FeCl3/K2S2O8/Et3SiH system-mediated α-methylation of β-ketosulfones with N,N-dimethylformamide (DMF) was developed. In the overall process, DMF takes up the role of one methyl group in the generation of α-methyl β-ketosulfones via single carbon-carbon (C-C) bond formation under the reflux condition. Herein, a plausible reaction mechanism is proposed.
{"title":"FeCl3/K2S2O8/Et3SiH System-Mediated α-Methylation of β-Ketosulfones with DMF","authors":"Meng-Yang Chang, Chi-Ru Yang","doi":"10.1002/adsc.202400476","DOIUrl":"https://doi.org/10.1002/adsc.202400476","url":null,"abstract":"FeCl3/K2S2O8/Et3SiH system-mediated α-methylation of β-ketosulfones with N,N-dimethylformamide (DMF) was developed. In the overall process, DMF takes up the role of one methyl group in the generation of α-methyl β-ketosulfones via single carbon-carbon (C-C) bond formation under the reflux condition. Herein, a plausible reaction mechanism is proposed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141858041","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}
Organic electrosynthesis has become a green, efficient and sustainable alternative to traditional organic transformation for the redox reactions. In this connection, indirect electrolysis employing redox mediators is attaining increasing significance as it offers a chance to improve reaction selectivity and avoids the over-oxidation/reduction issues encountered in direct electrolysis. Triarylamines and triarylimidazoles, as representative organic molecular mediators, have attracted widespread attention in recent years due to the advantages of well-defined easy structural modification and tunable redox ability. Hence, in this minireview, the recent growth of triarylamine and triarylimidazole derivatives mediated electrochemical oxidation reactions were presented, highlighting the structural optimization, electrochemical performance and reaction mechanism of these organic mediators. Moreover, the photocatalytic and photoelectrocatalytic cases with these molecular mediators were also highlighted. To conclude, the current challenges and future prospects of this field are also discussed.
{"title":"Molecular Electro(photo)catalysis: Triarylamine and Triarylimidazole Derivatives Mediated Oxidation Systems In Organic Electrosynthesis","authors":"Shuai Liu, Li Ma, Feixiang Hao, Wei Gao, Baoying Li, Siyuan Liu, Zunqi Liu, Yuehui Li, Jianbin Chen","doi":"10.1002/adsc.202400435","DOIUrl":"https://doi.org/10.1002/adsc.202400435","url":null,"abstract":"Organic electrosynthesis has become a green, efficient and sustainable alternative to traditional organic transformation for the redox reactions. In this connection, indirect electrolysis employing redox mediators is attaining increasing significance as it offers a chance to improve reaction selectivity and avoids the over-oxidation/reduction issues encountered in direct electrolysis. Triarylamines and triarylimidazoles, as representative organic molecular mediators, have attracted widespread attention in recent years due to the advantages of well-defined easy structural modification and tunable redox ability. Hence, in this minireview, the recent growth of triarylamine and triarylimidazole derivatives mediated electrochemical oxidation reactions were presented, highlighting the structural optimization, electrochemical performance and reaction mechanism of these organic mediators. Moreover, the photocatalytic and photoelectrocatalytic cases with these molecular mediators were also highlighted. To conclude, the current challenges and future prospects of this field are also discussed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141858040","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}
Shiping Zhong, Jianwei Zhou, Boda Li, Zunting Zhang, Tao Wang
Monophosphine ligands based on C–N axially chiral N-Arylpyrrole backbones are prepared starting from amino acids and evaluated in Pd-catalyzed asymmetric allylic substitutions. 20.7- 99.9% ees are achieved in the reactions of rac-1,3-diphenylallyl acetates with O-, N- and C-nucleophiles. Ligand screening revealed that the steric hindrance from 3- or 4- position of the pyrrole is crucial for the enantioselectivity of the reaction. The synthetic utilization of the products was demonstrated by the transformation of one product by a gold-catalyzed oxidative rearrangement reaction.
{"title":"Palladium-Catalyzed Asymmetric Allylic Substitutions Achieved by C–N Axially Chiral N-Arylpyrrole Derived Monophosphine Ligands","authors":"Shiping Zhong, Jianwei Zhou, Boda Li, Zunting Zhang, Tao Wang","doi":"10.1002/adsc.202400206","DOIUrl":"https://doi.org/10.1002/adsc.202400206","url":null,"abstract":"Monophosphine ligands based on C–N axially chiral N-Arylpyrrole backbones are prepared starting from amino acids and evaluated in Pd-catalyzed asymmetric allylic substitutions. 20.7- 99.9% ees are achieved in the reactions of rac-1,3-diphenylallyl acetates with O-, N- and C-nucleophiles. Ligand screening revealed that the steric hindrance from 3- or 4- position of the pyrrole is crucial for the enantioselectivity of the reaction. The synthetic utilization of the products was demonstrated by the transformation of one product by a gold-catalyzed oxidative rearrangement reaction.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141858001","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}
The rapid development of photo-synergistic transition metal catalytic systems has provided a green paradigm to complement thermal transition metal catalytic methods. However, the most commonly used iridium or ruthenium complexes involve expensive in nature, in contrast to the abundant copper elements in the earth's crust, which are highly valued for their unique electronic structure and light-absorbing properties. Recently, the application of copper and photocatalytic synergistic strategies in radical cyclization reactions has progressed considerably, leading to a renaissance in the synthesis of functional natural products, drugs and their analogues, but summary work addressing this aspect has not been reported. In this review, we briefly analyze the effect of ligand choice on copper complexes and some inorganic copper salts and even on light sources. We then summarize the copper and photocatalytic synergistic strategies in radical cyclization reactions and classify them into three categories, C, N and O radicals, according to the class of the central atom of the radical in each work, and in each category will be elaborated in turn from coordination cyclization via Cu catalysts, direct radical cyclization and other cyclization mode. For individual more complex reactions, the mechanisms are explored and briefly discussed.
光协同过渡金属催化系统的快速发展为热过渡金属催化方法提供了一种绿色范例。然而，最常用的铱或钌络合物价格昂贵，而地壳中丰富的铜元素则因其独特的电子结构和光吸收特性而备受青睐。最近，铜与光催化协同策略在自由基环化反应中的应用取得了长足的进步，导致了功能性天然产物、药物及其类似物合成的复兴，但有关这方面的总结性工作尚未见报道。在本综述中，我们简要分析了配体选择对铜络合物和一些无机铜盐甚至光源的影响。然后，我们总结了自由基环化反应中的铜与光催化协同策略，并根据每种工作中自由基中心原子的类别，将其分为 C、N 和 O 自由基三类，在每一类中将依次从通过铜催化剂的配位环化、直接自由基环化和其他环化模式进行阐述。对于个别更复杂的反应，将对其机理进行探讨和简要讨论。
{"title":"Copper and Photocatalytic Synergistic Strategies for Radical Cyclization Reactions","authors":"Yue-Jiao Lu, Nan-Nan Dai, Mu-Han Li, Wen-Chan Tian, Qiang Li, Zheng-Jun Wang, Keqi Tang, Wen-Ting Wei","doi":"10.1002/adsc.202400665","DOIUrl":"https://doi.org/10.1002/adsc.202400665","url":null,"abstract":"The rapid development of photo-synergistic transition metal catalytic systems has provided a green paradigm to complement thermal transition metal catalytic methods. However, the most commonly used iridium or ruthenium complexes involve expensive in nature, in contrast to the abundant copper elements in the earth's crust, which are highly valued for their unique electronic structure and light-absorbing properties. Recently, the application of copper and photocatalytic synergistic strategies in radical cyclization reactions has progressed considerably, leading to a renaissance in the synthesis of functional natural products, drugs and their analogues, but summary work addressing this aspect has not been reported. In this review, we briefly analyze the effect of ligand choice on copper complexes and some inorganic copper salts and even on light sources. We then summarize the copper and photocatalytic synergistic strategies in radical cyclization reactions and classify them into three categories, C, N and O radicals, according to the class of the central atom of the radical in each work, and in each category will be elaborated in turn from coordination cyclization via Cu catalysts, direct radical cyclization and other cyclization mode. For individual more complex reactions, the mechanisms are explored and briefly discussed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141795069","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}
Yuanyuan Li, Xingyu Liu, Guanghui Lv, Yanning Xu, Meiling Ye, Jian Chen, Jinyu Hou, Li Guo, Zhongzhen Yang, Yong Wu
Here we reported the photo‐catalyzed C‐H alkylation of pyridyl‐substituted N‐benzyl anilines through nitrogen‐centred radical 1,5‐hydrogen atom transfer. A broad range of methylpyridyl‐substituted aniline and hydroxylamine acid derivatives were successfully transformed into the corresponding products in good to excellent yields without adding any base and metal. This protocol features mild reaction conditions, a broad range of substrates, remarkable functional group tolerance and simple operation procedure.
{"title":"C‐H alkylation of N‐benzyl anilines via visible‐light‐driven 1,5‐hydrogen atom transfer (1,5‐HAT) of hydroxamic acid derivatives","authors":"Yuanyuan Li, Xingyu Liu, Guanghui Lv, Yanning Xu, Meiling Ye, Jian Chen, Jinyu Hou, Li Guo, Zhongzhen Yang, Yong Wu","doi":"10.1002/adsc.202400642","DOIUrl":"https://doi.org/10.1002/adsc.202400642","url":null,"abstract":"Here we reported the photo‐catalyzed C‐H alkylation of pyridyl‐substituted N‐benzyl anilines through nitrogen‐centred radical 1,5‐hydrogen atom transfer. A broad range of methylpyridyl‐substituted aniline and hydroxylamine acid derivatives were successfully transformed into the corresponding products in good to excellent yields without adding any base and metal. This protocol features mild reaction conditions, a broad range of substrates, remarkable functional group tolerance and simple operation procedure.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141791154","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}
The front cover picture illustrates the synthesis of quinolines based on the strategy of isomerization of allylic alcohols catalyzed by the complex of 1,10-phenanthroline and tBuONa. The honeycomb symbolizes the catalyst and development of bees metaphorize the domino isomerization/oxidant-free dehydrogenative annulation sequences. The flying bees stand for the application of this protocol for the synthesis of bioactive molecules. Details can be found in the research article by Jia-Qi Li and co-workers (X. Zhou, X. Li, C. Le, J.-Q. Li, Adv. Synth. Catal. 2024, 366, DOI: 10.1002/adsc.202400465)
封面图片说明了基于 1,10-菲罗啉和 tBuONa 复合物催化的烯丙基醇异构化策略合成喹啉的过程。蜂巢象征着催化剂，蜜蜂的发展隐喻着多米诺异构化/无氧化剂脱氢环化序列。飞舞的蜜蜂代表着该方案在生物活性分子合成中的应用。详情请见李佳琦及其合作者的研究文章（X. Zhou, X. Li, C. Le, J.-Q. Li, Adv. Synth.Li，Adv.Catal.2024, 366, DOI: 10.1002/adsc.202400465)
{"title":"Base-Catalyzed Domino Isomerization/Oxidant-Free Dehydrogenative Annulation of Allylic Alcohols: Scope, Mechanism, and Application.","authors":"X. Zhou, X. Li, C. Le, J.-Qi Li","doi":"10.1002/adsc.202400879","DOIUrl":"https://doi.org/10.1002/adsc.202400879","url":null,"abstract":"The front cover picture illustrates the synthesis of quinolines based on the strategy of isomerization of allylic alcohols catalyzed by the complex of 1,10-phenanthroline and <sup><i>t</i></sup>BuONa. The honeycomb symbolizes the catalyst and development of bees metaphorize the domino isomerization/oxidant-free dehydrogenative annulation sequences. The flying bees stand for the application of this protocol for the synthesis of bioactive molecules. Details can be found in the research article by Jia-Qi Li and co-workers (X. Zhou, X. Li, C. Le, J.-Q. Li, <i>Adv. Synth. Catal</i>. <b>2024</b>, <i>366</i>, DOI: 10.1002/adsc.202400465)","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141794995","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}
Alkynes are simple yet important organic feedstocks. The selenylation of alkynes is able to produce complex selenium‐containing compounds in a facile way. Although there are some reviews about the selenylation of alkynes, most of them focus on one specific reaction or what types of products that can be obtained. There is a lack of attention given to the various uses of different selenium reagents and their mechanisms. This review mainly focuses on recent advances (2013‐2023) based on diverse selenium reagents. Mechanisms and how the added reagents work will be discussed. Different reaction types, including difunctionalization, Se‐annulation, spiro‐cyclization, C‐Se coupling, click reaction will be recorded in this review. The regioselectivity can be achieved through various mechanisms, including radicals, seleniraniums or electrophilic cyclization. We hope it will do help for future research in this area.
{"title":"Recent Developments in Selenylation of Alkynes","authors":"Yuemei Xu, Dayun Huang, Jinjing Wu, Xiangmei Wu","doi":"10.1002/adsc.202400794","DOIUrl":"https://doi.org/10.1002/adsc.202400794","url":null,"abstract":"Alkynes are simple yet important organic feedstocks. The selenylation of alkynes is able to produce complex selenium‐containing compounds in a facile way. Although there are some reviews about the selenylation of alkynes, most of them focus on one specific reaction or what types of products that can be obtained. There is a lack of attention given to the various uses of different selenium reagents and their mechanisms. This review mainly focuses on recent advances (2013‐2023) based on diverse selenium reagents. Mechanisms and how the added reagents work will be discussed. Different reaction types, including difunctionalization, Se‐annulation, spiro‐cyclization, C‐Se coupling, click reaction will be recorded in this review. The regioselectivity can be achieved through various mechanisms, including radicals, seleniraniums or electrophilic cyclization. We hope it will do help for future research in this area.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141791155","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}
Abstract. In synthetic carbohydrate chemistry, the modification of glycosyl radicals pathway stands as a central area of focus. The radical-based reactions often demonstrate remarkable compatibility with various functional groups owing to the mild initiation conditions. In particular, the identification of novel glycosyl radical precursors, combined with advanced reaction techniques, has substantially broadened the scope of glycosyl compound synthesis. Despite the presence of versatile donors, the synthesis of noble donors is still addressed as a synthetic need and challenges associated with sugar chemistry. Currently, a new class of glycosyl radical precursors has been developed which enables the production of C-, S-, O-, and N-glycosides efficiently. In this light, we highlight strategies towards bench-stable glycosyl sulfoxides, sulphone, and sulfite donors that can enable the site-, regio- and stereoselective transformation of protected or naked sugar synthons in synthetic carbohydrate chemistry. Here, this review article covers the recent developments in the selective glycosyl radical diversification such as glycosyl alkylation, arylation, alkenylation, sulfuration, C-H activation, and DNA conjugation via the bench-stable donors along with mechanistic aspects, challenges, and future directions. 1. Introduction 2. Generation of glycosyl radical from glycosyl sulfoxide, glycosyl sulfone, and glycosyl sulfinate 3. Glycosyl radicals and the stereoselectivity 4. Early history of glycosyl sulfoxides, sulfones, and sulfinate donors 5. Generation of glycosyl radicals from glycosyl sulfoxides 6. Generation of glycosyl radicals from glycosyl sulfones 6.1 Allyl glycosyl sulfones 6.2 Heteroaryl glycosyl sulfones 7. Generation of glycosyl radicals from glycosyl sulfinates 8. Summary and Outlook
{"title":"Emerging Advances of the Radical Pathway Glycosylation Enabled by Bench-Stable Glycosyl Donors: Glycosyl Sulfoxides, Glycosyl Sulfones, and Glycosyl Sulfinates","authors":"Shashiprabha Dubey, Zanjila Azeem, Pintu Kumar Mandal","doi":"10.1002/adsc.202400695","DOIUrl":"https://doi.org/10.1002/adsc.202400695","url":null,"abstract":"Abstract. In synthetic carbohydrate chemistry, the modification of glycosyl radicals pathway stands as a central area of focus. The radical-based reactions often demonstrate remarkable compatibility with various functional groups owing to the mild initiation conditions. In particular, the identification of novel glycosyl radical precursors, combined with advanced reaction techniques, has substantially broadened the scope of glycosyl compound synthesis. Despite the presence of versatile donors, the synthesis of noble donors is still addressed as a synthetic need and challenges associated with sugar chemistry. Currently, a new class of glycosyl radical precursors has been developed which enables the production of C-, S-, O-, and N-glycosides efficiently. In this light, we highlight strategies towards bench-stable glycosyl sulfoxides, sulphone, and sulfite donors that can enable the site-, regio- and stereoselective transformation of protected or naked sugar synthons in synthetic carbohydrate chemistry. Here, this review article covers the recent developments in the selective glycosyl radical diversification such as glycosyl alkylation, arylation, alkenylation, sulfuration, C-H activation, and DNA conjugation via the bench-stable donors along with mechanistic aspects, challenges, and future directions. 1. Introduction\u00002. Generation of glycosyl radical from glycosyl sulfoxide, glycosyl sulfone, and glycosyl sulfinate 3. Glycosyl radicals and the stereoselectivity 4. Early history of glycosyl sulfoxides, sulfones, and sulfinate donors 5. Generation of glycosyl radicals from glycosyl sulfoxides\u00006. Generation of glycosyl radicals from glycosyl sulfones 6.1 Allyl glycosyl sulfones 6.2 Heteroaryl glycosyl sulfones 7. Generation of glycosyl radicals from glycosyl sulfinates\u00008. Summary and Outlook","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141795070","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}
Predrag Jovanovic, Milos Jovanovic, Milos Petkovic, Milena Simic, Gordana Tasic, Marko Rodic, Srdjan Rakic, Filip Vlahovic, Vladimir Savic
The front cover picture was generated by artificial intelligence around our description of the landscape we intended to create. The cascade waterfall symbolizes the cascade transformation depicted schematically on the image. The starting oxime containing a proximal allene in palladium catalyzed process undergoes several in situ transformations to afford the triquinane type product. The cascade stream involves three components and creates four new bonds in a single operation. More details can be found in article by P. Jovanovic, V. Savic and co-workers (P. Jovanovic, M. Jovanovic, M. Petkovic, M. Simic, G. Tasic, M. Rodic, S. Rakic, F. Vlahovic, V. Savic, Adv. Synth. Catal. 2024, 366, DOI: 10.1002/adsc.202400253)
{"title":"Three Component Cascade Processes Involving Palladium Catalyzed Transformations/Dipolar Cycloadditions for the Synthesis of Angular Heterotriquinane Derivatives.","authors":"Predrag Jovanovic, Milos Jovanovic, Milos Petkovic, Milena Simic, Gordana Tasic, Marko Rodic, Srdjan Rakic, Filip Vlahovic, Vladimir Savic","doi":"10.1002/adsc.202400840","DOIUrl":"https://doi.org/10.1002/adsc.202400840","url":null,"abstract":"The front cover picture was generated by artificial intelligence around our description of the landscape we intended to create. The cascade waterfall symbolizes the cascade transformation depicted schematically on the image. The starting oxime containing a proximal allene in palladium catalyzed process undergoes several <i>in situ</i> transformations to afford the triquinane type product. The cascade stream involves three components and creates four new bonds in a single operation. More details can be found in article by P. Jovanovic, V. Savic and co-workers (P. Jovanovic, M. Jovanovic, M. Petkovic, M. Simic, G. Tasic, M. Rodic, S. Rakic, F. Vlahovic, V. Savic, <i>Adv. Synth. Catal</i>. <b>2024</b>, <i>366</i>, DOI: 10.1002/adsc.202400253)","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141795071","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}
Bailey N Rutkowski, Ella R Talley, Jasney Combs, Jordan Froese
Rieske dioxygenase enzymes can perform the cis‐dihydroxylation of aliphatic olefins, representing a potential green alternative to established methods of performing this important transformation. However, the activity of the natural enzymes in this context is low relative to their more well‐known activity in the cis‐dihydroxylation of aromatics. To enable the engineering of dioxygenase enzymes for improved activity in the dihydroxylation of aliphatic olefins, we have developed an assay system to detect the relevant diol metabolites produced from whole‐cell fermentation cultures. Optimization studies were carried out to maximize the sensitivity of the assay system, and its utility in the in vitro screening of enzyme variant libraries was demonstrated. The assay system was utilized in screening studies that identified Rieske dioxygenase variants with significantly improved activity in the dihydroxylation of aliphatic olefins relative to the wild‐type enzyme.
{"title":"A High‐Throughput in vitro Assay System for the Detection of the Enzymatic Dihydroxylation of Aliphatic Olefins","authors":"Bailey N Rutkowski, Ella R Talley, Jasney Combs, Jordan Froese","doi":"10.1002/adsc.202400656","DOIUrl":"https://doi.org/10.1002/adsc.202400656","url":null,"abstract":"Rieske dioxygenase enzymes can perform the cis‐dihydroxylation of aliphatic olefins, representing a potential green alternative to established methods of performing this important transformation. However, the activity of the natural enzymes in this context is low relative to their more well‐known activity in the cis‐dihydroxylation of aromatics. To enable the engineering of dioxygenase enzymes for improved activity in the dihydroxylation of aliphatic olefins, we have developed an assay system to detect the relevant diol metabolites produced from whole‐cell fermentation cultures. Optimization studies were carried out to maximize the sensitivity of the assay system, and its utility in the in vitro screening of enzyme variant libraries was demonstrated. The assay system was utilized in screening studies that identified Rieske dioxygenase variants with significantly improved activity in the dihydroxylation of aliphatic olefins relative to the wild‐type enzyme.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141769179","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}
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