Xin‐Ming Xu , Jiping Wang , Sen Chen , Xiaoxu Chen , Jinchun Chen , Qian Liu , Zu‐Li Wang , Miao Tian , Kai Sun
{"title":"Visible Light‐Promoted Cascade Sulfonylation‐Cyclization‐Aromatization of Tertiary Enamides to Access Multi‐Substituted Pyridines and 1,2‐Dihydropyridines","authors":"Xin‐Ming Xu , Jiping Wang , Sen Chen , Xiaoxu Chen , Jinchun Chen , Qian Liu , Zu‐Li Wang , Miao Tian , Kai Sun","doi":"10.1002/adsc.202401516","DOIUrl":"10.1002/adsc.202401516","url":null,"abstract":"<div><div>Functionalized pyridines and 1,2‐dihydropyridines are crucial organic entities in natural products, organic materials, drugs and catalysts. Despite progress, a facile and eco‐friendly synthesis remains desirable so far. In this context, we disclose a novel visible light‐promoted radical cascade sulfonylation‐cyclization‐aromatization of <em>N</em>‐propargyl enamides with selenosulfonates. This approach avoids the use of metal‐ or photocatalyst, bases and external oxidants, marking a significant advance in sustainable and green chemistry accords. Utilizing this protocol, we successfully synthesized a diverse range of sulfonated 1,2‐dihydropyridines and pyridines, featuring good functional group compatibility, simple operation and mild condition.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401516"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050528","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}
Natalie Härterich , Andreas Schneider , Philip Horz , Nicolas D. Travnicek , Bernhard Hauer
{"title":"Structure‐Guided Engineering of Oleate Hydratase for the Synthesis of Small Chiral Alcohols without Decoy Molecule","authors":"Natalie Härterich , Andreas Schneider , Philip Horz , Nicolas D. Travnicek , Bernhard Hauer","doi":"10.1002/adsc.202401358","DOIUrl":"10.1002/adsc.202401358","url":null,"abstract":"<div><div>Small and chiral secondary alcohols are sought‐after compounds that are frequently used in the synthesis of biologically active compounds. However, their stereochemically correct synthesis remains a challenge for the chemical industry. Synthetic routes are restrained by multiple steps and thus low atom efficiency. Here we employ engineered variants from the oleate hydratase from <em>E. meningoseptica</em> to produce chiral C5‐C8 secondary alcohols within a single step. First, we established a two‐phase system (2‐PS) to trap the volatile substrates/products which facilitated semi‐rational mutagenesis in the active site and tunnel of the enzyme. These efforts led to variants with an up to 20‐fold increase in catalytic activity and >99% <em>ee</em>, notably, without the use of a decoy molecule. Computational analysis indicated structural changes in the tunnel radius, ligand transport and energy profiles, which gave us hints to explain the enhanced performance of the variants. Interestingly, scaling up the reaction volume demonstrated significant increases in product concentrations, leading up to a 100‐fold increase in comparison to the current benchmark. This new 2‐PS and the engineered enzyme variants offer a promising approach for a scalable, asymmetric hydration of small unactivated alkenes, which would drastically ease the access to chiral alcohol‐based pheromones or drugs.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401358"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142934978","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":"Regio‐ and Diastereoselective Cascade Synthesis of 5‐Alkylidene‐γ‐Lactams via Copper‐Catalyzed Hydro‐Oxycarbonylation","authors":"Galder Llorente , Maria Teresa Herrero , Garazi Urgoitia , Raul SanMartin","doi":"10.1002/adsc.202401535","DOIUrl":"10.1002/adsc.202401535","url":null,"abstract":"<div><div>Transition metal‐catalyzed hydrofunctionalization of alkynes and, more precisely, the intramolecular hydro‐oxycarbonylation (cycloisomerization) of acetylenic acids, has been widely employed as a key step in cascade processes for the construction of valuable and complex molecules. However, in contrast with other aminonucleophiles, no method has been reported for the reaction between primary monoamines and non‐activated alkynoic acids. Hence, a procedure has been devised for the regio‐ and diastereoselective preparation of 5‐alkylidene‐γ‐lactams via a copper‐catalyzed cascade reaction between alkynoic acids and amines. The developed protocol proves to be scalable and demonstrates significant tolerance to a wide range of structurally diverse alkynoic acids and amines bearing various functional groups, as evidenced by 60 high‐yielding examples. An exhaustive experimental and computational analysis of the reaction is also provided to unravel the nature and role of the copper catalyst, the observed regioselectivity and the mechanism of the reaction.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401535"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961627","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}
Martin Becerra‐Ruiz , Bethan Winterson , Edwin G. Pérez , Thomas Wirth
{"title":"Hydrofluoroether Synthesis through One‐Pot Anodic Iodoalkoxylation of Alkenes","authors":"Martin Becerra‐Ruiz , Bethan Winterson , Edwin G. Pérez , Thomas Wirth","doi":"10.1002/adsc.202401108","DOIUrl":"10.1002/adsc.202401108","url":null,"abstract":"<div><div>The incorporation of carbon‐fluorine bonds can profoundly influence the chemical and physical properties of drugs, agrochemicals, and materials. Different methods allow the installation of CF<sub>3</sub>, CF<sub>2</sub>H units and C−F bonds including trifluoro‐ and difluoromethoxylations, reflecting the limited diversity of reactions available to synthetic chemists. We introduce the 2,2,2‐trifluoroethoxy group through an electro‐oxidative iodination of alkenes as a versatile substituent for fluorine chemists. An iodoarene serves as an unusual iodine source facilitating the 1,2‐iodoalkoxylation of a broad range of industrially relevant aliphatic alkenes in high yields (31–98%) showing high Markovnikov regioselectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401108"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431752","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":"Au(I)‐Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines","authors":"Pengyu Zhou , Pascal Retailleau , Vincent Gandon , Arnaud Voituriez , Xavier Guinchard","doi":"10.1002/adsc.202401541","DOIUrl":"10.1002/adsc.202401541","url":null,"abstract":"<div><div>Allenes tethered to pyrroles undergo Au(I)‐catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl‐gem‐disubstituted allenes preferentially lead to tetrahydrodiazepines via 7‐<em>exo</em>‐cyclizations, while aryl‐substituted allenes preferentially lead to tetrahydrodiazonines via 9‐<em>endo</em>‐cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7‐<em>exo</em> vs 9‐<em>endo</em>) of these gold(I)‐catalyzed cyclizations.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401541"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981648","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}
Hong‐Ping Pu , Chao‐Jiu Long , Zhe‐Kai Liu , Zhi Guan , Yan‐Hong He
{"title":"Combined Electrooxidation and Proline Catalysis for Asymmetric Formal Cross‐Dehydrogenative Coupling of Benzylic Alcohols with Ketones","authors":"Hong‐Ping Pu , Chao‐Jiu Long , Zhe‐Kai Liu , Zhi Guan , Yan‐Hong He","doi":"10.1002/adsc.202401466","DOIUrl":"10.1002/adsc.202401466","url":null,"abstract":"<div><div>This article presents a method for asymmetric formal cross‐dehydrogenative coupling of benzylic alcohols with ketones through combined electrooxidation and organocatalysis. Employing inexpensive and environmentally friendly proline as a chiral organocatalyst, various benzylic alcohols and simple ketones serve as substrates to directly obtain diverse chiral β‐hydroxycarbonyl compounds with moderate to good yields (up to 85%) and excellent stereoselectivity (up to 99% ee and 99:1 dr). The reaction proceeds under mild conditions at room temperature in air, without oxidants or additives, demonstrating robust functional group tolerance and atom efficiency. Hydrogen gas released at the cathode is the sole byproduct. Using L‐ or D‐proline allows straightforward access to both chiral configurations of β‐hydroxycarbonyl compounds.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401466"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050531","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":"Photoinduced Catalytic Alkylation of Active Methine Compounds with Nonactivated Alkenes Using Yttrium Triflate as a Lewis Acid Catalyst","authors":"Yasuhiro Yamashita , Rentaro Enokijima , Yoshihiro Ogasawara , Tomoya Hisada , Shū Kobayashi","doi":"10.1002/adsc.202401568","DOIUrl":"10.1002/adsc.202401568","url":null,"abstract":"<div><div>Photoinduced catalytic alkylation reactions of active methine compounds with nonactivated alkenes have been developed using an organophotocatalyst, a metal Lewis acid, an arylthiol, and an amine base catalyst system. The alkylation reactions proceeded smoothly under ambient conditions with blue light irradiation, affording the desired products bearing quaternary carbon centers in high yields. Furthermore, enantioselective alkylation with an nonactivated alkene was achieved using a chiral Lewis acid.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401568"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981647","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":"Regio‐ and Stereoselective β‐C(sp3)−H Activation/ Functionalization of Saturated Nitrogen Heterocycles, Amines and Amides","authors":"Sanjay Yadav , V. Murugesh , Surisetti Suresh","doi":"10.1002/adsc.202401398","DOIUrl":"10.1002/adsc.202401398","url":null,"abstract":"<div><div>Regio‐ and stereoselective <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond functionalizations of saturated nitrogen heterocycles, amines/amides are challenging and have emerged as an important topic of research in the area of C(<em>sp</em><sup>3</sup>)−H activation. Herein, we have summarized various <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H activation/functionalization methods; this review provides an overview of various trending approaches for <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond activation/functionalization of saturated nitrogen heterocycles, amines/amides. The regio‐ and stereoselective <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond activation methods are classified based on the reaction pathways. The literature methods including directing group or ligand‐assisted transformations, reactions proceeding through enamine intermediate, redox‐neutral methods and other trending methods including photoredox and transitional metal‐free methods are discussed with recent updates.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401398"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991421","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}
Anjali Dahiya , Kalyan Dhara , Jordan Garo , Julien Gicquiaud , Alexandre Karnat , Murielle Berlande , Philippe Hermange , Jean‐Marc Sotiropoulos , Patrick Y. Toullec
{"title":"Brønsted Acid‐Catalyzed Enantioselective and Para‐Selective Addition of Phenols to 1‐Alkynylnaphth‐2‐Ols","authors":"Anjali Dahiya , Kalyan Dhara , Jordan Garo , Julien Gicquiaud , Alexandre Karnat , Murielle Berlande , Philippe Hermange , Jean‐Marc Sotiropoulos , Patrick Y. Toullec","doi":"10.1002/adsc.202401457","DOIUrl":"10.1002/adsc.202401457","url":null,"abstract":"<div><div>A chiral Brønsted acid‐catalyzed synthesis of axially chiral alkenes was developed via an enantioselective and <em>para</em>‐selective Friedel–Crafts reaction between phenols and 1‐alkynylnaphth‐2‐ols. This methodology features an efficient hydroarylation with high functional group tolerance, complete <em>para</em>‐selectivity, excellent yields (up to 99%), and enantioselectivities (up to 94% ee) in the presence of a <em>N</em>‐triflylphosphoramide catalyst. DFT calculations were performed to investigate <em>para</em>‐selectivity and results indicate that both kinetics and thermodynamics parameters are more favorable compared to <em>ortho</em>‐selectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401457"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992654","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}
Maria Nicolas , Jan‐Dirk Küsters‐Spöring , Chiara Aufderheide , Helen Traving , Carina Ronja Kipp , Victoria S. Pfennig , Carsten Bolm , Petra Siegert , Dörte Rother
{"title":"Enzymatic Asymmetric Synthesis of All Stereoisomers of Aliphatic, Vicinal Diols in Conventional and Non‐Conventional Media","authors":"Maria Nicolas , Jan‐Dirk Küsters‐Spöring , Chiara Aufderheide , Helen Traving , Carina Ronja Kipp , Victoria S. Pfennig , Carsten Bolm , Petra Siegert , Dörte Rother","doi":"10.1002/adsc.202401143","DOIUrl":"10.1002/adsc.202401143","url":null,"abstract":"<div><div>Chiral, vicinal diols are of high interest for academic research and industrial applications. For synthesizing chiral diols, enzymes are important catalysts due to their high selectivity and ability to work under tolerable temperature and no pressure. In this study, two consecutive enzyme‐catalyzed steps were used for the asymmetric synthesis of aliphatic, vicinal diols with high product concentrations and chiral purity. The reaction comprised a ligation step employing lyases and a subsequent reduction step using oxidoreductases. Either in an aqueous buffer or an organic solvent, the potentially biobased aldehydes acetaldehyde, propanal, butanal, and pentanal were used as substrates. Here, all possible stereoisomers of 2,3‐butanediol, 3,4‐hexanediol, 4,5‐octanediol, and 5,6‐decanediol were produced with <em>isomeric content</em> values between 72% and >99%, and concentrations between 4.1 and 115 mM. This work shows how four symmetric, chiral, vicinal diols can be synthesized by combining enzymes in a modular way, including exemplarily scaling.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401143"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939521","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}