{"title":"Direct Access to Aminocyclopentenones through Rh‐Catalyzed Cascade Wolff Rearrangement and Decarbonylative Amination","authors":"Lvlv Gao, Jianwei Wu, Jian Wang, Enshen Zhang, Yongjia Shang, Xinwei He","doi":"10.1002/adsc.70110","DOIUrl":"https://doi.org/10.1002/adsc.70110","url":null,"abstract":"The cascade reaction of cyclic 2‐diazo‐1,3‐diketones and diarylamines is efficiently developed, enabling straightforward access to a series of 2‐aminocyclopentenones in good to excellent yields (71–90%). The procedure is proposed to go through a sequence of Wolff rearrangement via initial ketene formation, nucleophilic addition/keto‐enol tautomerization, and Rh<jats:sub>2</jats:sub>(OAc)<jats:sub>4</jats:sub>‐catalyzed decarbonylative amination followed by an oxidation process. A broad range of substrates are compatible with this mild reaction system, thereby providing a facile and practical approach for constructing important skeleton of aminocyclopentenone.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"87 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145181134","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}
Jian Wang , Cheng‐Feng Gao , Houwen Zhou , Feng Li , Jing Nie , Jun‐An Ma , Fa‐Guang Zhang
{"title":"DBU‐Triggered One‐Pot Domino Transformation of Trifluoromethyl Ketones and Dicyanoalkenes into gem‐Difluoroalkenyl γ‐Lactams","authors":"Jian Wang , Cheng‐Feng Gao , Houwen Zhou , Feng Li , Jing Nie , Jun‐An Ma , Fa‐Guang Zhang","doi":"10.1002/adsc.70090","DOIUrl":"10.1002/adsc.70090","url":null,"abstract":"<div><div>The direct conversion of trifluoromethyl ketones to valuable <em>gem</em>‐difluoroalkenes remains a synthetically useful but underexplored transformation. Herein, we report a base‐catalyzed, one‐pot domino reaction of trifluoromethyl ketones with dicyanoalkenes, enabling formal dual deoxygenation and defluorination. This protocol affords a diverse range of <em>gem</em>‐difluoroalkenyl unsaturated <em>γ</em>‐lactams in yields of 62–95% under mild and operationally simple conditions. A proposed mechanism involves a sequential vinylogous aldol reaction, cyclization, rearrangement, and defluorination.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70090"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901674","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}
Yosephine Tania Limanto , Karen Ka‐Yan Kung , Aries Kwok‐Heung Chan , Nathanael Chun‐Him Lai , Man‐Kin Wong
{"title":"5,7‐Membered Cyclometallated Gold(III) Complexes with Pyridine‐Phenyl‐Oxazoline N^C^N Ligands as Catalysts for Organic Transformation Reactions Under Silver‐Free Conditions","authors":"Yosephine Tania Limanto , Karen Ka‐Yan Kung , Aries Kwok‐Heung Chan , Nathanael Chun‐Him Lai , Man‐Kin Wong","doi":"10.1002/adsc.70038","DOIUrl":"10.1002/adsc.70038","url":null,"abstract":"<div><div>A series of 5,7‐membered cyclometallated gold(III) complexes with N^C^N tridentate ligands are developed as catalysts, which are prepared <em>via</em> transmetalation of pyridine‐phenyl‐oxazoline ligand‐containing organomercury compounds with potassium gold(III) chloride (KAuCl<sub>4</sub>) with up to 86% yields. Investigation on the synthesis and catalytic activity of the newly developed gold(III) complexes under silver‐free conditions results in >90% conversion for propargylamines and up to >99% conversion for bifunctional modification of oligosaccharides <em>via</em> three‐component (A<sup>3</sup>)‐coupling reactions. Employment of the tridentate gold(III) complexes also successfully catalyzes the carboalkoxylation reaction of acetal alkynes. These results reveal potential applications of such 5,7‐membered tridentate gold(III) complexes as catalysts for organic transformation reactions and modification of biomolecules.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70038"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901710","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}
Zeyu Tian , Dongqin He , Jun Liang , Qing Liu , Meiling Ye , Li Hai , Guanghui Lv , Yong Wu
{"title":"Organic Photoredox‐Catalyzed 1,2‐Hydrogen Atom Transfer Enables the Synthesis of Cyclopropanes via Radical‐Polar Crossover Cyclization Cascade","authors":"Zeyu Tian , Dongqin He , Jun Liang , Qing Liu , Meiling Ye , Li Hai , Guanghui Lv , Yong Wu","doi":"10.1002/adsc.70045","DOIUrl":"10.1002/adsc.70045","url":null,"abstract":"<div><div>Cyclopropane is a prevalent synthetic building block present in pharmaceuticals and natural products, becoming a significant dimension for exploration in the fields of medicinal chemistry. However, the current synthesis methods for cyclopropane face numerous environmental and practical challenges, emphasizing the necessity of constructing more sustainable protocols. Herein, an organic photoredox‐catalyzed radical‐polar crossover cyclization cascade protocol for the synthesis of cyclopropanes enabled by 1,2‐hydrogen atom transfer is disclosed, which is distinguished by mild conditions, a broad range of substrates. Besides, drug molecules compatibility, scale‐up experiment, and synthetic transformations are performed to prove the potential application value of this protocol.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70045"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144763510","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}
Giulia De Santis , Andrea Maranzana , Federica Lauria , Mauro Spennacchio , Michael Andresini , Rosa Purgatorio , Marco Colella , Renzo Luisi , Leonardo Degennaro
{"title":"Tunable Preparation of α‐Aminoacyl Fluorides and α‐Fluoroamides via Base‐Induced Cascade Multiple‐Cleavage Processes from Bromodifluorohydrin Reagents and Amines","authors":"Giulia De Santis , Andrea Maranzana , Federica Lauria , Mauro Spennacchio , Michael Andresini , Rosa Purgatorio , Marco Colella , Renzo Luisi , Leonardo Degennaro","doi":"10.1002/adsc.70083","DOIUrl":"10.1002/adsc.70083","url":null,"abstract":"<div><div>A concise strategy for the divergent synthesis of α‐fluoroamides and α‐aminoacyl fluorides is developed via multiple bond‐cleavage processes of 2‐bromo‐2,2‐difluoro alcohols in the presence of amines. The transformation proceeds under mild conditions, displays a broad substrate scope, and features operational simplicity. Mechanistic studies, supported by density functional theory calculations, suggest the involvement of a putative <em>gem</em>‐difluoroepoxide intermediate that triggers a cascade of atom recombination events.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70083"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135427","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}
Mei Hong , Aoshi Xie , Shaoziyu Chen , Xu Chen , Chenjingyi Huang , Jianlin Han , Zupeng Chen
{"title":"Merging Cu2O Photo‐Thermo‐Catalyst with Lignosulfonate‐Supported Tempo for Aerobic Oxidation of 5‐Hydroxymethylfurfural into 2,5‐Diformylfuran","authors":"Mei Hong , Aoshi Xie , Shaoziyu Chen , Xu Chen , Chenjingyi Huang , Jianlin Han , Zupeng Chen","doi":"10.1002/adsc.70046","DOIUrl":"10.1002/adsc.70046","url":null,"abstract":"<div><div>The selective oxidation of 5‐hydroxymethylfurfural (HMF) into 2,5‐diformylfuran (DFF) represents a critical step in the sustainable synthesis of high‐value chemicals from renewable biomass. A significant challenge in achieving this transformation lies in developing an effective visible light‐driven heterogeneous photocatalytic method that excludes the use of dye‐based sensitizers. While solar energy presents an exceptionally promising renewable energy source for extensive future applications, its overall utilization remains suboptimal. To address these challenges, we introduce an innovative photo‐thermo‐catalyst system comprising octahedral Cu<sub>2</sub>O particles, which, when combined with lignosulfonate (LS)‐supported 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO), demonstrates decent catalytic performance for the selective oxidation of HMF into DFF under the illumination of a 400 nm light‐emitting diode light. This system achieves a remarkable 95% DFF yield at 60 °C under ambient oxygen conditions. This study successfully demonstrates the effective integration of a non‐noble metal photo‐thermo‐catalyst with a supported TEMPO system, which enables the efficient HMF‐to‐DFF transformation driven by visible light, eliminating the need for dye sensitizers in the process.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70046"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135306","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}
Sergio Torres‐Oya , Manuel A. Fernández‐Rodríguez , Mercedes Zurro
{"title":"Synthesis of 3,4‐Dihydroquinazolinones via Base‐Promoted Formal [4 + 2] Cycloadditions","authors":"Sergio Torres‐Oya , Manuel A. Fernández‐Rodríguez , Mercedes Zurro","doi":"10.1002/adsc.70056","DOIUrl":"10.1002/adsc.70056","url":null,"abstract":"<div><div>3,4‐dihydroquinazolin‐2(<em>1H</em>)‐one (3,4‐DHQ) is a key structural motif found in many biologically active molecules. Although several synthetic methods have been developed to date, harsh reaction conditions, and/or metal toxic reagents are often required. In this work, a general, metal‐free methodology for the synthesis of 3,4‐DHQs is described. This novel protocol relies on a formal [4 + 2] cycloaddition of in situ formed aza‐<em>ortho</em>‐quinone methides and isocyanates leading to a wide variety of 3,4‐DHQs in yields up to 98%.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70056"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135428","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}
Hui Wang , Fachao Yan , Yanan Hou , Long Shu , Xiaowei Li , Mingxia Zhang , Hongyou Cui , Hui Liu
{"title":"Barbier Reactions with Gaseous CO2 via Electromagnetic Milling","authors":"Hui Wang , Fachao Yan , Yanan Hou , Long Shu , Xiaowei Li , Mingxia Zhang , Hongyou Cui , Hui Liu","doi":"10.1002/adsc.70061","DOIUrl":"10.1002/adsc.70061","url":null,"abstract":"<div><div>The Barbier reaction has been utilized in the construction of CX (X = C, Si, B, N, etc.)bondsin organic chemistry for over a century. However, all reported strategies have been carried out in organic solvents or solvent‐free conditions involving solid–liquid or solid–solid phases, and gas‐phase Barbier reactions in one step are rare. In this work, a one‐step gas‐involved Barbier reaction for the synthesis of carboxylic acids under electromagnetic mill conditions is presented. This approach utilizes gas CO<sub>2</sub> at ambient pressure, which holds significant promise for isotope‐labeling chemistry. A variety of <sup>13</sup>C‐labeled carboxylic acids is synthesized efficiently using this method. This gas‐involved, liquid‐assisted grinding transformation could accelerate the advancement of this field.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70061"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901558","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}
Aleksandra Szymańska , Mateusz Nowicki , Subhabrata De , Barbara Krupa , Jakub Szyling , Katarina Ležaić , Marc‐Etienne Moret , Jędrzej Walkowiak
{"title":"Catalytic Hydroboration of Ketones Using Mn(CO)5Br and Mn2(CO)10","authors":"Aleksandra Szymańska , Mateusz Nowicki , Subhabrata De , Barbara Krupa , Jakub Szyling , Katarina Ležaić , Marc‐Etienne Moret , Jędrzej Walkowiak","doi":"10.1002/adsc.70092","DOIUrl":"10.1002/adsc.70092","url":null,"abstract":"<div><div>The commercially available and easy‐to‐handle manganese complexes Mn(CO)<sub>5</sub>Br and Mn<sub>2</sub>(CO)<sub>10</sub> effectively catalyze the hydroboration of ketones under mild conditions, yielding secondary alcohols after hydrolysis. These simple catalysts exhibit broad tolerance to different functional groups including esters, halides, and nitroarenes. Moreover, the reaction proceeds with high chemoselectivity toward CO bonds in the presence of esters, nitriles, nitro groups, or double CC bond. The proposed procedure enables fast, efficient synthesis of O‐borylated products, which are easily hydrolyzed in a one‐pot manner to various aryl and alkyl alcohols (even unsaturated ones) in excellent yields. Thus, the developed procedure compares favorably with other Mn catalytic systems, which require lengthy preparation, the application of structurally and electronically advanced ligands, and oxygen‐ and moisture‐free conditions.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70092"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915959","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}
{"title":"Visible Light‐Driven Photoredox Carboarylation of N‐Acryloyl Phosphinimides with Sulfoxonium Ylides","authors":"Ning Xian , Huawen Huang","doi":"10.1002/adsc.70095","DOIUrl":"10.1002/adsc.70095","url":null,"abstract":"<div><div>A mild visible light‐driven photoredox cascade radical cyclization of <em>N</em>‐acryloyl phosphinamides with sulfoxonium ylides for the modular synthesis of value‐added cyclic phosphinamides under additive‐free conditions has been reported. This scalable protocol uses sulfoxonium ylides as novel carbon radical precursors in an eco‐friendly MeCN/H<sub>2</sub>O solvent system, eliminating the need for stoichiometric oxidants or bases while maintaining broad functional group tolerance. The carboarylation reaction has been successfully implemented at ambient temperature, providing an efficient and viable access to P–N scaffolds bearing a quaternary carbon center. Mechanistic studies support a proton‐coupled electron transfer pathway for radical generation from sulfoxonium ylides under visible‐light irradiation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70095"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910717","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}