Advanced Synthesis & Catalysis最新文献_第3页

Controlling Catalyst Speciation to Achieve Room Temperature Pd‐Catalyzed Aminations with Aryl and Heteroaryl Chlorides 控制催化剂形态实现室温钯催化芳基和杂芳基氯化物胺化

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401337

Mariur Rodriguez Moreno , Mary L. Setelin , Joshua D. Hansen , James L. Corey , Kirt L. Noble , Lillian R. Stillwell , Emily Angell , Olivia A. Stubbs , Jugal Kumawat , Carlos S. Muñoz Gomez , Stacey J. Smith , Daniel H. Ess , David J. Michaelis

{"title":"Controlling Catalyst Speciation to Achieve Room Temperature Pd‐Catalyzed Aminations with Aryl and Heteroaryl Chlorides","authors":"Mariur Rodriguez Moreno , Mary L. Setelin , Joshua D. Hansen , James L. Corey , Kirt L. Noble , Lillian R. Stillwell , Emily Angell , Olivia A. Stubbs , Jugal Kumawat , Carlos S. Muñoz Gomez , Stacey J. Smith , Daniel H. Ess , David J. Michaelis","doi":"10.1002/adsc.202401337","DOIUrl":"10.1002/adsc.202401337","url":null,"abstract":"<div><div>The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401337"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986776","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

Base‐Mediated Four‐Component Intramolecular Cyclization Reaction: One‐Pot Access to Imidazole‐4‐(2H)‐Ones 碱介导的四组分分子内环化反应：咪唑- 4 - (2H) -酮的一罐途径

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401433

Ganesh P. Pawar , Indrajeet J. Barve , Li‐Ching Shen , Chung‐Ming Sun

引用次数: 0

Synthesis of Layered Copper‐Based 2D‐MOFs for Enhanced Catalytic Regioselective Phosphorylation of Alkynes and P−H Bonds 层状铜基2D-MOFs的合成及其对炔烃和P-H键催化区域选择性磷酸化的影响

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401414

Shipan Xu , Biquan Xiong , Minjing Yuan , Weifeng Xu , Renfeng Cao , Fan Cao , Longzhi Zhu , Shuang‐Feng Yin

{"title":"Synthesis of Layered Copper‐Based 2D‐MOFs for Enhanced Catalytic Regioselective Phosphorylation of Alkynes and P−H Bonds","authors":"Shipan Xu , Biquan Xiong , Minjing Yuan , Weifeng Xu , Renfeng Cao , Fan Cao , Longzhi Zhu , Shuang‐Feng Yin","doi":"10.1002/adsc.202401414","DOIUrl":"10.1002/adsc.202401414","url":null,"abstract":"<div><div>A functionalized heterogeneous Cu‐based metal‐organic framework (Cu‐2D‐MOF) was synthesized through the reaction of Cu(NO<sub>3</sub>)<sub>2</sub> ⋅ 3H<sub>2</sub>O with 2,3,5,6‐tetrafluoroterephthalic acid and 4,4′‐bipyridine. The synthesized material underwent comprehensive characterization using various techniques, including FT‐IR spectroscopy, N<sub>2</sub> physical adsorption, scanning electron microscopy (SEM), and X‐ray photoelectron spectroscopy (XPS). Subsequently, the catalytic performance of Cu‐2D‐MOFs was assessed in the hydrophosphorylation and aerobic oxidative dehydrogenative coupling reactions involving alkynes and P−H bonds. The catalyst demonstrated remarkable catalytic activity in both transformations, effectively yielding a wide variety of (<em>E</em>)‐alkenyl‐phosphoryl and alkynyl‐phosphoryl compounds, respectively. Notably, the incorporation of this MOF material facilitated the phosphorylation reaction to proceed seamlessly, eliminating the necessity for supplementary small molecular organic ligands. Furthermore, the catalyst demonstrated ease of recovery and recyclability through a simple recovery process. Employing a systematic approach of sequential control experiments, we have delineated the potential transformation pathway of the reaction and consequently hypothesized a probable reaction mechanism for the observed transformation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401414"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031276","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

Photo‐Induced Oxidative C−H Esterification of Quinoxalinones with Arylaldehydes under Mild Conditions 温和条件下喹啉酮与芳醛的光诱导C-H氧化酯化反应

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202500018

Kai Zheng , Zhaoyang Wang , Yacong Wang , Chao Chen , Chao Shen

引用次数: 0

Visible Light‐Promoted Cascade Sulfonylation‐Cyclization‐Aromatization of Tertiary Enamides to Access Multi‐Substituted Pyridines and 1,2‐Dihydropyridines 可见光促进三级烯酰胺的级联磺酰化-环化-芳香化反应以获得多取代吡啶和 1,2-二氢吡啶

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401516

Xin‐Ming Xu , Jiping Wang , Sen Chen , Xiaoxu Chen , Jinchun Chen , Qian Liu , Zu‐Li Wang , Miao Tian , Kai Sun

引用次数: 0

Structure‐Guided Engineering of Oleate Hydratase for the Synthesis of Small Chiral Alcohols without Decoy Molecule 无诱骗分子油酸水合物合成小手性醇的结构导向工程

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401358

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}

引用次数: 0

Regio‐ and Diastereoselective Cascade Synthesis of 5‐Alkylidene‐γ‐Lactams via Copper‐Catalyzed Hydro‐Oxycarbonylation 铜催化氢氧羰基化合成5 -烷基烯- γ -内酰胺的区域和非对映选择性级联反应

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401535

Galder Llorente , Maria Teresa Herrero , Garazi Urgoitia , Raul SanMartin

{"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}

引用次数: 0

Hydrofluoroether Synthesis through One‐Pot Anodic Iodoalkoxylation of Alkenes 通过烯烃的一锅式阳极碘烷氧基化合成氢氟醚

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401108

Martin Becerra‐Ruiz , Bethan Winterson , Edwin G. Pérez , Thomas Wirth

引用次数: 0

Au(I)‐Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines 金(I)催化四氢二氮卓类或四氢二氮卓类烯烯的区域发散氢化芳基化反应

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401541

Pengyu Zhou , Pascal Retailleau , Vincent Gandon , Arnaud Voituriez , Xavier Guinchard

引用次数: 0

Combined Electrooxidation and Proline Catalysis for Asymmetric Formal Cross‐Dehydrogenative Coupling of Benzylic Alcohols with Ketones 苯甲酸醇与酮不对称形式交叉脱氢偶联的电氧化与脯氨酸联合催化

IF 4.4 2区化学

Advanced Synthesis & Catalysis Pub Date : 2025-04-15 DOI: 10.1002/adsc.202401466

Hong‐Ping Pu , Chao‐Jiu Long , Zhe‐Kai Liu , Zhi Guan , Yan‐Hong He

引用次数: 0