{"title":"Contrasting Facial Selectivity of a Squaramide‐Tagged Proline in the Asymmetric Michael Addition of Ketones to Maleimides","authors":"Kiran Kumari , Akram Gulam Hussain Khan , Srinivasan Easwar","doi":"10.1002/adsc.202400791","DOIUrl":"10.1002/adsc.202400791","url":null,"abstract":"<div><div>A squaramide moiety was introduced at the C‐4 position of proline to afford an organocatalyst that served as a stereocontrol element to promote the asymmetric Michael addition of cyclic ketones to maleimides. A variety of chiral succinimides were obtained by the conjugate addition in 84–98% yield accompanied by 58–96% enantioselectivity. The results also include an interesting contrast in the facial selectivity observed with cyclohexanones and cycloheptanones, whereas an asymmetric desymmetrization of 4‐alkyl cyclohexanones was also achieved using the transformation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"366 22","pages":"Pages 4715-4722"},"PeriodicalIF":4.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141986688","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":"Selective Access to Sultams and Spirocyclic Sultams by the Divergent Annulations of (N‐Aryl)‐Alkynyl Sulphonamides","authors":"Chada Raji Reddy , Anjali Rathaur , Banoth Karuna Sagar , Agnuru Theja , Amol D. Patil , Muppidi Subbarao","doi":"10.1002/adsc.202400382","DOIUrl":"10.1002/adsc.202400382","url":null,"abstract":"<div><div>Herein, we present the first annulation reaction of (<em>N</em>‐aryl)‐alkynyl sulphonamides leading to sultams or spirocyclic sultams. The selective formation of aforesaid products is based on the variable reactivity, intramolecular <em>ortho</em>‐cyclization or dearomative <em>ipso</em>‐annulation, guided by the substituent on <em>N</em>‐aryl group of the substrate. The <em>ortho</em>‐annulation is mediated by electrophile, while the <em>ipso</em>‐annulation is promoted by the radical, enabling the functionalization (selenyl or iodo) on sultams. The synthetic potential of this method is illustrated by modifications of the functional groups present in the products obtained.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"366 22","pages":"Pages 4772-4777"},"PeriodicalIF":4.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141177304","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}
Zenghui Zhang , Wenjing Yang , Changji Liu , Xiao Yu , Shuyong Song , Chengcai Xia
{"title":"Tandem Electrochemical Redox/Condensation Reaction Between 2‐Amino Nitrobenzenes and Aliphatic Alcohols: An Approach to Benzimidazoles","authors":"Zenghui Zhang , Wenjing Yang , Changji Liu , Xiao Yu , Shuyong Song , Chengcai Xia","doi":"10.1002/adsc.202400771","DOIUrl":"10.1002/adsc.202400771","url":null,"abstract":"<div><div>Tandem reactions <em>via</em> electrocatalytic annulations have emerged as a strategy for the construction of heterocycles. Herein, a two‐component electrochemical annulation <em>via</em> sequential reduction, oxidation, and condensation steps to synthesize valuable benzimidazoles motifs is reported. This reaction, which utilizes electricity as both the oxidants and reductants, tolerates a broad range of functional groups. Detailed mechanistic studies including control experiments, cyclic voltammetry (CV) analysis, and key reaction intermediate characterization, reveals an intermolecular electrochemical redox/cyclization pathway.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"366 22","pages":"Pages 4667-4673"},"PeriodicalIF":4.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102001","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":"Synthesis of Difuropyridines from Chitin-Derived 3-Acetamidofuran and their Application to Photocatalytic Reactions","authors":"Haifeng Gan, Peipei Ma, Taixiang Yang, Fei Cao, Jianliang Zhu","doi":"10.1002/adsc.202401164","DOIUrl":"https://doi.org/10.1002/adsc.202401164","url":null,"abstract":"<p>Difuropyridines have been prepared from aldehydes and chitin-derived 3-acetamidofuran (3AF) under acid-catalyzed conditions. Difuropyridines were comprehensively synthesized for the first time. The synthesized difuropyridines can be applied to prepare fluorescent probe analogs or catalyze decarboxylative reactions as photocatalysts.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665560","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":"The Chemistry of α-Enolizable Alkynones: a Comprehensive Review","authors":"Sofia Karnakova, Marina Dvorko, Dmitrii Shabalin","doi":"10.1002/adsc.202401312","DOIUrl":"https://doi.org/10.1002/adsc.202401312","url":null,"abstract":"This comprehensive review summarizes the published literature data concerning the chemistry of α-enolazible alkynones, also denoted aliphatic or C-H active alkynones, where an alkyl group is adjacent to the carbonyl function, from the first example in 1949 to the present day. Starting from a historical perspective, the reader will be introduced to the recent achievements and future challenges in this field. The review covers around 100 references.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"249 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670394","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":"Synergistic Palladium/Silver/Ligand Catalysis for C−H Alkenylation of 2,1,3-Benzofused Heterodiazoles","authors":"Siyeon Jeong, Chaerin Lee, Jung Min Joo","doi":"10.1002/adsc.202401139","DOIUrl":"https://doi.org/10.1002/adsc.202401139","url":null,"abstract":"<p>The combination of palladium and silver complexes has emerged as a bimetallic catalytic system in C−H activation, frequently outperforming palladium-only systems. Beyond the conventional roles of silver (I) salts serving as oxidants, halide scavengers, and Lewis acids, Pd−Ag bimetallic synergism has been shown to facilitate C−H cleavage. In this study, we explore the incorporation of a pyrazolopyridone (PzPyOH) ligand into a Pd−Ag bimetallic catalytic system, which together promote both C−H cleavage and migratory insertion processes. This synergistic approach enables dehydrogenative C−H alkenylations at the C4 position of 2,1,3-benzothiadiazole, 2,1,3-benzoxadiazole, and 2,1,3-benzotriazole with alkenes. These results demonstrate the potential of combining novel ligands with heterobimetallic systems to facilitate other elementary steps beyond C−H cleavage, suggesting their broader applicability in C−H functionalization.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"8 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665559","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":"Synthesis of Functionalized Benzo[f]chromanes and Hydroxyalkyl Naphthols: Catalytic Coupling of Naphthols and Allylic Alcohols","authors":"Raman Sankar, Chidambaram Gunanathan","doi":"10.1002/adsc.202401243","DOIUrl":"https://doi.org/10.1002/adsc.202401243","url":null,"abstract":"Catalytic dearomatization of arenols is an uphill task that can serve as a powerful method to construct C-C bonds with unsaturated coupling partners. Herein, a simple and efficient strategy for coupling naphthols with allylic alcohols is reported. A single Ru(II) pincer catalyzed coupling of naphthols with primary allylic alcohols led to the formation of benzo(f)chromanes, whereas the use of secondary alcohols delivered the hydroxyalkyl naphthols. Broad substrate scope and good functional group tolerance are demonstrated. Notably, a high diastereoselectivity is attained on chromanes. Hydroxyalkyl naphthols are synthetically transformed into spiroethers, and dearomative bromination is achieved on chromanes. Mechanistic studies revealed the involvement of tandem reactions, a formal O-H bond activation of allylic alcohols by an active catalyst via amine-amide metal-ligand cooperation provided α-β, unsaturated carbonyl intermediates, which further underwent 1,4 conjugate addition with dearomatized naphthols. One of the crucial intermediates, naphthyl radical, is elucidated by EPR studies and trapped using a radical scavenger. Liberated hydrogen and water molecules are the only byproducts in these transformations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670393","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}
Rong-Rong Ma, Bo-Yang Liu, Lei Yan, Jun-Bing Lin, Peng-Fei Xu
{"title":"Recent Advances in Organocatalytic Asymmetric Synthesis of Bicyclo[3.3.1]nonane Frameworks","authors":"Rong-Rong Ma, Bo-Yang Liu, Lei Yan, Jun-Bing Lin, Peng-Fei Xu","doi":"10.1002/adsc.202401158","DOIUrl":"https://doi.org/10.1002/adsc.202401158","url":null,"abstract":"The bicyclo[3.3.1]nonane ring represents an attractive yet challenging synthetic targets in the field of organic synthesis, especially in a stereocontrolled fashion. Over the past two decades, organocatalysis has emerged as an enabling technology for the facile construction of enantioenriched molecules with remarkably increasing complexity and diversity, and a myriad of chiral architectures containing bicyclo[3.3.1]nonane units were elegantly assembled through organocatalytic asymmetric transformations. This review summarizes recent advancements on this topic (mainly from 2010 to 2023), emphasizing the reaction types such as desymmetrization and cascade reactions of different prochiral starting materials toward various chiral bicyclo[3.3.1]nonanes as well as their aza, oxa and thio derivatives. Meanwhile, the synthetic strategy, reaction mechanism, substrate scope and synthetic applications of these catalytic reactions are also discussed. We hope that this review will motivate further development and application of organocatalytic asymmetric synthesis of bicyclo[3.3.1]nonane frameworks.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"75 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642606","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":"Rh(III)‐Catalyzed C‐H Cyclization of 2‐Arylbenzimidazoles with CF3‐Imidoyl Sulfoxonium Ylides and Further Sc(III)‐Catalyzed Deaminative Hydroxylation","authors":"Juting Liao, Ruirui Zhai, Xiaoyang Gao, Hongliang Wu, Dulin Kong, Shuojin Wang, Xun Chen","doi":"10.1002/adsc.202401220","DOIUrl":"https://doi.org/10.1002/adsc.202401220","url":null,"abstract":"An efficient Rh(III)‐catalyzed C‐H bond activation/cyclization of 2‐arylbenzimidazoles with CF3‐imidoyl sulfoxonium ylides has been achieved, yielding diverse CF3‐ and amino‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines, which could undergo a deaminative hydroxylation to access CF3‐ and hydroxy‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines under Sc(OTf)3 catalyst. This developed strategy features easily available starting materials, broad substrate scope, ready scalability and high efficiency. Moreover, the antitumor activities of selected products against some human cancer cell lines were also investigated, and the results indicated that several products show the effective antiproliferative activities.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642947","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":"Synthesis of Tetrahydro-β-carbolines via Cascade Sigmatropic Rearrangements","authors":"Daiki Oka, Tomomi Ohtsuka, Ken-ichi Takao, Akihiro Ogura","doi":"10.1002/adsc.202401189","DOIUrl":"https://doi.org/10.1002/adsc.202401189","url":null,"abstract":"We have developed a synthesis for tetrahydro-β-carbolines involving cascade sigmatropic rearrangements. The substrates were conveniently prepared from parent anilines via a [2,3]-sigmatropic rearrangement and cyanomethylation. Silver-mediated decyanation afforded the corresponding iminium cation, which underwent a cascade consisting of an aza-Cope rearrangement, an aza-oxa-Cope rearrangement, an aromatization, and a Pictet–Spengler reaction, and tetrahydro-β-carbolines were obtained as the single product. The reaction involved seven bond scissions and four bond formations and was triggered by a single reagent.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609892","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}