Pub Date : 2026-03-03Epub Date: 2025-12-23DOI: 10.1002/adsc.70212
Li Zhang , Xiang Li , Jin Zhou , Yulin Luo , Qiwen Pang , Wei Huang , Bo Han , Xiang‐Hong He
The development of oxygen‐containing three‐dimensional bicyclic scaffolds as bioisosteres of aromatic rings is of increasing importance for improving physicochemical and pharmacokinetic profiles in modern pharmaceutical development. Herein, we report a catalyst‐ and additive‐free strategy to access a series of multifunctional oxa‐bicyclo[2.1.1]hexane derivatives in a single operation from readily accessible α‐diazoketones and bicyclo[1.1.0]butanes. The process involves a visible‐light‐mediated sequential Wolff rearrangement/[2π + 2σ] cycloaddition. Generally, this reaction proceeds under mild conditions and features broad substrate scope, good functional group tolerance, and high regiospecificity. The synthetic utility of this method is demonstrated through diverse synthetic transformations of the resulting products. Furthermore, control experiments and mechanistic studies were conducted, and a plausible mechanism is proposed to rationalize the observed efficiency.
{"title":"Visible Light‐Driven Wolff Rearrangement/Formal (3+2) Cyclization of α‐Diazoketones with Bicyclo[1.1.0]butanes: Efficient and Highly Regioselective Access Oxabicyclo‐[2.1.1]hexane Scaffolds","authors":"Li Zhang , Xiang Li , Jin Zhou , Yulin Luo , Qiwen Pang , Wei Huang , Bo Han , Xiang‐Hong He","doi":"10.1002/adsc.70212","DOIUrl":"10.1002/adsc.70212","url":null,"abstract":"<div><div>The development of oxygen‐containing three‐dimensional bicyclic scaffolds as bioisosteres of aromatic rings is of increasing importance for improving physicochemical and pharmacokinetic profiles in modern pharmaceutical development. Herein, we report a catalyst‐ and additive‐free strategy to access a series of multifunctional oxa‐bicyclo[2.1.1]hexane derivatives in a single operation from readily accessible α‐diazoketones and bicyclo[1.1.0]butanes. The process involves a visible‐light‐mediated sequential Wolff rearrangement/[2<em>π</em> + 2<em>σ</em>] cycloaddition. Generally, this reaction proceeds under mild conditions and features broad substrate scope, good functional group tolerance, and high regiospecificity. The synthetic utility of this method is demonstrated through diverse synthetic transformations of the resulting products. Furthermore, control experiments and mechanistic studies were conducted, and a plausible mechanism is proposed to rationalize the observed efficiency.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70212"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145801133","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}
Regioselective, metal‐free, CH chlorination of phenols is challenging. These reactions generally proceed via electrophilic aromatic substitution, resulting in pure 2‐ or 4‐chlorinated products or a mixture of 2‐ and 4‐substituted isomers. However, 3‐substitution is electronically forbidden in these cases. Electrophilic aromatic chlorination involves toxic reagents, low tolerance for functional groups, and the generation of waste products from the chlorinating agent. Improvizations involving classical preformed chlorinating agents, oxidative chlorination, and transition metal catalysis, among others, require harsh conditions, high temperatures, directing groups, and low atom economy, despite achieving high selectivity. Few reports have also utilized the activation of arenes to facilitate regioselective nucleophilic chlorination. In a unique progression in phenol chemistry, we report a regioselective, indirect, catalyst‐ and metal‐free synthesis of 2‐chlorophenols via the chlorination of quinone monoacetals (QMA), derived from the oxidative dearomatization of phenol, using dimethyl chlorohydrosilane as a chloride source. Further, Brønsted acid‐catalyzed chlorination of QMA–MBH adducts afforded regioselective, metal‐free, solvent‐switchable 3‐ or 2‐chlorophenols via a one‐pot cascade reaction. C‐2‐chlorination proceeds via Michael addition of Cl− ion to the intermediate phenoxonium ion, while C‐3 chlorination occurs via Cl− addition to a silane‐activated quinone intermediate. This approach is well‐suited for late‐stage functionalization in pharmaceuticals, natural products, and complex molecules.
{"title":"Solvent‐Switchable Regiodivergent Chlorination of Quinone Monoacetals: A Practical Route to 2‐ and 3‐Chlorophenols","authors":"Pragya Sharma , Sharda Pasricha , Sunny Singh , Mainak Dey , Chinmoy Kumar Hazra","doi":"10.1002/adsc.70234","DOIUrl":"10.1002/adsc.70234","url":null,"abstract":"<div><div>Regioselective, metal‐free, CH chlorination of phenols is challenging. These reactions generally proceed via electrophilic aromatic substitution, resulting in pure 2‐ or 4‐chlorinated products or a mixture of 2‐ and 4‐substituted isomers. However, 3‐substitution is electronically forbidden in these cases. Electrophilic aromatic chlorination involves toxic reagents, low tolerance for functional groups, and the generation of waste products from the chlorinating agent. Improvizations involving classical preformed chlorinating agents, oxidative chlorination, and transition metal catalysis, among others, require harsh conditions, high temperatures, directing groups, and low atom economy, despite achieving high selectivity. Few reports have also utilized the activation of arenes to facilitate regioselective nucleophilic chlorination. In a unique progression in phenol chemistry, we report a regioselective, indirect, catalyst‐ and metal‐free synthesis of 2‐chlorophenols via the chlorination of quinone monoacetals (QMA), derived from the oxidative dearomatization of phenol, using dimethyl chlorohydrosilane as a chloride source. Further, Brønsted acid‐catalyzed chlorination of QMA–MBH adducts afforded regioselective, metal‐free, solvent‐switchable 3‐ or 2‐chlorophenols via a one‐pot cascade reaction. C‐2‐chlorination proceeds via Michael addition of Cl<sup>−</sup> ion to the intermediate phenoxonium ion, while C‐3 chlorination occurs via Cl<sup>−</sup> addition to a silane‐activated quinone intermediate. This approach is well‐suited for late‐stage functionalization in pharmaceuticals, natural products, and complex molecules.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70234"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320088","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70314
Long‐Jin Zhong , Shu‐Zheng Ou , Peng‐Fei Huang , Ke‐Wen Tang , Quan Zhou , Yu Liu
We developed a three‐component intermolecular alkoxysulfurization or estersulfurization of styrenes for the synthesis of emote alkoxy (ester) substituted thioether derivatives through copper/visible light catalyzed strategy. A variety of substrates were successfully converted into the desired sulfur‐containing products in moderate to good yields, demonstrating good functional group tolerance and excellent regioselectivity. Moreover, this method can be readily applied to modify bioactive molecules. A range of substrates, including perillyl alcohol, citronellol, geraniol, L‐menthol, and cholesterol, were successfully install to olefins with high selectivity.
{"title":"Visible‐Light Driven Copper‐Catalyzed Oxidative Alkylation of Styrenes with Sulfonium Salts and Alcohol or Acids","authors":"Long‐Jin Zhong , Shu‐Zheng Ou , Peng‐Fei Huang , Ke‐Wen Tang , Quan Zhou , Yu Liu","doi":"10.1002/adsc.70314","DOIUrl":"10.1002/adsc.70314","url":null,"abstract":"<div><div>We developed a three‐component intermolecular alkoxysulfurization or estersulfurization of styrenes for the synthesis of emote alkoxy (ester) substituted thioether derivatives through copper/visible light catalyzed strategy. A variety of substrates were successfully converted into the desired sulfur‐containing products in moderate to good yields, demonstrating good functional group tolerance and excellent regioselectivity. Moreover, this method can be readily applied to modify bioactive molecules. A range of substrates, including perillyl alcohol, citronellol, geraniol, <em>L</em>‐menthol, and cholesterol, were successfully install to olefins with high selectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70314"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320089","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}
Pub Date : 2026-03-03Epub Date: 2025-12-24DOI: 10.1002/adsc.70176
Xinwan Zhao , Minjun Lei , Xiaoli Ma , Zhiliang Jin
To address the rapid photogenerated carrier recombination issue that limits the efficiency of photocatalytic applications in semiconductors, this article presents for the first time the application of NiCeOx bimetallic oxides synthesized by the hydrothermal method in photocatalytic hydrogen production. By forming an S‐shaped heterojunction with cadmium sulfide (CdS) nanorods, an internal electric field is simultaneously generated to enhance the efficiency of surface carrier separation. Experimental findings reveal that the hydrogen evolution rate for NiCeOx/CdS achieves 8604.78 μmolg−1 h−1. This result indicates that the establishment of this unique heterojunction facilitates more effective electron movement from NiCeOx to CdS, leading to accelerated charge separation and transfer processes. Both experiments and theoretical calculations have jointly demonstrated that the composite material enhances the hydrogen production rate through photocatalysis and have also revealed the charge transfer mechanism of the S‐scheme heterojunction. This research provides a promising strategy for utilizing novel bimetallic oxide within the domain of photocatalysis and realizing directed electron migration in photocatalytic hydrogen evolution.
为了解决限制半导体光催化应用效率的光生载流子快速重组问题，本文首次介绍了水热法合成NiCeO x双金属氧化物在光催化制氢中的应用。通过与硫化镉（CdS）纳米棒形成S形异质结，同时产生内部电场以提高表面载流子分离的效率。实验结果表明，NiCeO x /CdS的析氢速率达到8604.78 μmolg−1 h−1。这一结果表明，这种独特异质结的建立促进了更有效的电子从NiCeO x向CdS的移动，从而加速了电荷分离和转移过程。实验和理论计算共同证明了复合材料通过光催化提高了产氢速率，并揭示了S -图式异质结的电荷转移机理。本研究为新型双金属氧化物在光催化领域的应用以及在光催化析氢过程中实现定向电子迁移提供了一种有前景的策略。
{"title":"Synergistic Photocatalytic Hydrogen Evolution of NiCeOx Bimetallic Oxide Nanosheets and Cadmium Sulfide Heterojunction","authors":"Xinwan Zhao , Minjun Lei , Xiaoli Ma , Zhiliang Jin","doi":"10.1002/adsc.70176","DOIUrl":"10.1002/adsc.70176","url":null,"abstract":"<div><div>To address the rapid photogenerated carrier recombination issue that limits the efficiency of photocatalytic applications in semiconductors, this article presents for the first time the application of NiCeO<sub><em>x</em></sub> bimetallic oxides synthesized by the hydrothermal method in photocatalytic hydrogen production. By forming an S‐shaped heterojunction with cadmium sulfide (CdS) nanorods, an internal electric field is simultaneously generated to enhance the efficiency of surface carrier separation. Experimental findings reveal that the hydrogen evolution rate for NiCeO<sub><em>x</em></sub>/CdS achieves 8604.78 μmolg<sup>−1 </sup>h<sup>−1</sup>. This result indicates that the establishment of this unique heterojunction facilitates more effective electron movement from NiCeO<sub><em>x</em></sub> to CdS, leading to accelerated charge separation and transfer processes. Both experiments and theoretical calculations have jointly demonstrated that the composite material enhances the hydrogen production rate through photocatalysis and have also revealed the charge transfer mechanism of the S‐scheme heterojunction. This research provides a promising strategy for utilizing novel bimetallic oxide within the domain of photocatalysis and realizing directed electron migration in photocatalytic hydrogen evolution.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70176"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807526","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70322
David G. Groves , Reece H. Hoogesteger , Balakumar Emayavaramban , Craig P. Johnston
Accessing alcohols from readily available chemical feedstocks is a critical process within synthetic methodology. The hydration of olefins is a convenient method for the introduction of an alcohol functional group, ideally via the direct addition of water across the alkene. However, current transition metal‐catalysed protocols (Mukaiyama‐type hydration) are dominated by radical addition to molecular oxygen. Ionic processes involving direct hydration with water are underexplored, yet highly desirable due to the simplicity of the reagents required. Herein, we report a cobalt‐salen catalysed hydration of alkenes proceeding via a radical–polar crossover mechanism and subsequent nucleophilic attack of water. This is a complementary protocol to previously reported radical‐based hydrations, which display analogous reactivity to traditional acid‐catalysed methods. The mild reaction conditions employed make the protocol synthetically practical and convenient for accessing alcohols from the corresponding alkenes.
{"title":"Cobalt‐Salen Catalysed Hydration of Alkenes With Water: A Complementary Ionic Approach to the Mukaiyama Hydration","authors":"David G. Groves , Reece H. Hoogesteger , Balakumar Emayavaramban , Craig P. Johnston","doi":"10.1002/adsc.70322","DOIUrl":"10.1002/adsc.70322","url":null,"abstract":"<div><div>Accessing alcohols from readily available chemical feedstocks is a critical process within synthetic methodology. The hydration of olefins is a convenient method for the introduction of an alcohol functional group, ideally via the direct addition of water across the alkene. However, current transition metal‐catalysed protocols (Mukaiyama‐type hydration) are dominated by radical addition to molecular oxygen. Ionic processes involving direct hydration with water are underexplored, yet highly desirable due to the simplicity of the reagents required. Herein, we report a cobalt‐salen catalysed hydration of alkenes proceeding via a radical–polar crossover mechanism and subsequent nucleophilic attack of water. This is a complementary protocol to previously reported radical‐based hydrations, which display analogous reactivity to traditional acid‐catalysed methods. The mild reaction conditions employed make the protocol synthetically practical and convenient for accessing alcohols from the corresponding alkenes.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70322"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329962","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70337
Haiyan Liu , Jianjing Yang , Qiuhong Liang , Kelu Yan , Xiangyu Wang , Jiangwei Wen
The donor–acceptor–donor (DAD) complex model provides a reliable strategy for mediating direct decarboxylative coupling between two electron donors, effectively eliminating the need for amino acid preactivation, external photocatalysts, or transition‐metal catalysts. Herein, a metal‐ and photocatalyst‐free direct decarboxylative amination has been developed through photoactive DAD complexes. This strategy enables efficient access to valuable sulfur‐containing heterocycles, including key intermediates for NEK2 inhibitors and cumene oxidation inhibitors, under mild blue‐light irradiation. Mechanistic studies confirm the formation of a DAD complex, which, upon photoexcitation, undergoes a single‐electron transfer (SET) process to generate radical species, followed by decarboxylation and selective CN coupling. The method features broad substrate scope, operational simplicity, and scalability, providing a practical and sustainable alternative to conventional photocatalytic systems.
{"title":"Donor–Acceptor–Donor Complex Enabled, Metal‐, and Photocatalyst‐Free Synthesis of NEK2 and Cumene Oxidation Inhibitors via Direct Decarboxylative Amination of N‐Aryl Glycines","authors":"Haiyan Liu , Jianjing Yang , Qiuhong Liang , Kelu Yan , Xiangyu Wang , Jiangwei Wen","doi":"10.1002/adsc.70337","DOIUrl":"10.1002/adsc.70337","url":null,"abstract":"<div><div>The donor–acceptor–donor (DAD) complex model provides a reliable strategy for mediating direct decarboxylative coupling between two electron donors, effectively eliminating the need for amino acid preactivation, external photocatalysts, or transition‐metal catalysts. Herein, a metal‐ and photocatalyst‐free direct decarboxylative amination has been developed through photoactive DAD complexes. This strategy enables efficient access to valuable sulfur‐containing heterocycles, including key intermediates for NEK2 inhibitors and cumene oxidation inhibitors, under mild blue‐light irradiation. Mechanistic studies confirm the formation of a DAD complex, which, upon photoexcitation, undergoes a single‐electron transfer (SET) process to generate radical species, followed by decarboxylation and selective CN coupling. The method features broad substrate scope, operational simplicity, and scalability, providing a practical and sustainable alternative to conventional photocatalytic systems.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70337"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329957","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}
Pub Date : 2026-03-03Epub Date: 2025-12-20DOI: 10.1002/adsc.70273
Yile Song , Kui Liu , Weisi Guo , Ming Li , Lirong Wen , Lin‐Bao Zhang
We propose an electrochemical regioselective chlorination strategy for the α‐position of indanone. In this strategy, AlCl3 or MgCl2 plays a dual role as both a chlorine source and an electrolyte, allowing for the selective generation of mono‐ or dichlorinated products under mild conditions by utilizing AlCl3 or MgCl2 as the chlorine source. This method not only aligns with green chemistry principles but also demonstrates good substrate universality and scalability, providing an efficient and environmentally friendly approach for the synthesis of α‐chloroindanone.
{"title":"Electrochemical α‐Selective Chlorination of Indanones with AlCl3/MgCl2","authors":"Yile Song , Kui Liu , Weisi Guo , Ming Li , Lirong Wen , Lin‐Bao Zhang","doi":"10.1002/adsc.70273","DOIUrl":"10.1002/adsc.70273","url":null,"abstract":"<div><div>We propose an electrochemical regioselective chlorination strategy for the <em>α</em>‐position of indanone. In this strategy, AlCl<sub>3</sub> or MgCl<sub>2</sub> plays a dual role as both a chlorine source and an electrolyte, allowing for the selective generation of mono‐ or dichlorinated products under mild conditions by utilizing AlCl<sub>3</sub> or MgCl<sub>2</sub> as the chlorine source. This method not only aligns with green chemistry principles but also demonstrates good substrate universality and scalability, providing an efficient and environmentally friendly approach for the synthesis of <em>α</em>‐chloroindanone.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70273"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786309","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70326
Yuxuan He , Changmei Zhang , Yuanyuan An , Jing Ding , Xiaojing Wei , Danqing Zheng
A sustainable protocol for the direct C3‐alkylation of quinoxalin‐2‐ones using graphitic carbon nitride (g‐C3N4) as a heterogeneous photocatalyst is reported. This article is the first to use g‐C3N4 to enable N‐heterocyclic alkylation via direct decarboxylation, thereby overcoming the limitations of homogeneous Ir/Ru systems. The reaction proceeds under mild conditions with O2 as the oxidant, tolerating diverse functional groups and affording products in 65%–92% yields. The g‐C3N4 catalyst, prepared from earth‐abundant precursors, is readily recycled by centrifugation and maintains its activity over five cycles. This method offers advantages in cost, environmental impact, and scalability, making it a green and promising candidate for industrial applications.
{"title":"Metal‐Free Decarboxylative Alkylation of Quinoxaline‐2(1H)‐ones Enabled by Heterogeneous g‐C3N4 Photoredox Catalysis","authors":"Yuxuan He , Changmei Zhang , Yuanyuan An , Jing Ding , Xiaojing Wei , Danqing Zheng","doi":"10.1002/adsc.70326","DOIUrl":"10.1002/adsc.70326","url":null,"abstract":"<div><div>A sustainable protocol for the direct C3‐alkylation of quinoxalin‐2‐ones using graphitic carbon nitride (g‐C<sub>3</sub>N<sub>4</sub>) as a heterogeneous photocatalyst is reported. This article is the first to use g‐C<sub>3</sub>N<sub>4</sub> to enable N‐heterocyclic alkylation via direct decarboxylation, thereby overcoming the limitations of homogeneous Ir/Ru systems. The reaction proceeds under mild conditions with O<sub>2</sub> as the oxidant, tolerating diverse functional groups and affording products in 65%–92% yields. The g‐C<sub>3</sub>N<sub>4</sub> catalyst, prepared from earth‐abundant precursors, is readily recycled by centrifugation and maintains its activity over five cycles. This method offers advantages in cost, environmental impact, and scalability, making it a green and promising candidate for industrial applications.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70326"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147373999","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}
Pub Date : 2026-03-03Epub Date: 2025-12-24DOI: 10.1002/adsc.70235
Yu Wang , Zhao Sun , Zhihan Zhang , Yinlong Guo , Qinglei Chong , Fanke Meng
A cobalt‐catalyzed protocol for diastereo‐ and enantioselective reductive coupling of unactivated cyclobutenes and aldimines through oxidative cyclization promoted by a chiral bisphosphine–cobalt is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable umpolung reactivity of cyclobutenes with imines and incorporation of a chiral amino‐containing fragment onto the four‐membered ring scaffold, delivering a broad scope of enantioenriched cyclobutyl amines in up to 98% yield and >99.5:0.5 er as a single diastereomer. Functionalization provided a variety of densely functionalized cyclobutanes that are otherwise difficult to access. Preliminary mechanistic studies revealed that the reaction proceeded through diastereo‐ and enantioselective oxidative cyclization followed by protonation. Density functional theory calculations elucidated the origin of stereoselectivity in detail.
{"title":"Cobalt‐Catalyzed Diastereo‐ and Enantioselective Reductive Coupling of Cyclobutenes and Aldimines","authors":"Yu Wang , Zhao Sun , Zhihan Zhang , Yinlong Guo , Qinglei Chong , Fanke Meng","doi":"10.1002/adsc.70235","DOIUrl":"10.1002/adsc.70235","url":null,"abstract":"<div><div>A cobalt‐catalyzed protocol for diastereo‐ and enantioselective reductive coupling of unactivated cyclobutenes and aldimines through oxidative cyclization promoted by a chiral bisphosphine–cobalt is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable umpolung reactivity of cyclobutenes with imines and incorporation of a chiral amino‐containing fragment onto the four‐membered ring scaffold, delivering a broad scope of enantioenriched cyclobutyl amines in up to 98% yield and >99.5:0.5 er as a single diastereomer. Functionalization provided a variety of densely functionalized cyclobutanes that are otherwise difficult to access. Preliminary mechanistic studies revealed that the reaction proceeded through diastereo‐ and enantioselective oxidative cyclization followed by protonation. Density functional theory calculations elucidated the origin of stereoselectivity in detail.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70235"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807525","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}
Harnessing chlorine radicals (Cl•) for selective organic transformations has remained challenging due to their extreme reactivity and dependence on unstable chlorine precursors. Here, we present a visible‐light strategy that directly generates Cl• from sodium chloride (NaCl), an abundant, benign, and previously inaccessible chlorine source. Using perylenediimide (PDI) as a sustainable, metal‐free photocatalyst and N‐fluorobenzenesulfonimide (NFSI) as a radical cargo, chloride anions were oxidized to Cl•, which drove efficient oxydihalogenation of terminal and internal alkynes. This approach could overcome long‐standing solubility and redox barriers, affording gem‐dihaloketones in high yields. Mechanistic studies confirmed radical intermediacy and revealed the unprecedented role of NaCl as a chlorine radical progenitor. This work establishes inorganic halide salts as renewable radical precursors and provides a sustainable platform for green halogenation chemistry.
{"title":"Organic Halogenation of Alkynes with Inorganic Halides Using Perylenediimide as Visible‐Light Photocatalyst","authors":"Pravat Nayek , Chidananda Biswal , Sandeepan Maity , Prasenjit Mal","doi":"10.1002/adsc.70245","DOIUrl":"10.1002/adsc.70245","url":null,"abstract":"<div><div>Harnessing chlorine radicals (Cl<sup>•</sup>) for selective organic transformations has remained challenging due to their extreme reactivity and dependence on unstable chlorine precursors. Here, we present a visible‐light strategy that directly generates Cl<sup>•</sup> from sodium chloride (NaCl), an abundant, benign, and previously inaccessible chlorine source. Using perylenediimide (PDI) as a sustainable, metal‐free photocatalyst and <em>N</em>‐fluorobenzenesulfonimide (NFSI) as a radical cargo, chloride anions were oxidized to Cl<sup>•</sup>, which drove efficient oxydihalogenation of terminal and internal alkynes. This approach could overcome long‐standing solubility and redox barriers, affording <em>gem</em>‐dihaloketones in high yields. Mechanistic studies confirmed radical intermediacy and revealed the unprecedented role of NaCl as a chlorine radical progenitor. This work establishes inorganic halide salts as renewable radical precursors and provides a sustainable platform for green halogenation chemistry.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70245"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807524","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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