Advanced Synthesis & Catalysis最新文献

Cleaner Production of Acetals/Ketals Using a Phosphorus‐Doped Biomass‐Based Carbon Catalyst via Acetalization Reaction 利用掺磷生物质基碳催化剂通过缩醛反应清洁生产缩醛/酮

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-10 DOI: 10.1002/adsc.70142

Yuguo Dong, Shiyun Xiao, Dongsheng Huang, Changle Zhao, Yongdian Xu, Lin Dong, Zupeng Chen, Xiaoli Gu

{"title":"Cleaner Production of Acetals/Ketals Using a Phosphorus‐Doped Biomass‐Based Carbon Catalyst via Acetalization Reaction","authors":"Yuguo Dong, Shiyun Xiao, Dongsheng Huang, Changle Zhao, Yongdian Xu, Lin Dong, Zupeng Chen, Xiaoli Gu","doi":"10.1002/adsc.70142","DOIUrl":"https://doi.org/10.1002/adsc.70142","url":null,"abstract":"The transformation of aldehydes and ketones into acetals and ketals has garnered significant attention due to their wide applications as fragrances, bio‐oil additives, and organic synthetic intermediates. Conventional acetalization methods, however, often rely on corrosive acids or stoichiometric additives, necessitating harsh conditions and increasing production costs. Here, the development of a phosphorus‐doped carbon catalyst is presented, that enables the acetalization of aldehydes and ketones into acetals and ketals under mild conditions (e.g., 60 °C, atmospheric pressure). This catalyst achieves a high yield of 2‐phenyl‐1,3‐dioxolane (87.1%) from benzaldehyde and exhibits exceptional stability, operating continuously for 120 h in a continuous fixed‐bed reactor. In the continuous reaction, the yield of 2‐phenyl‐1,3‐dioxolane remains over 96% in the first 18 h and slightly decreases to 86% after 120 h of continuous operation. Comprehensive physicochemical characterizations reveal that phosphorus acts as a Lewis acid sites and plays a critical role in modulating the Lewis acid sites of the PC catalysts. This work highlights the significance of optimizing acid properties for the efficient acetalization reaction, offering a promising approach to sustainable chemical synthesis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255491","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

Electrochemical Decarboxylative Functionalizations through Carbocation Intermediates 通过碳正离子中间体的电化学脱羧功能化

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-10 DOI: 10.1002/adsc.70137

Fei Lian, Zhoumei Tan, Kun Xu

引用次数: 0

Recent Advances in Transition‐Metal‐Catalyzed Thiolation and Sulfonylation of Alkenes 过渡金属催化烯烃硫代和磺化反应的研究进展

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-09 DOI: 10.1002/adsc.70131

Anee Taj, Zhen Wang, Luomo Li, Xiao‐Hui Yang

{"title":"Recent Advances in Transition‐Metal‐Catalyzed Thiolation and Sulfonylation of Alkenes","authors":"Anee Taj, Zhen Wang, Luomo Li, Xiao‐Hui Yang","doi":"10.1002/adsc.70131","DOIUrl":"https://doi.org/10.1002/adsc.70131","url":null,"abstract":"The development of efficient and selective strategies for constructing CS bonds has garnered significant attention in organic and medicinal chemistry, owing to the widespread presence of this linkage in biologically active molecules, pharmaceuticals, agrochemicals, and functional materials. Among the various approaches, alkene thiolation and sulfonylation stand out as one of the most straightforward methods for organosulfur synthesis, enabling the direct introduction of sulfur‐containing functionalities into unsaturated hydrocarbons. This review provides a comprehensive summary of recent advances (2013–present) in transition‐metal‐catalyzed CS bond formation via alkene thiolation and sulfonylation. We systematically discuss the synthetic methodologies, including transition‐metal‐catalyzed hydrothiolation, carbothiolation, hydrosulfonylation, and carbosulfonylation, highlighting their respective substrate scope, chemoselectivity, regioselectivity, enantioselectivity, and reaction mechanisms. By consolidating the latest developments and critical perspectives, this review aims to serve as a valuable resource for researchers, encouraging further exploration and innovation in this dynamic field. The continued evolution of transition‐metal‐catalyzed CS bond formation is expected to unlock new opportunities in drug discovery, materials science, and synthetic methodology.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"114 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246954","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

Ruthenium-Catalyzed Azide-Selenoalkyne Cycloadditions: A Combined Synthetic–Computational Study into Reaction Scope, Mechanism, and Origins of Regioselectivity 钌催化叠氮化物-硒代炔环加成：区域选择性范围、机理和来源的合成-计算联合研究

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-09 DOI: 10.1002/adsc.70096

Frances E. Bugden, Andrew D. Bage, Ashima Bajaj, Bin Wang, Fiona J. Gibson, Henry Stone, Yingjian Xu, Frank De Proft, Mercedes Alonso, Mark D. Greenhalgh

{"title":"Ruthenium-Catalyzed Azide-Selenoalkyne Cycloadditions: A Combined Synthetic–Computational Study into Reaction Scope, Mechanism, and Origins of Regioselectivity","authors":"Frances E. Bugden, Andrew D. Bage, Ashima Bajaj, Bin Wang, Fiona J. Gibson, Henry Stone, Yingjian Xu, Frank De Proft, Mercedes Alonso, Mark D. Greenhalgh","doi":"10.1002/adsc.70096","DOIUrl":"https://doi.org/10.1002/adsc.70096","url":null,"abstract":"A ruthenium-catalyzed azide–alkyne cycloaddition (RuAAC) reaction involving selenoalkynes is reported for the synthesis of selenium-substituted 1,2,3-triazole products (26 examples, up to 89% yield). The reaction works well with a wide range of alkyl and aryl azides bearing both electron-donating and -withdrawing groups. This contrasts RuAAC reactions using regular terminal and internal alkynes, where aryl azides bearing electron-withdrawing groups are not generally tolerated. The regioselectivity of the cycloaddition is highly dependent on the identity of the non-selenium substituent of the alkyne. This challenges earlier reports on RuAAC reactions involving thioalkynes and questions the perceived understanding of the regioselectivity of these reactions. Computational modeling of the reaction profiles for four alkyne substrates that provided contrasting regioselectivities accurately reproduces the experimental results. The observed regioselectivity is primarily attributed to the relative nucleophilicity of the alkyne carbons upon coordination to ruthenium and an approach is proposed in which reaction regioselectivity may be predicted.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"85 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247665","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

Visible-Light-Induced Controlled C–H Cyanation or Thiocyanation of Indolizines 可见光诱导的受控碳-氢氰化或硫氰化

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-09 DOI: 10.1002/adsc.70140

Yuhao Jiang, Qiongying Yang, Dongrong Lin, Xin Jiang, Jubin Liu, Hua Cao, Yue Yu

引用次数: 0

Recent Advances in Terminal Alkyne-Involved Alkynylation and Alkynylation-Triggered Tandem Reactions 末端炔基参与的炔基化和炔基化引发的串联反应研究进展

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-08 DOI: 10.1002/adsc.70145

Kai-Cheng Yang, Zhi-Kui Cao, Hai-Liang Ni, Long Chen

引用次数: 0

Mechanistic Investigation on an NHC-Catalyzed [3 + 3] Annulation of 2-Bromoenals with β-Oxodithioester: Mechanism, Origins of Stereoselectivity nhc催化2-溴烯醛与β-氧二硫酯[3 + 3]环化的机理研究：立体选择性的机理和来源

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-08 DOI: 10.1002/adsc.70143

Sai-Bo Cao, Yang Wang

{"title":"Mechanistic Investigation on an NHC-Catalyzed [3 + 3] Annulation of 2-Bromoenals with β-Oxodithioester: Mechanism, Origins of Stereoselectivity","authors":"Sai-Bo Cao, Yang Wang","doi":"10.1002/adsc.70143","DOIUrl":"https://doi.org/10.1002/adsc.70143","url":null,"abstract":"An increasing number of studies have demonstrated the cooperative use of chiral N-heterocyclic carbenes (NHCs) and Lewis acid to enhance catalytic efficiency in stereoselective annulation reactions. Herein, molecular-level insights into the NHC-catalyzed [3 + 3] annulation of 2-bromoenals with β-oxodithioester are elucidated through density functional theory calculations. The reaction proceeds via multiple key steps: formation of the Breslow intermediate, CBr bond cleavage, α-protonation generating α,β-unsaturated acylazolium, stereoselective Si-face addition between the acylazolium and LiCl-coordinated β-oxodithioester, intramolecular proton transfer, and catalyst regeneration. The stereoselectivity-determining CC bond formation step exhibits enhanced facial control through cooperative effects. Noncovalent interaction (NCI) and atoms-in-molecules analyses reveal that hydrogen-bond networks, LP···π, and O···S interactions preferentially stabilize the RS-configured isomer. Notably, LiCl plays dual roles: (1) it amplifies stereocontrol by facilitating multiple NCIs during the CC bond formation, and (2) reduces transition-state polarity through solvent–solute interactions, thereby lowering the activation barrier. The work deepens the understanding of how Lewis acid additive modulate both electronic and steric landscapes in NHC catalysis, offering valuable insights for stereocontrolled annulation reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247199","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

Installation of Trifluoromethylated Quaternary Carbon Stereocenters via Asymmetric Epoxidation of Tetrasubstituted Alkenes 四取代烯烃不对称环氧化装置三氟甲基化季碳立体中心

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-08 DOI: 10.1002/adsc.70153

Vincenzo Battaglia, Isaac G. Sonsona, Andrea Pellegrini, Andrea Mazzanti, Alessandra Lattanzi

{"title":"Installation of Trifluoromethylated Quaternary Carbon Stereocenters via Asymmetric Epoxidation of Tetrasubstituted Alkenes","authors":"Vincenzo Battaglia, Isaac G. Sonsona, Andrea Pellegrini, Andrea Mazzanti, Alessandra Lattanzi","doi":"10.1002/adsc.70153","DOIUrl":"https://doi.org/10.1002/adsc.70153","url":null,"abstract":"The construction of vicinal quaternary carbon centers via epoxidation of tetrasubstituted alkenes remains a formidable challenge in asymmetric synthesis. Herein, a first catalytic enantioselective epoxidation of acyclic tetrasubstituted alkenes is reported, prepared through the Knoevenagel condensation of trifluoromethyl ketones with malononitrile. (S)‐ and (R)‐configured epoxides are obtained in generally excellent yields (up to 98%) and with good to high enantioselectivities (up to 89% ee), employing a commercially available system, comprising Takemoto's catalysts and tert‐butyl hydroperoxide (TBHP). Highly reactive new tetrasubtituted alkenes allow the first successful use of Takemoto's catalyst under oxidative conditions. Interestingly, density functional theory studies show that TBHP is exclusively activated by the amino thiourea, with halogen‐bonding interactions playing a critical role in affecting the stereochemical outcome of the epoxidation. Derivatizations provide access to densely functionalized trifluoromethylated compounds, featuring one or two vicinal carbon quaternary stereocenters, with the second center being introduced in a highly stereoselective manner.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"112 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241640","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

Monofluorinated C1 Synthon Strategy for the Construction of Fluoromethylene-Linked Bicyclo[1.1.1]Pentane Derivatives 单氟化C1合成策略构建氟亚甲基双环[1.1.1]戊烷衍生物

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-08 DOI: 10.1002/adsc.70119

Arturs Sperga, Toms Pfeifers, Janis Veliks

引用次数: 0

Enantioselective Synthesis of 3,4‐Dihydropyranones via Low‐Loading Squaramide Catalysis “on Water” 低负荷方酰胺在水中催化3,4 -二氢吡喃酮的对映选择性合成

IF 5.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-10-07 DOI: 10.1002/adsc.70141

Tianxing Li, Xinxin Li, Jinfeng Zhang, Hui Jin, Lixin Zhang

引用次数: 0