of ...Photoinduced charge transfer reaction of benzophenone(BP) with, mine was carried out in the vesicles of dicetyldimethylammonium bromide (DCDAB) over wide ranges of amine concentration (0. 01～4. 0M). Linear plots of φ^(-1) vs. [TEA]^(-1) at low concentration of amine (<0.02M) and Φ^(-1) vs. [TEA]^(-2) at high concentration were obtained. Kinetic data demonstrate that the electron transfer is promoted significantly by DCDAB vesicles and proton transfer becomes more efficient at high Rmlne concentrations, leading to a decrease of Kd/Kr and increase of Kh/Ke. The kinetic expressions of photoreaction of BP bound to DCDAB bilayer are developed.展开更多
The title compound 1 (C23H21NO2) was obtained by photoinduced reaction of flavone and N, N- dimethylaniline. The crystal structure of 1 has been determined by X-ray analysis. The crystal belongs to orthorhombic system...The title compound 1 (C23H21NO2) was obtained by photoinduced reaction of flavone and N, N- dimethylaniline. The crystal structure of 1 has been determined by X-ray analysis. The crystal belongs to orthorhombic system, space group isPbca with a= 11. 799(2), b=11. 979(1), c=25. 972(3), V=3670. 9(5) , Z=8, Mr= 343. 4, Dc = 1.26 g/cm3, μ= 5. 98 cm-1, F(000) = 876 and the final R=0.073 and Rw =0.070 for 2235 observed diffractions. Structure analysis reveals thatthe pyran ring is distorted into a C(1)-sofa con formation.展开更多
基金Financial support from National Natural Science Foundation of China(Nos.21871053 and 21532001)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01005)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD04)。
文摘Hydrogen-atom-transfer(HAT)is an efficient way for direct C-H functionalization of inert C-H bonds,therefore it has attracted great interests in recent years.So far,various HAT catalysts have been developed.Among them,quinuclidine and its derivatives show different characters toward other HAT catalysts as they tend to abstract electron-rich and hydridic hydrogens in the presence of weak and neutral C-H bonds.These features enable direct C-H functionalization of compounds with various groups which are unable or difficult by other methods.This review summarizes recent advance of photoinduced reactions with quinuclidine and its derivatives as HAT catalysts and exhibits powerful synthetic potential by using quinuclidine and its derivatives as HAT catalysts.
文摘U.V. irradiation of N-methylphenothiazine 1 in carbon tetrachloride produced 3-(phenothiazin-N-yl-carbonyl)-N-methylphenothiazine 2 together with the radical cation salt 1(+) CCl4- and methyl chloride, presumably via a photoinduced electron transfer mechanism.
文摘Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to ~3TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.
文摘Photoinduced charge transfer reaction of benzophenone(BP) with, mine was carried out in the vesicles of dicetyldimethylammonium bromide (DCDAB) over wide ranges of amine concentration (0. 01～4. 0M). Linear plots of φ^(-1) vs. [TEA]^(-1) at low concentration of amine (<0.02M) and Φ^(-1) vs. [TEA]^(-2) at high concentration were obtained. Kinetic data demonstrate that the electron transfer is promoted significantly by DCDAB vesicles and proton transfer becomes more efficient at high Rmlne concentrations, leading to a decrease of Kd/Kr and increase of Kh/Ke. The kinetic expressions of photoreaction of BP bound to DCDAB bilayer are developed.
文摘The title compound 1 (C23H21NO2) was obtained by photoinduced reaction of flavone and N, N- dimethylaniline. The crystal structure of 1 has been determined by X-ray analysis. The crystal belongs to orthorhombic system, space group isPbca with a= 11. 799(2), b=11. 979(1), c=25. 972(3), V=3670. 9(5) , Z=8, Mr= 343. 4, Dc = 1.26 g/cm3, μ= 5. 98 cm-1, F(000) = 876 and the final R=0.073 and Rw =0.070 for 2235 observed diffractions. Structure analysis reveals thatthe pyran ring is distorted into a C(1)-sofa con formation.
