Chenxi Yang, Saad Megahed, Miao Feng, Alaaldin M. Alkilany, Florian Schulz, Wolfgang J. Parak
Amphiphilic copolymers can be effectively used to encapsulate a broad range of nanomaterials. Since the surface charge and charge distribution can strongly affect relevant effects like protein adsorption, effective routes are required to tune it. Herein, a straightforward strategy is presented to tune the formal charge of poly (isobutylene-alt-maleic anhydride), converting it into an amphiphilic polymer with negative charge, zwitterionic character, or positive charge. This is a route of surface modification in which impact on other colloidal parameters apart for surface charge is minimized. The encapsulation of quantum dots are tested with the resulting polymers and confirm their robust stabilization over a range of pH values and ionic strengths.
{"title":"Synthesis of an Amphiphilic Polymer With Adjustable Surface Charge and Polarity and its Use for Obtaining Water-Soluble Nanoparticles","authors":"Chenxi Yang, Saad Megahed, Miao Feng, Alaaldin M. Alkilany, Florian Schulz, Wolfgang J. Parak","doi":"10.1002/adsc.70136","DOIUrl":"https://doi.org/10.1002/adsc.70136","url":null,"abstract":"Amphiphilic copolymers can be effectively used to encapsulate a broad range of nanomaterials. Since the surface charge and charge distribution can strongly affect relevant effects like protein adsorption, effective routes are required to tune it. Herein, a straightforward strategy is presented to tune the formal charge of poly (isobutylene-<i>alt</i>-maleic anhydride), converting it into an amphiphilic polymer with negative charge, zwitterionic character, or positive charge. This is a route of surface modification in which impact on other colloidal parameters apart for surface charge is minimized. The encapsulation of quantum dots are tested with the resulting polymers and confirm their robust stabilization over a range of pH values and ionic strengths.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665180","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}
Polysubstituted alkenes are versatile molecules and their multidimensional transformations have significant promotion for the creation and screening of chemotherapeutic agents and polyolefin functional materials. The difunctionalization of alkynes is an inevitable pathway for the generation of highly substituted alkenes with specific conformations. However, there is currently limited development on the construction of β-alkylated enamides through 1,2-alkylamination of alkynes, and the newly generated CC and CN bonds in traditional reports maintain syn-stereoselectivity. In addition, the formation of anti CC/CN bonds through difunctionalization of alkynes via free radical processes is overly dependent on electron deficient fluorinated alkyl radicals. We therefore seek to explore anti-stereoselective and β-regioselective 1,2-alkylamination of alkynes with amides and azobis(alkylcarbonitriles). Dozens of all-new β-alkylated enamides, including those containing biologically active patterns, are exported in 38%–88% yields by combining the addition of alkyl radicals to CC triple bonds with copper chelate-assisted functionalization of vinyl radicals. In addition, extensive mechanism explorations and synthetic applications are also conducted to explore the details and potential of this protocol.
{"title":"Synthesis of β-Alkylated Enamides by Copper-Catalyzed Anti-Stereoselective and β-Regioselective 1,2-Alkylamination of Alkynes","authors":"Xiaoyu Wang, Kelu Yan, Jiangwei Wen, Qiuyun Li, Yuhang Sun, Mingyu Zhao, Jianjing Yang","doi":"10.1002/adsc.70262","DOIUrl":"https://doi.org/10.1002/adsc.70262","url":null,"abstract":"Polysubstituted alkenes are versatile molecules and their multidimensional transformations have significant promotion for the creation and screening of chemotherapeutic agents and polyolefin functional materials. The difunctionalization of alkynes is an inevitable pathway for the generation of highly substituted alkenes with specific conformations<b>.</b> However, there is currently limited development on the construction of <i>β</i>-alkylated enamides through 1,2-alkylamination of alkynes, and the newly generated C<span></span>C and C<span></span>N bonds in traditional reports maintain <i>syn</i>-stereoselectivity. In addition, the formation of <i>anti</i> C<span></span>C/C<span></span>N bonds through difunctionalization of alkynes via free radical processes is overly dependent on electron deficient fluorinated alkyl radicals. We therefore seek to explore <i>anti</i>-stereoselective and <i>β</i>-regioselective 1,2-alkylamination of alkynes with amides and azobis(alkylcarbonitriles). Dozens of all-new <i>β</i>-alkylated enamides, including those containing biologically active patterns, are exported in 38%–88% yields by combining the addition of alkyl radicals to C<span></span>C triple bonds with copper chelate-assisted functionalization of vinyl radicals. In addition, extensive mechanism explorations and synthetic applications are also conducted to explore the details and potential of this protocol.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"131 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665182","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}
Soma Gergely Csik, Szabolcs Márk Orosz, Sára Spátay, Ádám Golcs
We report a covalently immobilized crown ether‐based platform that enables phase‐transfer‐catalyzed S N 2 reactions under fully automated microplate conditions. This regenerable system overcomes key limitations of HT synthesis—solubility mismatches, mixing constraints, and purification demands—offering a zero‐waste solution for expanding the accessible reaction space in robotized synthetic workflows. The approach relies on silanized glass microvials bearing dibenzo‐18‐crown‐6 functionalities, providing a well‐defined catalytic interface between immiscible organic and aqueous phases. The dynamic movement of the phase boundary during orbital shaking ensures continuous reagent exchange without the need for mechanical stirring. Model transformations using benzyl chloride and alkali metal salts (KCN, NaSCN) validated the efficiency of the immobilized phase‐transfer system, showing comparable or superior yields relative to homogeneous conditions. The covalently anchored catalysts remained active over multiple cycles, demonstrating excellent stability and reusability. The results establish a generalizable strategy for integrating biphasic reactions into automated high‐throughput synthesis workflows by eliminating the need for free phase‐transfer catalysts.
{"title":"Breaking Technological Limits in HT Synthesis: A Platform Concept to Unlock Phase‐Transfer Catalysis in Microplate‐Based S N 2 Automation","authors":"Soma Gergely Csik, Szabolcs Márk Orosz, Sára Spátay, Ádám Golcs","doi":"10.1002/adsc.70256","DOIUrl":"https://doi.org/10.1002/adsc.70256","url":null,"abstract":"We report a covalently immobilized crown ether‐based platform that enables phase‐transfer‐catalyzed S <jats:sub> <jats:italic>N</jats:italic> </jats:sub> 2 reactions under fully automated microplate conditions. This regenerable system overcomes key limitations of HT synthesis—solubility mismatches, mixing constraints, and purification demands—offering a zero‐waste solution for expanding the accessible reaction space in robotized synthetic workflows. The approach relies on silanized glass microvials bearing dibenzo‐18‐crown‐6 functionalities, providing a well‐defined catalytic interface between immiscible organic and aqueous phases. The dynamic movement of the phase boundary during orbital shaking ensures continuous reagent exchange without the need for mechanical stirring. Model transformations using benzyl chloride and alkali metal salts (KCN, NaSCN) validated the efficiency of the immobilized phase‐transfer system, showing comparable or superior yields relative to homogeneous conditions. The covalently anchored catalysts remained active over multiple cycles, demonstrating excellent stability and reusability. The results establish a generalizable strategy for integrating biphasic reactions into automated high‐throughput synthesis workflows by eliminating the need for free phase‐transfer catalysts.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658030","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}
A practical and mild strategy for TMSCl-mediated electrophilic carbocyclization–phosphorothiolation of alkynes with N-phosphorothiosuccinimide has been developed. This method enables efficient access to a wide range of fused phosphorothiolated phenanthrene and 2H-chromene derivatives in 61–86% yields from readily available o-alkynylbiphenyls and but-1-yne-1,4-diyldibenzenes, showcasing a broad substrate scope. Notably, o-alkynylbiphenyls bearing electron-rich OMe groups undergo a phosphorothiolation/dearomatization process to deliver phosphorothiolated spiro-cyclohexa[4.5]trienones. The utility of this protocol is further demonstrated through scale-up synthesis and the introduction of a SP(O)(OR)2 motif into bioactive molecule derivatives.
{"title":"TMSCl-Mediated Carbocyclization-Phosphorothiolation of Alkynes to Access Phosphorothiolated Phenanthrene and 2H-Chromene Derivatives","authors":"Mingyang Chen, Yitai Fu, Wenchong Wu, Jinglin Liu, Xiang Liu, Hua Cao","doi":"10.1002/adsc.70166","DOIUrl":"https://doi.org/10.1002/adsc.70166","url":null,"abstract":"A practical and mild strategy for TMSCl-mediated electrophilic carbocyclization–phosphorothiolation of alkynes with <i>N</i>-phosphorothiosuccinimide has been developed. This method enables efficient access to a wide range of fused phosphorothiolated phenanthrene and 2<i>H</i>-chromene derivatives in 61–86% yields from readily available <i>o</i>-alkynylbiphenyls and but-1-yne-1,4-diyldibenzenes, showcasing a broad substrate scope. Notably, <i>o</i>-alkynylbiphenyls bearing electron-rich OMe groups undergo a phosphorothiolation/dearomatization process to deliver phosphorothiolated spiro-cyclohexa[4.5]trienones. The utility of this protocol is further demonstrated through scale-up synthesis and the introduction of a <span></span>S<span></span>P(O)(OR)<sub>2</sub> motif into bioactive molecule derivatives.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"115 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665178","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}
Kaijian Liu, Yumin Ding, Jie Li, Zhuobin Yu, Jiarui Guo, Yantao Zhou, Kejun Luo, Jinhua Ou
Multicomponent alkene difunctionalization is persistently challenged by the difficult recovery of homogeneous catalysts and limited applicability to unactivated alkenes. While single‐atom catalysts (SACs) hold promise for overcoming these limitations, their application to such complex transformations remains unexplored thus far. Herein, we developed a Cu SAC (Cu 1 @NC) featuring atomically dispersed Cu–N 4 sites that enable efficient three‐component coupling of alkenes, quinoxalinones, and polyhalogenated alkanes. This catalytic system simultaneously installs both gem‐dihaloalkyl and quinoxalinone pharmacophores across a broad substrate scope (52 examples), including traditionally challenging unactivated aliphatic alkenes. Remarkably, Cu 1 @NC maintains excellent catalytic stability over >10 cycles with >95% of its initial activity retained and demonstrates robust scalability (72%–77% isolated yields in gram‐scale reactions). Most significantly, this catalytic system enables efficient late‐stage difunctionalization of alkenes derived from complex bioactive molecules (e.g., ibuprofen, borneol derivatives), underscoring its potential for pharmaceutical applications. Mechanistic investigations reveal that Cu 1 @NC mediates the radical pathway through two essential single‐electron transfer processes: activating TBHP to generate oxygen‐centered radicals and oxidizing intermediate IM‐4 to regenerate the catalytic center. This study delivers an atom‐ and step‐economical route to valuable drug‐like scaffolds, thus opening new avenues for heterogeneous catalysis in multicomponent reactions.
多组分烯烃双官能化一直受到均相催化剂难以回收和对未活化烯烃适用性有限的挑战。虽然单原子催化剂（SACs）有望克服这些限制，但到目前为止，它们在这种复杂转化中的应用仍未得到探索。在此，我们开发了一种Cu SAC (Cu 1 @NC)，具有原子分散的Cu - n - 4位点，可以实现烯烃、喹草胺酮和多卤化烷烃的高效三组分偶联。该催化系统同时在广泛的底物范围内（52个例子）安装宝石-二卤烷基和喹诺沙林酮药效团，包括传统上具有挑战性的未活化脂肪族烯烃。值得注意的是，Cu 1 @NC在10个循环中保持了优异的催化稳定性，保留了95%的初始活性，并表现出强大的可扩展性（在克级反应中分离收率为72%-77%）。最重要的是，该催化系统能够对复杂生物活性分子（如布洛芬、冰片衍生物）衍生的烯烃进行高效的后期双官能化，强调了其在制药应用中的潜力。机制研究表明Cu 1 @NC通过两个重要的单电子转移过程介导自由基途径：激活TBHP生成氧中心自由基和氧化中间体IM - 4再生催化中心。这项研究提供了一个原子和步骤经济的途径来获得有价值的药物样支架，从而为多组分反应的多相催化开辟了新的途径。
{"title":"Heterogeneous Copper Single‐Atom Catalyzed Three‐Component Radical Difunctionalization of Alkenes","authors":"Kaijian Liu, Yumin Ding, Jie Li, Zhuobin Yu, Jiarui Guo, Yantao Zhou, Kejun Luo, Jinhua Ou","doi":"10.1002/adsc.70257","DOIUrl":"https://doi.org/10.1002/adsc.70257","url":null,"abstract":"Multicomponent alkene difunctionalization is persistently challenged by the difficult recovery of homogeneous catalysts and limited applicability to unactivated alkenes. While single‐atom catalysts (SACs) hold promise for overcoming these limitations, their application to such complex transformations remains unexplored thus far. Herein, we developed a Cu SAC (Cu <jats:sub>1</jats:sub> @NC) featuring atomically dispersed Cu–N <jats:sub>4</jats:sub> sites that enable efficient three‐component coupling of alkenes, quinoxalinones, and polyhalogenated alkanes. This catalytic system simultaneously installs both gem‐dihaloalkyl and quinoxalinone pharmacophores across a broad substrate scope (52 examples), including traditionally challenging unactivated aliphatic alkenes. Remarkably, Cu <jats:sub>1</jats:sub> @NC maintains excellent catalytic stability over >10 cycles with >95% of its initial activity retained and demonstrates robust scalability (72%–77% isolated yields in gram‐scale reactions). Most significantly, this catalytic system enables efficient late‐stage difunctionalization of alkenes derived from complex bioactive molecules (e.g., ibuprofen, borneol derivatives), underscoring its potential for pharmaceutical applications. Mechanistic investigations reveal that Cu <jats:sub>1</jats:sub> @NC mediates the radical pathway through two essential single‐electron transfer processes: activating TBHP to generate oxygen‐centered radicals and oxidizing intermediate IM‐4 to regenerate the catalytic center. This study delivers an atom‐ and step‐economical route to valuable drug‐like scaffolds, thus opening new avenues for heterogeneous catalysis in multicomponent reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658031","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}
We report a rhodium(II)-catalyzed ring expansion of dihydro-1,3-thiazines with diazomalonates that provides tetrahydro-1,4-thiazepines bearing multiple stereocenters. The reaction proceeds through nucleophilic addition of the thiazine to the metallocarbene, catalyst release to form a sulfonium ylide, and rearrangement via an addition–elimination sequence to afford the thiazepine. A pronounced stereochemical effect arises for some cycloalkane-fused thiazines: cis isomers efficiently furnish the corresponding cis-thiazepines, whereas trans isomers remain unreactive under standard conditions and react only at higher temperatures. Control experiments and density functional theory studies show that trans isomers coordinate more strongly to rhodium, thereby inhibiting the catalytic cycle. The synthetic versatility of the 1,4-thiazepine scaffold is demonstrated by post-transformations of the cyclic imine, including hydrolysis, reduction, and Krapcho decarboxylation.
{"title":"Synthesis of Polysubstituted Tetrahydro-1,4-Thiazepines by Rhodium-Catalyzed Ring Expansion of Dihydro-1,3-Thiazines with Diazoesters","authors":"Laurine Tual, Romain Pertschi, Gaëlle Blond, Mihaela Gulea","doi":"10.1002/adsc.70259","DOIUrl":"https://doi.org/10.1002/adsc.70259","url":null,"abstract":"We report a rhodium(II)-catalyzed ring expansion of dihydro-1,3-thiazines with diazomalonates that provides tetrahydro-1,4-thiazepines bearing multiple stereocenters. The reaction proceeds through nucleophilic addition of the thiazine to the metallocarbene, catalyst release to form a sulfonium ylide, and rearrangement via an addition–elimination sequence to afford the thiazepine. A pronounced stereochemical effect arises for some cycloalkane-fused thiazines: <i>cis</i> isomers efficiently furnish the corresponding <i>cis</i>-thiazepines, whereas <i>trans</i> isomers remain unreactive under standard conditions and react only at higher temperatures. Control experiments and density functional theory studies show that <i>trans</i> isomers coordinate more strongly to rhodium, thereby inhibiting the catalytic cycle. The synthetic versatility of the 1,4-thiazepine scaffold is demonstrated by post-transformations of the cyclic imine, including hydrolysis, reduction, and Krapcho decarboxylation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"123 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651260","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}
Adam Cieśliński, Artur Przydacz, Anna Skrzyńska, Łukasz Albrecht
In this article, we demonstrate that dearomative higher-order cycloaddition constitutes a useful method for the construction of biologically relevant dihydropyrimidin-4(1H)-one scaffold. The reaction utilizes indole-7-carbaldehydes acting as higherene precursors that under N-heterocyclic carbene (NHC) catalysis, lead to the generation of NHC-bound aza-o-quinodimethanes. Their cycloaddition with cyclic trifluoromethyl ketimines, acting as hetero-higherenophiles, proceeds in an asymmetric fashion opening access to high molecular complexity in a single step.
在本文中，我们证明了脱芳香高阶环加成是构建具有生物学意义的二氢嘧啶- 4(1 H) - 1支架的有效方法。该反应利用吲哚- 7 -乙醛作为高烯前体，在N -杂环碳（NHC）催化下生成NHC结合的偶氮- o -喹二甲烷。它们与环三氟甲基酮胺的环加成，作为高杂亲烯试剂，以不对称方式进行，一步即可获得高分子复杂性。
{"title":"Dearomative Higher-Order Cycloaddition for the Construction of Dihydropyrimidin-4(1H)-One Scaffold Employing N-Heterocyclic Carbene Catalysis","authors":"Adam Cieśliński, Artur Przydacz, Anna Skrzyńska, Łukasz Albrecht","doi":"10.1002/adsc.70197","DOIUrl":"10.1002/adsc.70197","url":null,"abstract":"<p>In this article, we demonstrate that dearomative higher-order cycloaddition constitutes a useful method for the construction of biologically relevant dihydropyrimidin-4(1<i>H</i>)-one scaffold. The reaction utilizes indole-7-carbaldehydes acting as higherene precursors that under <i>N</i>-heterocyclic carbene (NHC) catalysis, lead to the generation of NHC-bound aza-<i>o</i>-quinodimethanes. Their cycloaddition with cyclic trifluoromethyl ketimines, acting as hetero-higherenophiles, proceeds in an asymmetric fashion opening access to high molecular complexity in a single step.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 23","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.70197","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Y. Bharath Chaithanya Kumar, Polasani Samatha, Deekshia Bhattachan, Raju Adepu
Herein, we have reported chemodivergent Diels–Alder reaction of allene formed in situ via a base-catalyzed alkyne-to-allene isomerization for the synthesis of fused carbazoles in a cascade reaction manner. The regioselectivity of the cycloaddition reaction was achieved using copper additives. The present cascade reaction involved Knoevenagel condensation, in situ allene formation, regioselective Diels–Alder reaction, followed by oxidation or aromatization.
{"title":"Regioselective Synthesis of Carbazoles via Chemodivergent Cascade Intramolecular [4 + 2] Annulation","authors":"Y. Bharath Chaithanya Kumar, Polasani Samatha, Deekshia Bhattachan, Raju Adepu","doi":"10.1002/adsc.70258","DOIUrl":"https://doi.org/10.1002/adsc.70258","url":null,"abstract":"Herein, we have reported chemodivergent Diels–Alder reaction of allene formed in situ via a base-catalyzed alkyne-to-allene isomerization for the synthesis of fused carbazoles in a cascade reaction manner. The regioselectivity of the cycloaddition reaction was achieved using copper additives. The present cascade reaction involved Knoevenagel condensation, in situ allene formation, regioselective Diels–Alder reaction, followed by oxidation or aromatization.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651261","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}
Development of methods with newer strategies for organic radical generation has been a major thrust area of synthetic organic chemistry in the last decade and a half. Often, the radical generation is aided by photoirradiation or electrochemical activation. Phosphinium radical cations, accessed by single electron oxidation or hydrogen atom abstraction, have recently emerged as a unique tool to furnish a variety of organic radicals leading to diverse functional group installations, reductions, cyclization, rearrangements, etc. Herein, we provide an account for the working model of this chemistry and the recent progress of this elegant approach with exciting prospects in the future.
{"title":"Emergence of Phosphinium Radical Cations as Intermediates for Organic Radical Generation","authors":"Prasun Sinha, Priyasha Dey, Yash Aneja, Akhilesh Singh Tilara, Abhishek Dewanji","doi":"10.1002/adsc.70243","DOIUrl":"https://doi.org/10.1002/adsc.70243","url":null,"abstract":"Development of methods with newer strategies for organic radical generation has been a major thrust area of synthetic organic chemistry in the last decade and a half. Often, the radical generation is aided by photoirradiation or electrochemical activation. Phosphinium radical cations, accessed by single electron oxidation or hydrogen atom abstraction, have recently emerged as a unique tool to furnish a variety of organic radicals leading to diverse functional group installations, reductions, cyclization, rearrangements, etc. Herein, we provide an account for the working model of this chemistry and the recent progress of this elegant approach with exciting prospects in the future.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651167","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}
Anthony Saint Pol, Maxime Roger, Alexis Mifleur, Pauline Loxq, Laëtitia Chausset‐Boissarie, Aurélien Béthegnies, Maël Penhoat, Isabelle Suisse, Mathieu Sauthier
In the presence of a catalytic amount (1 mol%) of Ni(cod) 2 and dppmb (1,2‐bis(diphenylphosphinomethyl)benzene)), a three‐component coupling reaction between industrially available aldehydes, buta‐1,3‐diene, and amines leads to the formation of variety of homoallylic alcohols with a highly functionalized 5‐aminopent‐3‐en‐1‐ol structure. The reaction proceeds with 100% atom economy under mild conditions (80 °C) in isopropanol as solvent. The process accommodates both aliphatic and aromatic aldehydes in combination with cyclic and acyclic secondary dialkyl amines, demonstrating a broad substrates scope. Reaction monitoring shows that the initial rate of the reaction is 39 h −1 , and the process reaches a maximum within 3 h of reaction at 80 °C. A competitive reaction has been identified as the hydroamination of 1,3‐butadiene that affords light butenylamines. The key mechanistic feature of the three‐component nickel‐catalyzed reaction is the formation of an η3 : η1 ‐allylalkoxy nickel (II) intermediate obtained from the oxidative coupling reaction between a low valent nickel (0) precursor, buta‐1,3‐diene, and an aldehyde. The amine subsequently reacts as a nucleophile with the electrophilic allyl moiety of this intermediate, while the alkoxy group acts as an internal base facilitating proton transfer that enables the synthesis of 5‐aminopent‐3‐en‐1‐ol derivatives without any base and salt formation.
{"title":"Synthesis of Functionalized Homoallylic Alcohols via a Salt‐Free Three‐Component Nickel‐Catalyzed Coupling Reaction","authors":"Anthony Saint Pol, Maxime Roger, Alexis Mifleur, Pauline Loxq, Laëtitia Chausset‐Boissarie, Aurélien Béthegnies, Maël Penhoat, Isabelle Suisse, Mathieu Sauthier","doi":"10.1002/adsc.70183","DOIUrl":"https://doi.org/10.1002/adsc.70183","url":null,"abstract":"In the presence of a catalytic amount (1 mol%) of Ni(cod) <jats:sub>2</jats:sub> and dppmb (1,2‐bis(diphenylphosphinomethyl)benzene)), a three‐component coupling reaction between industrially available aldehydes, buta‐1,3‐diene, and amines leads to the formation of variety of homoallylic alcohols with a highly functionalized 5‐aminopent‐3‐en‐1‐ol structure. The reaction proceeds with 100% atom economy under mild conditions (80 °C) in isopropanol as solvent. The process accommodates both aliphatic and aromatic aldehydes in combination with cyclic and acyclic secondary dialkyl amines, demonstrating a broad substrates scope. Reaction monitoring shows that the initial rate of the reaction is 39 h <jats:sup>−1</jats:sup> , and the process reaches a maximum within 3 h of reaction at 80 °C. A competitive reaction has been identified as the hydroamination of 1,3‐butadiene that affords light butenylamines. The key mechanistic feature of the three‐component nickel‐catalyzed reaction is the formation of an <jats:italic>η</jats:italic> <jats:sup>3</jats:sup> : <jats:italic>η</jats:italic> <jats:sup>1</jats:sup> ‐allylalkoxy nickel (II) intermediate obtained from the oxidative coupling reaction between a low valent nickel (0) precursor, buta‐1,3‐diene, and an aldehyde. The amine subsequently reacts as a nucleophile with the electrophilic allyl moiety of this intermediate, while the alkoxy group acts as an internal base facilitating proton transfer that enables the synthesis of 5‐aminopent‐3‐en‐1‐ol derivatives without any base and salt formation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"68 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651169","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}
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