Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of triflu...Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of trifluoromethylated alkenes and hydrazones in good to high yield under mild conditions.展开更多
1,2,3-Triazoles, as one of the most significant nitrogen-containing heterocycles due to their extensive use in biology, material science and organic synthesis, have aroused great interest, 1,2,3-Triazoles are commonly...1,2,3-Triazoles, as one of the most significant nitrogen-containing heterocycles due to their extensive use in biology, material science and organic synthesis, have aroused great interest, 1,2,3-Triazoles are commonly synthe- sized by metal-catalyzed azide-alkyne cycloaddition and organocatalytic azide-carbonyl cycloaddition, which indispensably employ the toxic and potentially explosive azides. The azide-free synthetic approaches provide a powerful and straightforward alternative to the assembly of diverse 1,2,3-triazoles without the use of azides. In this review, we summarize the recent development of the construction of 1,2,3-triazoles under azide-free conditions.展开更多
A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synth...A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.展开更多
A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to...A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.展开更多
The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migrato...The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migratory insertion process are proposed as the key steps for this reaction.展开更多
A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluor...A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.展开更多
The study toward the total synthesis of （R）-（＋）-harmicine is reported in this paper. The enantioselective syn- thesis of pyrrolidinone, the main backbone of of （R）-（＋）-harmicine, has been completed by the me...The study toward the total synthesis of （R）-（＋）-harmicine is reported in this paper. The enantioselective syn- thesis of pyrrolidinone, the main backbone of of （R）-（＋）-harmicine, has been completed by the methodology based on photo-induced Wolff rearrangement of α-diazo-β-carbonyl compounds.展开更多
基金This work was supported financially by the National Natural Science Foundation of China （Nos. 21225208, 21472137, and 21532008）, the National Basic Research Program of China （973 Program： Nos. 2014CB745100, 2015CB856500）, and the Tianjin Municipal Science ＆ Technology Commission （No. 14JCQNJC06200）.
文摘Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of trifluoromethylated alkenes and hydrazones in good to high yield under mild conditions.
基金Acknowledgement We are grateful for the financial support from the National Natural Science Foundation of China （Grant Nos. 21602202）, the Science Foundation of Zhejiang Sci-Tech University （Grant Nos. 15062092-Y, 1206820-Y and 1206821-Y） as well as the Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University.
文摘1,2,3-Triazoles, as one of the most significant nitrogen-containing heterocycles due to their extensive use in biology, material science and organic synthesis, have aroused great interest, 1,2,3-Triazoles are commonly synthe- sized by metal-catalyzed azide-alkyne cycloaddition and organocatalytic azide-carbonyl cycloaddition, which indispensably employ the toxic and potentially explosive azides. The azide-free synthetic approaches provide a powerful and straightforward alternative to the assembly of diverse 1,2,3-triazoles without the use of azides. In this review, we summarize the recent development of the construction of 1,2,3-triazoles under azide-free conditions.
文摘A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.
文摘A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.
基金The project is supported by the National Basic Research Pro- gram of China （973 Program, No. 2015CB856600） and the Natio- anal Natural Science Foundation of China （Grant 21332002, 21472004）.
文摘The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migratory insertion process are proposed as the key steps for this reaction.
文摘A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.
基金The project is supported by the National Natural Science Foundation of China （No. 21072009, 21172005）, National Basic Research Program of China （973 Program, No. 2009CB825300） and the Research Fund for the Doctoral Program of Higher Education （No 20090001120014）.
文摘The study toward the total synthesis of （R）-（＋）-harmicine is reported in this paper. The enantioselective syn- thesis of pyrrolidinone, the main backbone of of （R）-（＋）-harmicine, has been completed by the methodology based on photo-induced Wolff rearrangement of α-diazo-β-carbonyl compounds.
基金Project supported by the National Natural Science Foundation of China(Nos.21432011,21772224)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(No.QYZDY-SSW-SLH016),the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB20000000)+1 种基金the Natural Science Foundation of Shanghai City(No.17ZR1436900)the Start-up Research Fund of Nanjing Agricultural University(No.050-804099)~~
