One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.
The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction...The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.展开更多
A cascade insertion-nucleophilic annulation reaction of salicyl N-tosylimines with aryne generated in situ from 2-（trimethyl- silyl） aryl triflate and KF-18-crown-6 has been developed, providing 9-aminoxanthenes eff...A cascade insertion-nucleophilic annulation reaction of salicyl N-tosylimines with aryne generated in situ from 2-（trimethyl- silyl） aryl triflate and KF-18-crown-6 has been developed, providing 9-aminoxanthenes efficiently in one step.展开更多
An efficient Pd-catalyzed double annulation reaction of 1-(2,6-dibro mophenyl)-1 H-pyrroles with arynes is developed to synthesizeπ-extended dibenzo[d,k]ullazines in good to excellent yields.For the first time,the pa...An efficient Pd-catalyzed double annulation reaction of 1-(2,6-dibro mophenyl)-1 H-pyrroles with arynes is developed to synthesizeπ-extended dibenzo[d,k]ullazines in good to excellent yields.For the first time,the parent dibenzo[d,k]ullazine core is obtained and characterized.展开更多
Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes,which are widely utilized as ligands in transition metal-catalyzed reactions.However,efficient sy...Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes,which are widely utilized as ligands in transition metal-catalyzed reactions.However,efficient synthetic methods to access such compounds are sparse.Herein,highly valuable ortho-sulfur substituted arylphosphine oxides and arylphosphonates were constructed via difunctionalization of aryne precursors with P(O)H and elemental sulfur.This method avoids the use of transition metal catalysts and corrosive phosphorus chloride.The synthetic utility of this reaction is further demonstrated by the reduction of the synthesized products to access monophosphine ligands and their applications in cross-coupling reactions.Moreover,by introducing an alkyne moiety into the P(O)H substrate,cyclic sulfur-containing phosphines could be obtained in a one-pot reaction,which represents a new P,S structure that is inaccessible by known strategies.展开更多
Aromatic carbonyls have evoked sustained attention in the field of room-temperature phosphorescence(RTP).The introduction of carbonyl groups is a general way to achieve RTP for their effective intersystem crossing(ISC...Aromatic carbonyls have evoked sustained attention in the field of room-temperature phosphorescence(RTP).The introduction of carbonyl groups is a general way to achieve RTP for their effective intersystem crossing(ISC)by improving spin-orbit coupling(SOC).With further molecular design and processing strategies,aromatic carbonyls materials with multi-functional and high efficiency ultralong organic phosphorescence(UOP)can be obtained.This review summarizes the mechanism of aromatic carbonyls with UOP in pure aromatic carbonyls and their multi-component systems.Some detailed strategies for improving UOP performance are further introduced.The summary and outlook are presented to expound on the advances and lack of aromatic carbonyls.Further development directions and requirements are also put forward.展开更多
基金We are grateful to the National Natural Science Foundation of China （Nos. 20332060 and 2472072）
文摘One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.
基金supported by the National Natural Science Foundation of China(22001065)the Science and Technology Foundation of Hunan Province(2021JJ30090)+3 种基金Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)Shenzhen Science and Technology Program(KQTD20210811090112004)supported by Center for Computational Science and Engineering at SUSTechthe CHEM high-performance supercomputer cluster(CHEM-HPC)located at the Department of Chemistry,SUSTech。
文摘The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.
基金the National Natural Science Foundation of China(No.21162022)the Team Innovation Project of Shihezi University(No.2011ZRKETD-04) for financial support
文摘A cascade insertion-nucleophilic annulation reaction of salicyl N-tosylimines with aryne generated in situ from 2-（trimethyl- silyl） aryl triflate and KF-18-crown-6 has been developed, providing 9-aminoxanthenes efficiently in one step.
基金the financial support from the National Natural Science Foundation of China(No.21772134)the Fundamental Research Funds for the Central Universities(No.20826041D4117)。
文摘An efficient Pd-catalyzed double annulation reaction of 1-(2,6-dibro mophenyl)-1 H-pyrroles with arynes is developed to synthesizeπ-extended dibenzo[d,k]ullazines in good to excellent yields.For the first time,the parent dibenzo[d,k]ullazine core is obtained and characterized.
基金Financial support from National Natural Science Foundation of China(grant nos.21772046 and 21931013)the Natural Science Foundation of Fujian Province of China(grant nos.2019J05095 and 2022J02009)the Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University(grant no.ZQN-705),and Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University are gratefully acknowledged.The authors also thank the Instrumental Analysis Center of Huaqiao University for analysis support.Y.Guo thank the Subsidized Project for Cultivating Postgraduates’Innovative Ability in Scientific Research of Huaqiao University.
文摘Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes,which are widely utilized as ligands in transition metal-catalyzed reactions.However,efficient synthetic methods to access such compounds are sparse.Herein,highly valuable ortho-sulfur substituted arylphosphine oxides and arylphosphonates were constructed via difunctionalization of aryne precursors with P(O)H and elemental sulfur.This method avoids the use of transition metal catalysts and corrosive phosphorus chloride.The synthetic utility of this reaction is further demonstrated by the reduction of the synthesized products to access monophosphine ligands and their applications in cross-coupling reactions.Moreover,by introducing an alkyne moiety into the P(O)H substrate,cyclic sulfur-containing phosphines could be obtained in a one-pot reaction,which represents a new P,S structure that is inaccessible by known strategies.
基金financially supported by the Shandong Provincial Natural Science Foundation(Nos.ZR2021JQ16,ZR2019YQ19and ZR2019BEM018)the Project of Shandong Province Higher Educational Science and Technology Program(No.2019KJA026)+1 种基金the National Natural Science Foundation of China(Nos.51403113 and 52072193)the Shandong Provincial College Students'Innovative Entrepreneurial Training(No.S202111065214).
文摘Aromatic carbonyls have evoked sustained attention in the field of room-temperature phosphorescence(RTP).The introduction of carbonyl groups is a general way to achieve RTP for their effective intersystem crossing(ISC)by improving spin-orbit coupling(SOC).With further molecular design and processing strategies,aromatic carbonyls materials with multi-functional and high efficiency ultralong organic phosphorescence(UOP)can be obtained.This review summarizes the mechanism of aromatic carbonyls with UOP in pure aromatic carbonyls and their multi-component systems.Some detailed strategies for improving UOP performance are further introduced.The summary and outlook are presented to expound on the advances and lack of aromatic carbonyls.Further development directions and requirements are also put forward.
