Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylate...Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.展开更多
A novel three-component reaction of o-bromobenzaldehyde, terminal alkynes and tert-butyl amine has been established, which proceeded smoothly to give 3-substituted isoquinolines in good yields in the presence of palla...A novel three-component reaction of o-bromobenzaldehyde, terminal alkynes and tert-butyl amine has been established, which proceeded smoothly to give 3-substituted isoquinolines in good yields in the presence of palladium/copper catalysts under microwave irradiation.展开更多
The 4,4′-biisofraxidin, isolated from balsamina L. was synthesized for the first time in the total yield of 7% by 11 steps, in which the key step was the cyclization and Ni(0)-catalyzed coupling reaction.
Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts,enabling the selective formation of[12]cycloparaphenylene precursor with...Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts,enabling the selective formation of[12]cycloparaphenylene precursor with separate yield up to 25%in one-pot reactions,much higher than that in homogeneous reaction.The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation,offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.展开更多
A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,...A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.展开更多
Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic s...Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic stability,lipophilicity,excellent chemical and thermal stability.Therefore,various synthetic strategies have been developed for the construction of fluoroalkyl-containing compounds,using highly active fluorinating reagents and fluorinated building blocks.Recently,the use of easily available and inexpensive trifluoroacetic anhydride(TFAA)and its anhydride analogues has attracted great attention to access numerous fluoroalkyl-containing compounds through cyclization and coupling reactions.In this review,we summarized the recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides as reagents.This review aims to provide a reference for researchers on how to develop new synthetic straregies of fluorine-containing organic compounds and achieve kilograms or even tons preparation of fluorine-containing organic compounds using fluoroalkyl anhydrides.展开更多
The first total synthesis of （±）-palstatin was achieved from commercially available 5-bromovanallin and 2,4,6-trihydroxyacetophenone. SeO2 promoted oxidative cyclization reaction and Ag20 catalyzed oxidative co...The first total synthesis of （±）-palstatin was achieved from commercially available 5-bromovanallin and 2,4,6-trihydroxyacetophenone. SeO2 promoted oxidative cyclization reaction and Ag20 catalyzed oxidative coupling reaction served as the key steps in the synthesis successfully.展开更多
While studying the electrophilic cyclization of acetylenic malonates in synthesizing malonate indene derivatives with high regio and stereo-selectivity, we found that the CH2 and CH3 protons of two COOCH2CH3 groups in...While studying the electrophilic cyclization of acetylenic malonates in synthesizing malonate indene derivatives with high regio and stereo-selectivity, we found that the CH2 and CH3 protons of two COOCH2CH3 groups in some diethyl malonate indene derivatives showed very interesting spin-spin coupling and signal multiplicity. To explain those phenomena, we synthesized several diethyl malonate indene derivatives, and then used 1H NMR spectra and molecular modeling to investigate the CH2CH3 spin system of these two COOCH2CH3 groups in detail. The results showed that the spin systems of CH3CH2 of the two COOCH2CH3 groups in those compounds may exist in different froms (AMX3, ABX3 and A2X3), and the effect of the aromatic ring induced by the phenyl group at the end of the triple bond is the main reason responsible for those phenomena.展开更多
A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized, and its structure was confirmed by ^1H NMR, ^13C NMR, MS, UV-vis and elemental analysis. The key steps of the synthesis invo...A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized, and its structure was confirmed by ^1H NMR, ^13C NMR, MS, UV-vis and elemental analysis. The key steps of the synthesis involved the Stille cross-coupling reaction and followed by selective β-β oxidative cyclization of pendant thienyl rings by FeCl3 under mild conditions.展开更多
The intermolecular reductive coupling cyclization reactions of 1,1-dicyanoalkenes promoted by Sm-0/cat. HgCl2 were studied. A possible reaction mechanism was proposed.
基金supported by NSFC(22371008),BNLMSLaboratory for Synthetic Chemistry and Chemical Biology of Health@InnoHK of ITC,HKSAR.
文摘Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.
基金Acknowledgement This work was supported by the National Natural Science Foundation of China （No. 21002038） and the Self-determined Research Funds of CCNU from the Colleges＇ Basic Research and Operation of MOE （No. CCNU09A01014）.
文摘A novel three-component reaction of o-bromobenzaldehyde, terminal alkynes and tert-butyl amine has been established, which proceeded smoothly to give 3-substituted isoquinolines in good yields in the presence of palladium/copper catalysts under microwave irradiation.
文摘The 4,4′-biisofraxidin, isolated from balsamina L. was synthesized for the first time in the total yield of 7% by 11 steps, in which the key step was the cyclization and Ni(0)-catalyzed coupling reaction.
基金the financial support from the National Natural Science Foundation of China(Nos.22171083,21674035)the Fundamental Research Funds for the Central Universities(No.22221818014)+1 种基金the Shanghai Leading Academic Discipline Project(No.B502)the“Eastern Scholar Professorship”support from the Shanghai local government。
文摘Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts,enabling the selective formation of[12]cycloparaphenylene precursor with separate yield up to 25%in one-pot reactions,much higher than that in homogeneous reaction.The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation,offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.
基金financial support from the National Natural Science Foundation of China(No.22171215)the Excellent Youth Foundation of Hubei Scientific Committee(No.2022CFA092)the GuangDong Basic and Applied Basic Research Foundation(No.2022A1515110113).
文摘A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.
基金supported by the National Natural Science Foundation of China(Nos.21772022,and 22171124)Minjiang University(No.MJY21041)Fuzhou University.
文摘Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic stability,lipophilicity,excellent chemical and thermal stability.Therefore,various synthetic strategies have been developed for the construction of fluoroalkyl-containing compounds,using highly active fluorinating reagents and fluorinated building blocks.Recently,the use of easily available and inexpensive trifluoroacetic anhydride(TFAA)and its anhydride analogues has attracted great attention to access numerous fluoroalkyl-containing compounds through cyclization and coupling reactions.In this review,we summarized the recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides as reagents.This review aims to provide a reference for researchers on how to develop new synthetic straregies of fluorine-containing organic compounds and achieve kilograms or even tons preparation of fluorine-containing organic compounds using fluoroalkyl anhydrides.
基金Project supported by the National Natural Science Foundation of China （Nos. 20472025 and QT 20021001）.
文摘The first total synthesis of （±）-palstatin was achieved from commercially available 5-bromovanallin and 2,4,6-trihydroxyacetophenone. SeO2 promoted oxidative cyclization reaction and Ag20 catalyzed oxidative coupling reaction served as the key steps in the synthesis successfully.
文摘While studying the electrophilic cyclization of acetylenic malonates in synthesizing malonate indene derivatives with high regio and stereo-selectivity, we found that the CH2 and CH3 protons of two COOCH2CH3 groups in some diethyl malonate indene derivatives showed very interesting spin-spin coupling and signal multiplicity. To explain those phenomena, we synthesized several diethyl malonate indene derivatives, and then used 1H NMR spectra and molecular modeling to investigate the CH2CH3 spin system of these two COOCH2CH3 groups in detail. The results showed that the spin systems of CH3CH2 of the two COOCH2CH3 groups in those compounds may exist in different froms (AMX3, ABX3 and A2X3), and the effect of the aromatic ring induced by the phenyl group at the end of the triple bond is the main reason responsible for those phenomena.
文摘A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized, and its structure was confirmed by ^1H NMR, ^13C NMR, MS, UV-vis and elemental analysis. The key steps of the synthesis involved the Stille cross-coupling reaction and followed by selective β-β oxidative cyclization of pendant thienyl rings by FeCl3 under mild conditions.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 33)andtheNaturalScienceFoundationofZhejiangProvince (No .2 980 6 7) .
文摘The intermolecular reductive coupling cyclization reactions of 1,1-dicyanoalkenes promoted by Sm-0/cat. HgCl2 were studied. A possible reaction mechanism was proposed.
