The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.I...The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.展开更多
The kinetic model for diffusion-controlled intermolecular reaction of homogenous polymer under steady shear was theoretically studied. The classic formalism and the concept of conformation ellipsoids were integrated t...The kinetic model for diffusion-controlled intermolecular reaction of homogenous polymer under steady shear was theoretically studied. The classic formalism and the concept of conformation ellipsoids were integrated to get a new equation, which directly correlates the rate constant with shear rate. It was found that the rate constant is not monotonic with shear rate. The scale of rate constant is N^-1.5 （N is the length of chains）, which is in consistent with de Gennes＇s result.展开更多
A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed d...A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed dimerization of biarylmercurials was studied, and shown to be mainly intermolecular reaction.展开更多
Three asymmetrically substituted cyclohexanes were prepared from one-pot reactions of aldehydes and methylketones, and the products were characterized by single crystal structure analysis, NMR spectroscopy and microan...Three asymmetrically substituted cyclohexanes were prepared from one-pot reactions of aldehydes and methylketones, and the products were characterized by single crystal structure analysis, NMR spectroscopy and microanalysis.展开更多
The miscibility of the blend,composed of a bisphenol A epoxy resins (Diglycidyl ether of bisphenol A) (DGEBA) and poly(ethylene oxide) (PEG) and crosslinked by phthalic anhydride (PA) was studied using dynamic mechani...The miscibility of the blend,composed of a bisphenol A epoxy resins (Diglycidyl ether of bisphenol A) (DGEBA) and poly(ethylene oxide) (PEG) and crosslinked by phthalic anhydride (PA) was studied using dynamic mechanical method. Single glass transition temperatures intermediate between the two pure components were observed for all blend levels. The secondary relaxation mechanism should relate to not only diester linkage, but also hydroxyether structural unit in the system. Fourier transform infrared spectroscopy (FTIR) is applied to study the curing reaction and intermolecular specific interaction of the system. The results indicate the PEO participates the crosslinking reaction, accelerates the curing reaction and make the reaction more perfect. The shifts of the hydroxyl band and carbonyl band demonstrate the presence of the intermolecular interaction in the cured blend. Moreover, the molecular interaction between the side hydroxyl in the hydroxyether units and the ether bond in PEO macromolecules is stronger.展开更多
A series of structurally novel multifunctional chiral aminophosphine catalysts were developed through a concise synthetic strategy from easily available starting materials.The highly enantioselective intermolecular cr...A series of structurally novel multifunctional chiral aminophosphine catalysts were developed through a concise synthetic strategy from easily available starting materials.The highly enantioselective intermolecular cross Rauhut-Currier reactions of vinyl ketones with 3-acyl acrylates and 2-ene-1,4-diones catalyzed by(S,S)-5a were well realized,generating a wide range of the structurally important chiral multicarbonyl products in good to excellent yields with high stereocontrol(up to 97%yield,99%ee).In addition,a series of 31P NMR experiments were carried out to further investigate the catalytic process.展开更多
The Diels–Alder(D–A)reaction is one of the most powerful reactions in organic synthesis.The intermolecular D–A reaction attracts much less attentions than its intramolecular counterpart in natural product synthesis...The Diels–Alder(D–A)reaction is one of the most powerful reactions in organic synthesis.The intermolecular D–A reaction attracts much less attentions than its intramolecular counterpart in natural product synthesis,possibly due to the issues of reactivity and selectivity.In the past decade,the intermolecular D–A reaction has been increasingly utilized in the total synthesis of structurally complex natural products.In this article,we present a few examples for the elegant applications of the intermolecular D–A reaction that are inspired by biosynthetic hypotheses of the target natural products.These examples demonstrate that D–A reaction is not only useful for preparing building blocks but also powerful for coupling structurally complicated and sterically demanding segments in a highly chemo-and stereo-controlled fashion,which may inspire further developments of intermolecular D–A reaction from both strategy and methodology perspectives.展开更多
基金financially supported by the State Key Program of National Natural Science Foundation of China(U21A20313)the Key Program of Qingyuan Innovation Laboratory(00221003)+2 种基金the“111”Program of Fuzhou Universitythe Natural Science Foundation of Fujian Province(2019J05040)the China Postdoctoral Science Foundation(2022M20739)。
文摘The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.
基金This work was financially supported by the National Natural Science Foundation of China (No. 50390090).
文摘The kinetic model for diffusion-controlled intermolecular reaction of homogenous polymer under steady shear was theoretically studied. The classic formalism and the concept of conformation ellipsoids were integrated to get a new equation, which directly correlates the rate constant with shear rate. It was found that the rate constant is not monotonic with shear rate. The scale of rate constant is N^-1.5 （N is the length of chains）, which is in consistent with de Gennes＇s result.
基金Supported by the Scientific Research Foundation for Returned Overseas Chinese Scholarsof Educational Ministry ofChina
文摘A series of symmetrical biaryls was synthesized from arylmercuric chlorides and biarylmercurials in the presence of [ClRh(CO) 2] 2 in hexamethylphosphoramide(HMPA). The mechanism of the [ClRh(CO) 2] 2 catalyzed dimerization of biarylmercurials was studied, and shown to be mainly intermolecular reaction.
文摘Three asymmetrically substituted cyclohexanes were prepared from one-pot reactions of aldehydes and methylketones, and the products were characterized by single crystal structure analysis, NMR spectroscopy and microanalysis.
基金This study is partially supported by the National Natural Science Foundation of China.
文摘The miscibility of the blend,composed of a bisphenol A epoxy resins (Diglycidyl ether of bisphenol A) (DGEBA) and poly(ethylene oxide) (PEG) and crosslinked by phthalic anhydride (PA) was studied using dynamic mechanical method. Single glass transition temperatures intermediate between the two pure components were observed for all blend levels. The secondary relaxation mechanism should relate to not only diester linkage, but also hydroxyether structural unit in the system. Fourier transform infrared spectroscopy (FTIR) is applied to study the curing reaction and intermolecular specific interaction of the system. The results indicate the PEO participates the crosslinking reaction, accelerates the curing reaction and make the reaction more perfect. The shifts of the hydroxyl band and carbonyl band demonstrate the presence of the intermolecular interaction in the cured blend. Moreover, the molecular interaction between the side hydroxyl in the hydroxyether units and the ether bond in PEO macromolecules is stronger.
基金support from the National Natural Science Foundation of China(Grant Nos.22071186,22071187)the Natural Science Foundation of Hubei Province(Grant Nos.2020CFA036,2021CFA069)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant No.BK20190213)the Fundamental Research Funds for the Central Universities(Grant No.2042022kf1180).
文摘A series of structurally novel multifunctional chiral aminophosphine catalysts were developed through a concise synthetic strategy from easily available starting materials.The highly enantioselective intermolecular cross Rauhut-Currier reactions of vinyl ketones with 3-acyl acrylates and 2-ene-1,4-diones catalyzed by(S,S)-5a were well realized,generating a wide range of the structurally important chiral multicarbonyl products in good to excellent yields with high stereocontrol(up to 97%yield,99%ee).In addition,a series of 31P NMR experiments were carried out to further investigate the catalytic process.
基金financially supported by the Ministry of Science&Technology(2013CB836900)the National Natural Science Foundation of China(21290180,21172235,and 21222202)the Chinese Academy of Sciences
文摘The Diels–Alder(D–A)reaction is one of the most powerful reactions in organic synthesis.The intermolecular D–A reaction attracts much less attentions than its intramolecular counterpart in natural product synthesis,possibly due to the issues of reactivity and selectivity.In the past decade,the intermolecular D–A reaction has been increasingly utilized in the total synthesis of structurally complex natural products.In this article,we present a few examples for the elegant applications of the intermolecular D–A reaction that are inspired by biosynthetic hypotheses of the target natural products.These examples demonstrate that D–A reaction is not only useful for preparing building blocks but also powerful for coupling structurally complicated and sterically demanding segments in a highly chemo-and stereo-controlled fashion,which may inspire further developments of intermolecular D–A reaction from both strategy and methodology perspectives.
