作者机构：
[Tang, Yong-Xing; Wu, An-Xin] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
The concept of "reaction network" represents a system that is constructed from reactions between different organic units basing on logical transformation relationships. This network is refined through multiple parallel cascade reaction sequences, showcasing attributes such as "self-direction, self-sorting, convergence and normalization". The ability of synthesizing tissues within molecular systems is a key aspect that could serve as a valuable tool for the rational design of new reactions. In this paper, we summarized our research work on self- organized reaction network in the past two decades from three aspects: self-sorting convergent integration reaction network, self-labor convergent integration reaction network and complex integration reaction network.
作者机构：
[Shen, Xi; Wu, An-Xin; Zhou, You; Yu, Zhi-Cheng; Wu, Yan-Dong; Chen, Xiang-Long; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
关键词：
Cyclization;Multisubstituted beta-pyrrolidinones;I-2-DMSO;C1 building blocks;Quaternary carbon center;Late-stage modification;Cracking
摘要：
A [2 + 1 + 1 + 1] cyclization reaction has been developed for the synthesis of multisubstituted β‐pyrrolidinones from commercially available aryl methyl ketones, primary amines, and ethyl nitroacetate. In this I2–DMSO‐meditated process, the C—NO2 bond of ethyl nitroacetate is cleaved, affording a C1 synthon, and the formation of two C—C and two C—N bonds and a quaternary carbon center are constructed in one pot. This method has good substrate compatibility and permits the late‐stage modification of pharmaceutical compounds. Comprehensive Summary A [2 + 1 + 1 + 1] cyclization reaction has been developed for the synthesis of multisubstituted β‐pyrrolidinones from commercially available aryl methyl ketones, primary amines, and ethyl nitroacetate. In this I2–DMSO‐meditated process, the C—NO2 bond of ethyl nitroacetate is cleaved, affording a C1 synthon, and the formation of two C—C and two C—N bonds and a quaternary carbon center are constructed in one pot. This method has good substrate compatibility and permits the late‐stage modification of pharmaceutical compounds.
作者机构：
[Tang, Yong-Xing; Wu, An-Xin; Wu, Chun-Yan; Wu, Yan-Dong; Chen, Xiang-Long; Yang, Dong-Sheng; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.;[Zhuang, Shi-Yi] China Jiliang Univ, Coll Life Sci, Key Lab Specialty Agri Prod Qual & Hazard Controll, Hangzhou 310018, Peoples R China.
通讯机构：
[Zhuang, SY ; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.;China Jiliang Univ, Coll Life Sci, Key Lab Specialty Agri Prod Qual & Hazard Controll, Hangzhou 310018, Peoples R China.
摘要：
A [3 + 1 + 1] cascade annulation reaction for the divergent construction of trisubstituted indolizines using sulfoxonium ylides, BrCF2CO2Me and pyridinium salts as readily available substrates has been developed. By changing the reaction conditions, this metal-free process realized selective cleavage of one or two C-F bonds of difluorocarbene and let it act as a C or CF source. Further transformation of the product presented the practicality of this reaction. A [3 + 1 + 1] cascade annulation reaction for the divergent construction of trisubstituted indolizines using sulfoxonium ylides, BrCF2CO2Me and pyridinium salts as readily available substrates has been developed.
作者机构：
[Tang, Yong-Xing; Wu, An-Xin; Wu, Chun-Yan; Wu, Yan-Dong; Du, Yong-Dong; Chen, Xiang-Long; Yang, Dong-Sheng; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
A three-component annulation reaction and trifluoromethylation for the construction of 3-(trifluoromethyl)-4H-pyrans using β-CF(3)-1,3-enynes, BrCF(2)CO(2)Et, and sulfoxonium ylides as readily available substrates has been developed. This metal-free process involves two C-F bond cleavages of β-CF(3)-1,3-enynes and a CF(3) group generated in situ from BrCF(2)CO(2)Et. This method is applicable to the late-stage modification of pharmaceutically active molecules.
作者机构：
[Wu, An-Xin; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Xiang, Jia-Chen; Xiang, JC] Southeast Univ, Sch Chem & Chem Engn, Nanjing 211189, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
通讯机构：
[Xiang, JC ] S;[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Southeast Univ, Sch Chem & Chem Engn, Nanjing 211189, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
Natural product total synthesis has trailblazed in the era of multistep synthesis. The strategic application of existing synthetic methodologies and the stepwise construction that revolves around newly developed, tailored key steps, are two basic tactics in the principle of classic retrosynthetic analysis. However, a new synthetic model, termed self-organized total synthesis, has emerged in recent years, enabling the rapid creation of specific natural products by a one-pot reaction. Distinct from conventional analysis associated with certain bond disconnections, the design of self-organized total synthesis focuses on seeking a series of self-organized reaction sequences which can be integrated compatibly under a uniform condition, therefore allowing the entire sequence to proceed in one pot, and most importantly, starting from commercially available feedstocks or biomass materials. Whilst dauntingly challenging, this synthetic strategy is more consistent with the biogenetic pathway of natural products compared with conventional counterparts, and will hopefully provide the shortest synthesis for such natural products. Through this rational analysis, one-pot total synthesis is no longer in the way of serendipity but can be precisely designed and manipulated. In this review, we account for the definition, delimitation, and categorization of self-organized total synthesis and then elucidate a comprehensive understanding of this synthetic strategy based on our intensive explorations. We also highlight the contributions of other research groups in this growing field and anticipate that it will give rise to advancing new methodologies, as well as new concepts within organic synthesis. In this review, we account for the definition, delimitation, and categorization of self-organized total synthesis and then elucidate a comprehensive understanding of this synthetic strategy based on our intensive explorations.
摘要：
An efficient synthetic method for constructing 2,3- and 2,4-disubstituted pyrimidio[1,2-b]indazole skeletons through I2-DMSO-mediated and substrate-controlled regioselective [4 + 2] cyclization is reported. The reaction conditions are mild, its operation is simple, and the substrate scope is wide. More than 60 pyrimidio[1,2-b]indazole derivatives have been synthesized, providing a new methodology for constructing related molecules and potentially enriching bioactive-molecule libraries.
作者机构：
[Xiao, Yong-Cheng; Chen, Xiang-Long; Wu, An-Xin; Wu, Chun-Yan; Wu, Yan-Dong; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.;[Tang, Bo-Cheng] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, State Key Lab Chem Biol & Drug Discovery, Kowloon, Hong Kong, Peoples R China.
通讯机构：
[Chen, XL; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
An unconventional [1 + 1 + 1 + 1 + 1 + 1] annulation process was developed for the construction of β,β-dithioketones by merging C–C and C–S bond cleavage. In this reaction, rongalite concurrently served as triple C1 units, dual sulfur(II) synthons, and a reductant for the first time. Mechanism investigation indicated that the reaction involved the self-mediated valence state change of rongalite. By performing this step-economical method, the challenging construction of C5-substituted 1,3-dithiane can be achieved under mild and simple conditions.
作者机构：
[Shen, Xi; Wu, An-Xin; Zhou, You; Yu, Zhi-Cheng; Wu, Yan-Dong; Chen, Xiang-Long; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Zheng, Kai-Lu] Guangdong Med Univ, Sch Pharm, Guangdong Prov Key Lab Res & Dev Nat Drugs, Dongguan 523808, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
In this paper, novel sulfur-containing 1,6-dihydrofuro[3,2-b]pyrazolo[3,4-e][1,4]thiazine skeletons were constructed from the simple and readily available materials enaminone, 5-aminopyrazole, and 1,4-dithiane-2,5-diol. Furthermore, a novel 1,4-dithiane-2,5-diol reaction mode has been developed through a double-dipole-reversal process induced by iodine that results in the formation of six new bonds and two new rings in a one-pot reaction. This method shows good substrate compatibility, and the products can be further modified with a variety of pharmaceuticals. Additionally, this novel skeleton exhibits good fluorescence properties in solution, enabling bright and stable green fluorescence imaging in HeLa cells.
作者机构：
[Yi, Yun-Ying; Liu, Yu-Ting; Song, Ying-Chun; Wang, Ming-Xuan; Zhang, Wen-Xin; Wang, Zi-Yue; Zhu, Yan-Ping; Sun, Yuan-Yuan] Yantai Univ, Minist Educ, Collaborat Innovat Ctr Adv Drug Delivery Syst & Bi, Sch Pharm,Key Lab Mol Pharmacol & Drug Evaluat, Yantai 264005, Shandong, Peoples R China.;[Wu, An-Xin] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;[Zhu, YP ] Y;Yantai Univ, Minist Educ, Collaborat Innovat Ctr Adv Drug Delivery Syst & Bi, Sch Pharm,Key Lab Mol Pharmacol & Drug Evaluat, Yantai 264005, Shandong, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
关键词：
Total synthesis;Oxidative cyclization;Natural products;Switchable synthesis;Luotonin alkaloids
摘要：
A total synthesis strategy was developed for the synthesis of luotonin A, B and their analogues using synergistic FeCl3/KI-catalyzed oxidative cyclization. This protocol utilizes cheap and widely available N-propargyl 2-methyl-quinazolinones and arylamines under mild conditions, and it has a wide substrate scope and high atom economy. Different natural products (luotonin A, B and derivatives) can be synthesized via a unique switchable approach. Further transformations from luotonin B to luotonin E and structural modification of natural products demonstrate the potential applications of this method. Moreover, camptothecin can also be modified with the reported protocol to afford the hydroxyl-substituted product.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年89(17):12832–12841 ISSN：0022-3263
通讯作者：
Zhu, YP;Wu, AX
作者机构：
[Wang, Run-Qing; Song, Ying-Chun; Cao, Wen-Hui; Wang, Ming-Xuan; Zhu, Yan-Ping; Sun, Yuan-Yuan] Yantai Univ, Minist Educ, Sch Pharm, Collaborat Innovat Ctr Adv Drug Delivery Syst,Key, Yantai 264005, Shandong, Peoples R China.;[Wu, An-Xin] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;[Zhu, YP ] Y;Yantai Univ, Minist Educ, Sch Pharm, Collaborat Innovat Ctr Adv Drug Delivery Syst,Key, Yantai 264005, Shandong, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
A cascade oxidation/Pictet-Spengler condensation/annulation process has been developed for the one-pot total synthesis of nitramarine, nitraridine, and their analogues. The procedure proceeded with easily available quinolines and tryptophan derivatives. A simple and metal-free approach, wide substrate scope, and functional group tolerance make it applicable for the synthesis of diverse bioactive nitramarine, nitraridine, and their derivatives. Furthermore, the bioactivity evaluation has identified two promising leading compounds 5d and 5e with potent antitumor proliferative activity against breast cancer cells.
作者：
Du, Yong-Dong;Ma, Lin-Lin;Wu, Chun-Yan;Wu, Rong-He;Yu, Zhi-Cheng;...
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年 ISSN：0022-3263
通讯作者：
Wang, JG;Wu, AX
作者机构：
[Wang, Jun-Gang; Wu, Rong-He; Ma, Lin-Lin; Du, Yong-Dong] Guizhou Minzu Univ, Sch Chem Engn, Guiyang 550025, Guizhou, Peoples R China.;[Wu, An-Xin; Zhou, You; Wu, Chun-Yan; Yu, Zhi-Cheng; Wu, Yan-Dong; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
通讯机构：
[Wu, AX ] C;[Wang, JG ] G;Guizhou Minzu Univ, Sch Chem Engn, Guiyang 550025, Guizhou, Peoples R China.;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.
摘要：
A facile one-pot synthetic method has been developed for constructing 6-oxa-spiro[4.5]decane skeletons by merging the ring-opening of benzo[c]oxepines and formal 1,2-oxygen migration reactions. More than 30 examples of the 6-oxa-spiro[4.5]decane derivatives have been synthesized under transition-metal-free conditions.
作者机构：
[Chen, Xiang-Long; Wu, An-Xin; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticides, Wuhan 430079, Peoples R China.
通讯机构：
[Chen, XL; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticides, Wuhan 430079, Peoples R China.
期刊：
Chemical Communications,2024年60(72):9781-9784 ISSN：1359-7345
通讯作者：
Wu, An-Xin
作者机构：
[Shen, Xi; Yu, Zhi-Cheng; Zhou, You; Wu, Yan-Dong] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China;State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China;[Wu, An-Xin] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China<&wdkj&>State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China
通讯机构：
[An-Xin Wu] N;National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China<&wdkj&>State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China
摘要：
An oxidant-controlled divergent synthesis of a pyrrolidone fused pyrimido[1,2-b]indazole skeleton was developed through selective cyclization of an in situ generated enone intermediate and 1H-indazol-3-amine. The one-pot, metal-free process formed three C-N bonds, one C-C bond, and a tetrasubstituted carbon stereocenter containing a hydroxyl group. This method not only allowed for the synthesis of over 60 new pyrrolidone fused pyrimido[1,2-b]indazole derivatives, but was also compatible with the transformation of complex active molecules and the derivation of target products. Significantly, product 4q exhibited aggregation-induced emission (AIE) characteristics without any further modification.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年89(4):2505-2515 ISSN：0022-3263
通讯作者：
Wu, AX
作者机构：
[Wang, Can; Zhao, Peng] Taizhou Univ, Sch Pharmaceut Sci, Inst Adv Studies, Taizhou 318000, Zhejiang, Peoples R China.;[Wu, An-Xin; Zhou, You; Zhao, Peng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
The venerable Mannich reaction using p-anisidine, an aldehyde, and a nucleophile affords a linear alpha-secondary amine motif. Herein, we report that a slight yet rational modification of the reaction inputs diverts this three-component reaction, providing a cyclic alpha-tertiary amine. 2,2-Disubstituted indolin-3-ones equipped with diverse substitution patterns on their de novo generated quaternary carbon centers are readily accessible through this unprecedented transformation. Mechanistically, a domino sequence involving a kinetically favored intramolecular 1,2-aryl migration and a copper-catalyzed aerobic oxidation of an activated alpha-aminoalkyl site is suggested to account for the reaction outcome. Three typical substrates for the Mannich reaction, p-anisidine, aldehyde, and a nucleophile, did not afford the predictable linear Mannich base under an aerobic copper oxidation condition, but rendering a 2,2-disubstituted indolin-3-one product.
期刊：
Chemical Communications,2024年60(56):7180-7183 ISSN：1359-7345
通讯作者：
Wu, AX;Zhuang, SY
作者机构：
[Tang, Yong-Xing; Wu, Hao-Xuan; Wu, An-Xin; Zhou, You; Wu, Chun-Yan; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Wu, An-Xin] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.;[Zhuang, Shi-Yi] China Jiliang Univ, Coll Life Sci, Key Lab Specialty Agriprod Qual & Hazard Controlli, Hangzhou 310018, Peoples R China.
通讯机构：
[Zhuang, SY ; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;China Jiliang Univ, Coll Life Sci, Key Lab Specialty Agriprod Qual & Hazard Controlli, Hangzhou 310018, Peoples R China.
摘要：
A novel process using N-benzylhydroxylamine hydrochloride as a “C1N1 synthon” in [2+2+1] cyclization for the construction of 1,2,5-trisubstituted imidazoles has been described for the first time. The key to realizing this process lies in capturing arylamines by in situ generated novel acyl ketonitrone intermediates. Subsequent tautomerization activates the α-C(sp3)–H of N-benzylhydroxylamines, and thus breaks through its inherent reaction mode and achieves N, α-C site-selective cyclization. Furthermore, this method enables scale-up synthesis and late-stage modification of complex molecules.
作者机构：
[Wang, Huai-Yu; Wu, Yan-Dong; Wu, An-Xin; Wu, Chun-Yan; Yu, Zhi-Cheng; Chen, Xiang-Long; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Tang, Bo-Cheng] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, State Key Lab Chem Biol & Drug Discovery, Kowloon, Hong Kong, Peoples R China.;[Li, Anling] Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;[Li, Anling] Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
通讯机构：
[Li, AL ] W;[Wu, YD; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
关键词：
Defluoroarylation;Transition metal free;gem-Difluoroalkenes;Rongalite;Single electron transfer;C—C coupling;Redox reactions;Cross-coupling
摘要：
A transition‐metal‐free allylic defluorination reductive cross‐coupling between CF3‐alkenes and diaryliodonium salts mediated by rongalite has been described for the first time. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates. The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs. Comprehensive Summary The conversion of CF3‐alkenes to gem‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem‐difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs.
作者机构：
[Lei, Shuang-Gui; Wu, An-Xin; Zhou, You; Chen, Ting; Yu, Zhi-Cheng; Wu, Yan-Dong; Wang, Li-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Gao, Meng] South China Univ Technol, Sch Mat Sci & Engn, Minist Educ, Key Lab Biomed Mat & Engn,Natl Engn Res Ctr Tissu, Guangzhou 510006, Peoples R China.
通讯机构：
[Wu, AX ] C;[Gao, M ] S;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;South China Univ Technol, Sch Mat Sci & Engn, Minist Educ, Key Lab Biomed Mat & Engn,Natl Engn Res Ctr Tissu, Guangzhou 510006, Peoples R China.
通讯机构：
[Xiang, Jia-Chen] S;[Ma, Jin-Tian] K;School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
作者机构：
[Wang, Huai-Yu; Ma, Jin-Tian; Wu, An-Xin; Wu, Chun-Yan; Zhuang, Shi-Yi; Yu, Zhi-Cheng; Wu, Yan-Dong; Chen, Xiang-Long; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Key Lab Pesticide & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China.;[Tang, Bo-Cheng] Hong Kong Polytech, Dept Appl Biol & Chem Technol, State Key Lab Chem Biol & Drug Discovery, Kowloon, Hong Kong 999077, Peoples R China.
通讯机构：
[Yan-Dong Wu; An-Xin Wu] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
摘要：
A concise and efficient hydrodefluorination process was developed for the synthesis of gem-difluoroalkenes. This reaction employs rongalite as a masked proton source and does not require any additional catalysts or reductants. Notably, trifluoromethyl alkenes having both terminal and internal double bonds are compatible with this process, allowing for a wider range of substrates. The successful late-stage functionalizations of pharmaceuticals and gram-scale syntheses were used to demonstrate the viability of this method.
