Advanced Synthesis & Catalysis最新文献_第3页

Photo-/Electrochemically Radical Cation-/Anion-Mediated Defluorinative Functionalization of Organofluorides 光/电化学自由基阳离子/阴离子介导的有机氟化物去氟功能化

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-03 DOI: 10.1002/adsc.70102

Chaozhihui Cheng, Yong-Fei Huang, Li-Jie Wang, Mu-Jia Luo, Qiang Xiao

{"title":"Photo-/Electrochemically Radical Cation-/Anion-Mediated Defluorinative Functionalization of Organofluorides","authors":"Chaozhihui Cheng, Yong-Fei Huang, Li-Jie Wang, Mu-Jia Luo, Qiang Xiao","doi":"10.1002/adsc.70102","DOIUrl":"https://doi.org/10.1002/adsc.70102","url":null,"abstract":"Radical cation- or anion-based defluorinative functionalization has rapidly emerged as a highly effective method for enhancing molecular complexity, with widespread applications in medicinal chemistry and materials science. Photo-/electrochemistry, as green and sustainable approaches, enable diverse chemical transformations. Remarkable achievements in photo(electro)chemical defluorinative functionalization of radical cations or anions is reported. The generation of radicals via defluorination of organofluorides occurs through three main mechanistic pathways: single-electron reduction, spin center shift, and single-electron oxidation. This review comprehensively summarizes recent advances in reactions involving photochemically, electrochemically, or photoelectrochemically initiated radical cation or anion CF functionalization of organofluorides to forge a CC or CX (X = N, B, O, S, or Se) bond. This review highlights challenges and identifies potential areas for improvement. Additionally, the full spectrum of photocatalysts applied in this strategy, including metal-based and organic photoredox catalysts, is reviewed in detail.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Switchable Annulation of 2‐Isocyanophenyl Propargylic Ester and Diethyl 2‐Aminomalonate: Synthesis of Quinoline‐Fused Pyrrole and Benzo[b]azepin‐2(3H)‐One Skeleton 2 -异氰苯丙酯和2 -氨基丙酸二乙酯的可切换环化：喹啉-熔融吡咯和苯并[b]氮平- 2(3H) -一骨架的合成

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-30 DOI: 10.1002/adsc.70111

Mengshan Lou, Weipeng Cao, Ruiqi Gao, Lei Cui, Chunju Li, Jian Li

引用次数: 0

Advancements and Challenges in Reductive Methylation of Carbon Dioxide 二氧化碳还原甲基化研究进展与挑战

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-30 DOI: 10.1002/adsc.70054

Yubo Long, Meilin Tang, Yixin Liao, Shiqi Xu, Haobing Deng, Jinyao Liu, Peiru Chen, Jinwu Zhao, Wenfang Xiong

{"title":"Advancements and Challenges in Reductive Methylation of Carbon Dioxide","authors":"Yubo Long, Meilin Tang, Yixin Liao, Shiqi Xu, Haobing Deng, Jinyao Liu, Peiru Chen, Jinwu Zhao, Wenfang Xiong","doi":"10.1002/adsc.70054","DOIUrl":"https://doi.org/10.1002/adsc.70054","url":null,"abstract":"Methylation reactions have extraordinary value in organic chemistry, ranging from the assembly of structurally diverse organic functional chemicals to the introduction of methyl groups into pharmaceutical and agrochemical intermediates. In the context of sustainable chemistry, carbon dioxide (CO2) has emerged as an idea and alternative greener C1 source. As a result, reductive methylation strategies utilizing CO2 as a methylating agent have garnered substantial research interest in recent decades, particularly for synthesizing methylated derivatives, compounds with broad applications in drug discovery and agrochemical development. In this review, reductive methylations using CO2 as C1 synthon have been summarized and discussed in detail with focus on metal‐catalyzed C/N‐methylation reactions, base catalyzed C/N‐methylation reactions, ionic liquids catalyzed C/N‐methylation reactions, and catalyst‐free C/N‐methylation reactions based on various reductants. We also elucidate substrate compatibility in these reductive methylations, competing side reactions, and representative reaction mechanisms. Furthermore, conclusions and future trends are depicted finally in this review.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"109 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cu(I) Catalyzed Germyl S‐Phosphorothiolation of Electron‐Deficient Alkene 铜(I)催化缺电子烯烃的Germyl S -磷硫基化

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-30 DOI: 10.1002/adsc.70147

Asim Kumar Ghosh, Alakananda Hajra

引用次数: 0

Organocatalytic Remote‐Controlled Enantioselective 1,10‐Additions of In Situ Generated Alkynyl 2,4′‐Biphenyl Quinone Methides 原位合成炔基2,4′-联苯醌类化合物的有机催化远程控制对映选择性1,10加成

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-30 DOI: 10.1002/adsc.70091

Tian Liang, Meiwen Liu, Aman Ullah, Zhibin Yue, Yan Xia, Fang Fang, Pengfei Li, Shao‐Fei Ni, Wenjun Li

{"title":"Organocatalytic Remote‐Controlled Enantioselective 1,10‐Additions of In Situ Generated Alkynyl 2,4′‐Biphenyl Quinone Methides","authors":"Tian Liang, Meiwen Liu, Aman Ullah, Zhibin Yue, Yan Xia, Fang Fang, Pengfei Li, Shao‐Fei Ni, Wenjun Li","doi":"10.1002/adsc.70091","DOIUrl":"https://doi.org/10.1002/adsc.70091","url":null,"abstract":"The strategic incorporation of auxiliary groups has recently established α‐functionalized alcohols as versatile electrophilic alkylation reagents, enabling remotely controlled conjugate additions. Strikingly, while quinone methide chemistry has been extensively developed, their extended analogues—featuring spatially separated carbonyl and methide units across biphenyl systems—remain unexplored. Building on the prior work with alkynyl 4,4′‐biphenyl quinone methides, an organocatalytic remotely controlled enantioselective 1,10‐additions of in situ‐generated alkynyl 2,4′‐biphenyl quinone methides from α‐[4‐(2‐ hydroxyphenyl)phenyl]propargyl alcohols with 3‐arylindoles and indole‐2‐carboxylates is reported, affording a broad scope of enantioenriched 3H‐pyrrolo[1,2‐a]indoles and axially chiral tetrasubstituted allenes, respectively. Combined with control experiments, density functional theory calculations elucidate the reaction mechanism, revealing that the dehydration of α‐functionalized alcohols to generate 2,4′‐biphenyl quinone methides constitutes the rate‐limiting step, while enantioselectivity arises from the nucleophilic addition of alkynyl biphenyl quinone methides. Notably, beyond proving 2,4′‐biphenyl quinone methides as competent intermediates, this work breaks new ground by demonstrating their participation in previously unreported stereoselective 1,10‐additions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"39 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photoredox/Nickel Dual Catalytic C(sp2)S Cross‐coupling of Bromoanilines Enabled by Mineral Acids 无机酸催化溴苯胺的光氧化还原/镍双催化C(sp2) - 5s交叉偶联

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-30 DOI: 10.1002/adsc.70026

Florence Babawale, Maksim Nikitin, Indrajit Ghosh, Burkhard König

{"title":"Photoredox/Nickel Dual Catalytic C(sp2)S Cross‐coupling of Bromoanilines Enabled by Mineral Acids","authors":"Florence Babawale, Maksim Nikitin, Indrajit Ghosh, Burkhard König","doi":"10.1002/adsc.70026","DOIUrl":"https://doi.org/10.1002/adsc.70026","url":null,"abstract":"Cross‐coupling reactions are essential tools in modern organic synthesis, enabling the formation of carbonheteroatom (CX) bonds. Despite significant advancements in method development, particularly with palladium, copper, and nickel catalysis, including recent progress in photoredox catalysis, their efficiency is often limited when sensitive functional groups, such as thiols and amines, are present in the nucleophile or electrophile, and typically requires extensive protection–deprotection strategies. Herein, a practical synthetic approach is reported that employs mineral acids as unconventional reagents to facilitate C(sp2)S cross‐coupling between bromoanilines (or other electrophiles bearing free primary amines as functional groups) and thiols, thereby eliminating the need for protecting group manipulations. Additionally, protonation alters the electronic influence of the aniline moiety, transforming it from an electron‐donating to an electron‐withdrawing group, which promotes oxidative addition, and the acidic medium suppresses polythiolate formation, enhancing nickel catalysts’ accessibility and reducing inner filter effects in photocatalysis. This strategy enables efficient and high‐yielding synthesis of amino thioethers across a broad substrate scope, underscoring the value of acid‐assisted cross‐coupling as a streamlined and robust photoredox methodology for C(sp2)S bond formation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"95 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Sequence‐Controlled Di‐Functionalization of an SO2‐Surrogate with Amines for the Synthesis of Sulfonamides SO2代物与胺的序列控制二功能化合成磺胺

IF 4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-29 DOI: 10.1002/adsc.70041

Yu‐Cheng Lee , Indrajit Karmakar , Zi‐Hong Qiu , Rekha Bai , Chin‐Fa Lee

引用次数: 0

Regioisomeric Tuning of Intermolecular Diels‐Alder Reaction by Electrostatic Field‐Dipole Interaction 分子间Diels - Alder反应的静电场-偶极子相互作用区域异构体调谐

IF 4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-09-29 DOI: 10.1002/adsc.70044

Jinwoo Kim , Xavier Roy , Tomislav Rovis

引用次数: 0

Direct Photoinitiated Bromosulfonylation of Alkenes and Alkynes 烯烃和炔的直接光引发溴磺化反应