The XCF_(3)groups(X=O,S,Se)play an increasingly important role in modern organic chemistry due to their unique electronegativity,lipophilic nature,metabolic stability,and bioavailability.Heterocyclic compounds are imp...The XCF_(3)groups(X=O,S,Se)play an increasingly important role in modern organic chemistry due to their unique electronegativity,lipophilic nature,metabolic stability,and bioavailability.Heterocyclic compounds are important scaffolds in many bioactive compounds and drugs.The incorporation of XCF_(3)groups into heterocyclic compounds can change their physicochemical and biological properties,which injects new vitality into the application of heterocyclic compounds in many fields such as organic chemistry,the pharmaceutical chemistry,and life sciences.In this paper,the recent progress in the synthesis of F_(3)CX-containing heterocycles is reviewed,and the application scope and mechanism of some reactions are discussed.展开更多
The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challen...The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challenge due to indirect synthetical strategies and volatile reagent which is hard to handle. Until very recently, several innovative reagents were developed to facilitate the trifluoromethoxylation reaction and make CF_3O-containing compounds more accessible. This review mainly focuses on the recent advances in new trifluoromethoxylation reagents and their usage.展开更多
The OCF_(3)group has good metabolic stability,suitable lipophilicity and special electrical properties,which can modify the properties of drugs and material molecules.In recent years,trifluoromethoxy compounds have re...The OCF_(3)group has good metabolic stability,suitable lipophilicity and special electrical properties,which can modify the properties of drugs and material molecules.In recent years,trifluoromethoxy compounds have received more and more attention.Both new reagents and new trifluoromethoxylation strategies got a breakthrough.Our group has been committed to the development of trifluoromethoxylation reagents and methods.This account focuses on describing various trifluoromethoxylation reactions with trifluoromethyl sulfonates(TFMS)and(E)-O-trifluoromethyl-benzaldoximes(TFBO)developed by our group.展开更多
Subject Code:B02 With the support by the National Natural Science Foundation of China,the research group led by Prof.Tang Pingping(汤平平)from Nankai University reported the asymmetric and direct trifluoromethoxylatio...Subject Code:B02 With the support by the National Natural Science Foundation of China,the research group led by Prof.Tang Pingping(汤平平)from Nankai University reported the asymmetric and direct trifluoromethoxylation with trifluoromethyl aryl sulfonate(TFMS)as a new展开更多
A rhodium/diene catalyzed asymmetric allylic trifluoromethoxylation reaction is reported,which afforded chiral trifluoromethoxylated allylic compounds in 52%–97%yields with up to 97%enantiomeric excess.These are the ...A rhodium/diene catalyzed asymmetric allylic trifluoromethoxylation reaction is reported,which afforded chiral trifluoromethoxylated allylic compounds in 52%–97%yields with up to 97%enantiomeric excess.These are the first examples of asymmetric allylic trifluoromethoxylation.The reactions proceed via a dynamic kinetic process that allowed for the use of racemic allylic trichloroacetimidates as substrates.Density functional theory calculations showed that the formation of the C–OCF_(3)bond occurs via outer-sphere nucleophilic attack.Importantly,the presence of the allylic group in the products enabled them to be converted into a diverse array of optically active trifluoromethylated molecules that are otherwise difficult to access.展开更多
Comprehensive Summary,The trifluoromethoxy functional group has received increasing attention in recent years due to its distinctive properties such as good metabolic stability,appropriate lipophilicity and special el...Comprehensive Summary,The trifluoromethoxy functional group has received increasing attention in recent years due to its distinctive properties such as good metabolic stability,appropriate lipophilicity and special electrical properties.Thus,the development of new reagents and new strategies of direct trifluoromethoxylation are attracting the enthusiasm of many fluorine chemical workers.At present,nucleophilic and radical trifluoromethoxylating reagents have made major breakthroughs,greatly promoting the development of trifluoromethoxy chemistry.展开更多
The synthesis of fluorine-containing molecules has received intensive attention in recent years due to the great value of fluorides, however, the transition metal-catalyzed asymmetric construction of C-F bonds is much...The synthesis of fluorine-containing molecules has received intensive attention in recent years due to the great value of fluorides, however, the transition metal-catalyzed asymmetric construction of C-F bonds is much less developed. This review presents the recent advancement of transition metal-catalyzed asymmetric fluorination reactions, in which the final C-F bond is from reductive elimination of organometallic complexes. In addition, the perspective of the field is also provided for the future studies of asymmetric fluorinations and the related transformations, such as trJfluoromethylation, trifluorometbylthiolation and trifluoromethoxylation.展开更多
基金supported by the National Natural Science Foundation of China(No.21801007)。
文摘The XCF_(3)groups(X=O,S,Se)play an increasingly important role in modern organic chemistry due to their unique electronegativity,lipophilic nature,metabolic stability,and bioavailability.Heterocyclic compounds are important scaffolds in many bioactive compounds and drugs.The incorporation of XCF_(3)groups into heterocyclic compounds can change their physicochemical and biological properties,which injects new vitality into the application of heterocyclic compounds in many fields such as organic chemistry,the pharmaceutical chemistry,and life sciences.In this paper,the recent progress in the synthesis of F_(3)CX-containing heterocycles is reviewed,and the application scope and mechanism of some reactions are discussed.
基金supported by the National Key Research and Development Program of China(2016YFA0602900)the National Natural Science Foundation of China(21522205,21672110)the Fundamental Research Funds for the Central Universities
文摘The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challenge due to indirect synthetical strategies and volatile reagent which is hard to handle. Until very recently, several innovative reagents were developed to facilitate the trifluoromethoxylation reaction and make CF_3O-containing compounds more accessible. This review mainly focuses on the recent advances in new trifluoromethoxylation reagents and their usage.
基金We are deeply indebted to all of the group members.We also thank the National Key Research and Development Program of China(2016YFA0602900)NFSC(21672110,21925105)+1 种基金the Natu-ral Science Foundation of Tianjin(Grant No.18JCIQJC47000)the Fundamental Research Funds for the Central Universities for financial support.
文摘The OCF_(3)group has good metabolic stability,suitable lipophilicity and special electrical properties,which can modify the properties of drugs and material molecules.In recent years,trifluoromethoxy compounds have received more and more attention.Both new reagents and new trifluoromethoxylation strategies got a breakthrough.Our group has been committed to the development of trifluoromethoxylation reagents and methods.This account focuses on describing various trifluoromethoxylation reactions with trifluoromethyl sulfonates(TFMS)and(E)-O-trifluoromethyl-benzaldoximes(TFBO)developed by our group.
文摘Subject Code:B02 With the support by the National Natural Science Foundation of China,the research group led by Prof.Tang Pingping(汤平平)from Nankai University reported the asymmetric and direct trifluoromethoxylation with trifluoromethyl aryl sulfonate(TFMS)as a new
基金supported by the National Key Research and Development Program of China(grant no.2021YFF0701700)the National Natural Science Foundation of China(grant nos.21925105,92156001,and 22101141)+1 种基金the Natural Science Foundation of Tianjin(grant no.18JCJQJC47000)the Haihe Laboratory of Sustainable Chemical Transformations,and the Fundamental Research Funds for the Central Universities.
文摘A rhodium/diene catalyzed asymmetric allylic trifluoromethoxylation reaction is reported,which afforded chiral trifluoromethoxylated allylic compounds in 52%–97%yields with up to 97%enantiomeric excess.These are the first examples of asymmetric allylic trifluoromethoxylation.The reactions proceed via a dynamic kinetic process that allowed for the use of racemic allylic trichloroacetimidates as substrates.Density functional theory calculations showed that the formation of the C–OCF_(3)bond occurs via outer-sphere nucleophilic attack.Importantly,the presence of the allylic group in the products enabled them to be converted into a diverse array of optically active trifluoromethylated molecules that are otherwise difficult to access.
基金supported by the National Key Research and Development Program of China(2021YFF0701700)NFSC(21925105,92156001)+2 种基金the Natural Science Foundation of Tianjin(Grant No.18JCJQJC47000)NCC Fund(NCC2020FH07)the Haihe Laboratory of Sustainable Chemical Transformations,and the Fundamental Research Funds for the Central Universities.
文摘Comprehensive Summary,The trifluoromethoxy functional group has received increasing attention in recent years due to its distinctive properties such as good metabolic stability,appropriate lipophilicity and special electrical properties.Thus,the development of new reagents and new strategies of direct trifluoromethoxylation are attracting the enthusiasm of many fluorine chemical workers.At present,nucleophilic and radical trifluoromethoxylating reagents have made major breakthroughs,greatly promoting the development of trifluoromethoxy chemistry.
基金Acknowledgement We are grateful for financial support from the National Basic Research Program of China （973- 2015CB856600）, the National Nature Science Foundation of China （Nos. 21532009, 21472219 and 21672236）, Program of Shanghai Academic/Technology Research Leader （17XD1404500）, and the Strategic Priority Research Program （No. XDB20000000）.
文摘The synthesis of fluorine-containing molecules has received intensive attention in recent years due to the great value of fluorides, however, the transition metal-catalyzed asymmetric construction of C-F bonds is much less developed. This review presents the recent advancement of transition metal-catalyzed asymmetric fluorination reactions, in which the final C-F bond is from reductive elimination of organometallic complexes. In addition, the perspective of the field is also provided for the future studies of asymmetric fluorinations and the related transformations, such as trJfluoromethylation, trifluorometbylthiolation and trifluoromethoxylation.
