Yujing Hu, Wenjing Wang, Mingye Zhao, Jie Chen, Shuyang Kong, Ning Zhu, Zheng Fang, Yongzhen Peng, Qi Wu, Kai Guo
Chiral tetrahydrofurans are prevalent structural motifs in biologically active compounds, approved drugs and natural products, but relevant enantiocomplementary synthesis remains underdeveloped. In this study, wild type halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1, was first discovered to enable the intramolecular substitution of δ‐halohydrins for the formation of tetrahydrofurans but with unsatisfied activity and stereoselectivity. Through structure‐guided protein engineering, two completely enantiocomplementary variants T134M and P84L/W139A of HheC were obtained for the synthesis of tetrahydrofurans by the kinetic resolution of δ‐halohydrins (both giving products with up to 99% e.e., E >200). This research unveiled the halohydrin dehalogenases’ catalytic ability to form chiral cyclic ethers larger ring size than three‐membered epoxides, which has hitherto been unexplored, and provided an enzymatic synthesis access to valuably enantiocomplementary tetrahydrofurans.
{"title":"Enantiocomplementary Synthesis of Tetrahydrofurans by Engineered Halohydrin Dehalogenases","authors":"Yujing Hu, Wenjing Wang, Mingye Zhao, Jie Chen, Shuyang Kong, Ning Zhu, Zheng Fang, Yongzhen Peng, Qi Wu, Kai Guo","doi":"10.1002/adsc.202400777","DOIUrl":"https://doi.org/10.1002/adsc.202400777","url":null,"abstract":"Chiral tetrahydrofurans are prevalent structural motifs in biologically active compounds, approved drugs and natural products, but relevant enantiocomplementary synthesis remains underdeveloped. In this study, wild type halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1, was first discovered to enable the intramolecular substitution of δ‐halohydrins for the formation of tetrahydrofurans but with unsatisfied activity and stereoselectivity. Through structure‐guided protein engineering, two completely enantiocomplementary variants T134M and P84L/W139A of HheC were obtained for the synthesis of tetrahydrofurans by the kinetic resolution of δ‐halohydrins (both giving products with up to 99% e.e., E >200). This research unveiled the halohydrin dehalogenases’ catalytic ability to form chiral cyclic ethers larger ring size than three‐membered epoxides, which has hitherto been unexplored, and provided an enzymatic synthesis access to valuably enantiocomplementary tetrahydrofurans.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102002","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}
Joanna Dybowska, Artur Przydacz, Anna Skrzyńska, Łukasz Albrecht
. The manuscript describes a formal [10+2] higher‐order cycloaddition between 2‐benzylideneindan‐1‐ones and α‐alkilidene azlactones as higherene precursors and higherenofiles respectively. The reaction is realized under Brønsted‐base catalysis utilizing the phase transfer catalysis approach. The key intermediate is an isobenzofulvene‐derived polyenolate which acts as a 10‐electron component in the higher‐order cycloaddition. By using this strategy, a series of structurally diverse compounds containing a polycyclic hydrocarbon scaffold was prepared in 79‐99% yields. In addition, the potential of the obtained [10+2]‐cycloadducts has been confirmed by transformations, including the synthesis of a highly‐valuable alpha,alpha‐disubstituted N‐protected alpha‐aminoester.
.手稿描述了分别作为高烯前体和高烯赝品的 2-亚苄基茚-1-酮和α-亚烷基氮内酯之间的正式 [10+2] 高阶环加成反应。该反应是在布氏碱催化下利用相转移催化法实现的。关键的中间体是异苯乙烯衍生的聚烯酸酯，它在高阶环化反应中充当 10 电子元件。通过使用这种策略，制备出了一系列含有多环烃支架的结构多样的化合物，产率为 79-99%。此外，所获得的[10+2]-环加载产物的潜力已通过转化得到证实，包括合成了一种极具价值的α,α-二取代 N 保护α-氨基酯。
{"title":"PTC in the polyenolate‐mediated [10+2]‐cycloaddition for the synthesis of α,α‐disubstituted amino acid precursors","authors":"Joanna Dybowska, Artur Przydacz, Anna Skrzyńska, Łukasz Albrecht","doi":"10.1002/adsc.202400792","DOIUrl":"https://doi.org/10.1002/adsc.202400792","url":null,"abstract":". The manuscript describes a formal [10+2] higher‐order cycloaddition between 2‐benzylideneindan‐1‐ones and α‐alkilidene azlactones as higherene precursors and higherenofiles respectively. The reaction is realized under Brønsted‐base catalysis utilizing the phase transfer catalysis approach. The key intermediate is an isobenzofulvene‐derived polyenolate which acts as a 10‐electron component in the higher‐order cycloaddition. By using this strategy, a series of structurally diverse compounds containing a polycyclic hydrocarbon scaffold was prepared in 79‐99% yields. In addition, the potential of the obtained [10+2]‐cycloadducts has been confirmed by transformations, including the synthesis of a highly‐valuable alpha,alpha‐disubstituted N‐protected alpha‐aminoester.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102000","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}
Shuyong Song, Chengcai Xia, Zenghui Zhang, Wenjing Yang, Changji Liu
Tandem reactions via electrocatalytic annulations have emerged as an effective strategy for the construction of heterocycles. Herein, a two‐component electrochemical annulation via 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.
{"title":"Tandem Electrochemical Redox/Condensation Reaction between 2‐Amino Nitrobenzenes and Aliphatic Alcohols: An Approach to Benzimidazoles","authors":"Shuyong Song, Chengcai Xia, Zenghui Zhang, Wenjing Yang, Changji Liu","doi":"10.1002/adsc.202400771","DOIUrl":"https://doi.org/10.1002/adsc.202400771","url":null,"abstract":"Tandem reactions via electrocatalytic annulations have emerged as an effective strategy for the construction of heterocycles. Herein, a two‐component electrochemical annulation via 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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-31","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}
A visible‐light‐promoted site‐selective difluoroalkoxylation of imidazo[1,2‐a]pyridines has been achieved using N‐fluorobenzenesulfonimide (NFSI) as a fluorinating agent. This practical reaction has a wide range of substrate scope for both imidazo[1,2‐a]pyridines and alcohols to give 3,3‐difluoro‐2‐alkoxy‐2‐arylimidazo[1,2‐a]pyridines in 65‐93% yields. The reaction proceeded at room temperature, showed high functional group tolerance, and was amenable to scale‐up. Based on mechanistic investigation, a radical pathway is proposed.
{"title":"Visible Light‐Driven Difluoroalkoxylation of Imidazopyridines using N‐Fluorobenzenesulfonimide as Fluorinating Agent","authors":"Amol Gadekar, Sonam *, Vikki N Shinde, Bhawani *, Krishnan Rangan, Anil Kumar","doi":"10.1002/adsc.202400755","DOIUrl":"https://doi.org/10.1002/adsc.202400755","url":null,"abstract":"A visible‐light‐promoted site‐selective difluoroalkoxylation of imidazo[1,2‐a]pyridines has been achieved using N‐fluorobenzenesulfonimide (NFSI) as a fluorinating agent. This practical reaction has a wide range of substrate scope for both imidazo[1,2‐a]pyridines and alcohols to give 3,3‐difluoro‐2‐alkoxy‐2‐arylimidazo[1,2‐a]pyridines in 65‐93% yields. The reaction proceeded at room temperature, showed high functional group tolerance, and was amenable to scale‐up. Based on mechanistic investigation, a radical pathway is proposed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102008","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}
Alex Prats Luján, Mohammad Faizan Bhat, Saravanan Thangavelu, Gerrit Poelarends
Flavin‐dependent nitroreductases are gaining attention as biocatalysts for the synthesis of pharmaceutically active compounds and their precursors. Here, we examined a panel of nitroreductase‐like flavoenzymes for their reductase activity towards a wide variety of aromatic and aliphatic nitro compounds, nitroolefins, and α,β‐unsaturated carbonyl compounds. Several of these flavoenzymes displayed high reductase activity and achieved excellent conversion of diverse nitroarenes, nitroolefins and α,β‐unsaturated carbonyl compounds, accomplishing good product yields in semi‐preparative scale reactions (up to 97%). In addition to the catalytic promiscuity of several of these flavoenzymes, being able to perform the reduction of nitro groups (nitroreductase activity) as well as C=C groups (ene‐reductase activity), this study also revealed that some flavoenzymes exhibit high chemo‐, regio‐ and/or enantioselectivity, making them attractive enzymes for use in organic synthesis.
{"title":"Exploring the Substrate Scope and Catalytic Promiscuity of Nitroreductase‐like Enzymes","authors":"Alex Prats Luján, Mohammad Faizan Bhat, Saravanan Thangavelu, Gerrit Poelarends","doi":"10.1002/adsc.202400220","DOIUrl":"https://doi.org/10.1002/adsc.202400220","url":null,"abstract":"Flavin‐dependent nitroreductases are gaining attention as biocatalysts for the synthesis of pharmaceutically active compounds and their precursors. Here, we examined a panel of nitroreductase‐like flavoenzymes for their reductase activity towards a wide variety of aromatic and aliphatic nitro compounds, nitroolefins, and α,β‐unsaturated carbonyl compounds. Several of these flavoenzymes displayed high reductase activity and achieved excellent conversion of diverse nitroarenes, nitroolefins and α,β‐unsaturated carbonyl compounds, accomplishing good product yields in semi‐preparative scale reactions (up to 97%). In addition to the catalytic promiscuity of several of these flavoenzymes, being able to perform the reduction of nitro groups (nitroreductase activity) as well as C=C groups (ene‐reductase activity), this study also revealed that some flavoenzymes exhibit high chemo‐, regio‐ and/or enantioselectivity, making them attractive enzymes for use in organic synthesis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102007","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}
A molybdenum‐catalyzed synthesis of N2,C3‐disubstituted 2H‐indazoles from readily available 2‐acylazobenzenes via deoxygenation of C=O and annulation has been described. The non‐noble metal catalytic system has good tolerance of functional groups, and various N2,C3‐disubstituted 2H‐indazoles have been constructed in 24% to 99% yield. This reaction is easy to scale‐up and has shown its applications in deriving valuable fluorescent and bioactive compounds. The plausible mechanism shows the plausible processes of molybdenum‐catalyzed deoxygenative annulation.
{"title":"Molybdenum‐Catalyzed Intramolecular Deoxygenative Annulation of 2‐Acylazobenzenes to Access N2,C3‐Disubstituted 2H‐indazoles","authors":"Haoke Chu, Quanyun Liu, Mei-Hua Shen, Hua-Dong Xu","doi":"10.1002/adsc.202400662","DOIUrl":"https://doi.org/10.1002/adsc.202400662","url":null,"abstract":"A molybdenum‐catalyzed synthesis of N2,C3‐disubstituted 2H‐indazoles from readily available 2‐acylazobenzenes via deoxygenation of C=O and annulation has been described. The non‐noble metal catalytic system has good tolerance of functional groups, and various N2,C3‐disubstituted 2H‐indazoles have been constructed in 24% to 99% yield. This reaction is easy to scale‐up and has shown its applications in deriving valuable fluorescent and bioactive compounds. The plausible mechanism shows the plausible processes of molybdenum‐catalyzed deoxygenative annulation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102006","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}
A copper or silver‐catalyzed cascade addition/5‐exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis of a variety of (Z)‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives with diverse substitutions in a single vessel. The method is featured with pot‐economy and high regio‐ and Z‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, the relevant indole‐fused and indole‐substituted thiophenone derivatives were also assembled in one pot by merging this strategy with other bond formation methods. Based on the experiments and the related reports, a cascade pathway triggered by the addition of ynone‐derived radical towards the C(sp)‐atom of isothiocyanate was proposed to elucidate the probable process of the transformation.
我们开发了一种铜或银催化的异硫氰酸盐与炔酮的级联加成/5-外-掘环化/异构化反应。这种策略可以在一个容器中合成多种具有不同取代结构的 (Z)-2- 亚基-5-氨基噻吩-3-酮衍生物。该方法具有罐装经济性、高区域选择性和 Z 选择性的特点。利用这种方法可以修饰多种生物活性分子。此外，通过将该方法与其他成键方法相结合，还能在一锅内组装出相关的吲哚融合和吲哚取代的噻吩酮衍生物。根据实验结果和相关报道，我们提出了一个由炔酮类自由基向异硫氰酸盐的 C(sp)原子加成引发的级联途径，以阐明转化的可能过程。
{"title":"One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives","authors":"Zefeng Jin, Cuiying Li, Guodong Shen, Honglan Kang, Xin Lv","doi":"10.1002/adsc.202400641","DOIUrl":"https://doi.org/10.1002/adsc.202400641","url":null,"abstract":"A copper or silver‐catalyzed cascade addition/5‐exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis of a variety of (Z)‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives with diverse substitutions in a single vessel. The method is featured with pot‐economy and high regio‐ and Z‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, the relevant indole‐fused and indole‐substituted thiophenone derivatives were also assembled in one pot by merging this strategy with other bond formation methods. Based on the experiments and the related reports, a cascade pathway triggered by the addition of ynone‐derived radical towards the C(sp)‐atom of isothiocyanate was proposed to elucidate the probable process of the transformation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102009","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}
Qiuyu Zhong, Changyu Yu, Jinlin Wang, Jiang Wang, Kaixian Chen, Hong Liu, Wenhao Dai
C‐alkyl glycosides play a crucial role in various bioactive compounds. However, the synthesis of C‐alkyl glycosides poses significant challenges, particularly through C(sp3)‐H glycosylation. Here, we report a set of reactions for constructing C‐alkyl glycosides through directing‐group‐mediated functionalization of unactivated γ‐C(sp3)‐H bonds under mild conditions. Those reactions not only achieve high regioselectivity and stereoselectivity in glycosylation, but also exhibit a wide substrate scope. They are compatible with both arene and alkane substrates, as well as natural and unnatural amino acid substrates. Mechanistic studies have shown that the directing‐group 8‐aminoquinoline (AQ) and picolinamide (PA) may affect the chirality of the β‐carbon of L‐valine through a sterically favorable trans‐palladacycle intermediate, resulting in (R) or (S) configuration of glycosylated amino acid, respectively. These reactions are promising to provide a convenient and powerful tool for constructing C‐alkyl glycosides and carbohydrate‐based drugs in the future.
{"title":"Palladium‐Catalyzed Directing‐group‐mediated γ‐C(sp3)‐H Glycosylation for Synthesis of C‐Alkyl Glycosides","authors":"Qiuyu Zhong, Changyu Yu, Jinlin Wang, Jiang Wang, Kaixian Chen, Hong Liu, Wenhao Dai","doi":"10.1002/adsc.202400564","DOIUrl":"https://doi.org/10.1002/adsc.202400564","url":null,"abstract":"C‐alkyl glycosides play a crucial role in various bioactive compounds. However, the synthesis of C‐alkyl glycosides poses significant challenges, particularly through C(sp3)‐H glycosylation. Here, we report a set of reactions for constructing C‐alkyl glycosides through directing‐group‐mediated functionalization of unactivated γ‐C(sp3)‐H bonds under mild conditions. Those reactions not only achieve high regioselectivity and stereoselectivity in glycosylation, but also exhibit a wide substrate scope. They are compatible with both arene and alkane substrates, as well as natural and unnatural amino acid substrates. Mechanistic studies have shown that the directing‐group 8‐aminoquinoline (AQ) and picolinamide (PA) may affect the chirality of the β‐carbon of L‐valine through a sterically favorable trans‐palladacycle intermediate, resulting in (R) or (S) configuration of glycosylated amino acid, respectively. These reactions are promising to provide a convenient and powerful tool for constructing C‐alkyl glycosides and carbohydrate‐based drugs in the future.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102010","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}
A method for the reductive difluoromethylation of alkenes with 2‐difluoromethylthio(benzothiazole) under photocatalytic conditions is described. The reaction involves the generation of the difluoromethyl radical by means of trimethyltriazinane, which serves as a precursor for the strongly reducing cyclic diaminoalkyl radical.
{"title":"Visible Light Mediated Difluoroalkylation of Alkenes Using Mercaptobenzothiazole‐Derived Sulfide Reagent","authors":"Artem Sorokin, Vitalij Levin, Alexander D. Dilman","doi":"10.1002/adsc.202400884","DOIUrl":"https://doi.org/10.1002/adsc.202400884","url":null,"abstract":"A method for the reductive difluoromethylation of alkenes with 2‐difluoromethylthio(benzothiazole) under photocatalytic conditions is described. The reaction involves the generation of the difluoromethyl radical by means of trimethyltriazinane, which serves as a precursor for the strongly reducing cyclic diaminoalkyl radical.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142101814","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}
Since the review of Yorimitsu and Oshima in 2010, the past 15 years have witnessed significant progresses in the application of 1-alkynylphosphorus compounds in organic synthesis. Owing to the reactive carbon-carbon triple bond in association with the electron-withdrawing phosphoryl group, they easily undergo transition metal-catalyzed nucleophilic addition reactions at the β-position with carbon- and heteroatom-based nucleophiles to afford structurally diverse 1-alkenyl phosphorus compounds. Especially, when 1-alkynylphosphonates or phosphinates are used, intramolecular substitution reactions on P-atom might occur in some cases, which would result in the formation of P-based heterocycles. In addition, the existing triple bond makes them prone to go through addition reaction initiated cyclization reactions and [2+2], [2+3], [2+4], [2+5] and [2+2+2] cycloaddition reactions with other unsaturated bonds, which provides an efficient access to various P-based heterocycles and phosphorylated carbon- and heterocycles.
自 Yorimitsu 和 Oshima 于 2010 年发表评论以来，过去 15 年间，1-炔基磷化合物在有机合成中的应用取得了重大进展。由于活性碳-碳三键与抽电子磷基的结合，1-炔基磷化合物很容易在β位与碳基和杂原子基亲核物发生过渡金属催化的亲核加成反应，从而得到结构多样的 1-炔基磷化合物。特别是当使用 1-烯基膦酸盐或膦酸盐时，在某些情况下可能会发生 P 原子上的分子内取代反应，从而形成 P 基杂环。此外，现有的三键使它们容易与其他不饱和键发生由加成反应引发的环化反应和[2+2]、[2+3]、[2+4]、[2+5]和[2+2+2]环加成反应，从而有效地获得各种 P 基杂环和磷酸化碳杂环。
{"title":"1-Alkynylphosphorus Compounds in Organic Synthesis，2010-2024","authors":"Long Chen, Hai-Liang Ni, Zhong Wen, Huan-Zhu Xue","doi":"10.1002/adsc.202400847","DOIUrl":"https://doi.org/10.1002/adsc.202400847","url":null,"abstract":"Since the review of Yorimitsu and Oshima in 2010, the past 15 years have witnessed significant progresses in the application of 1-alkynylphosphorus compounds in organic synthesis. Owing to the reactive carbon-carbon triple bond in association with the electron-withdrawing phosphoryl group, they easily undergo transition metal-catalyzed nucleophilic addition reactions at the β-position with carbon- and heteroatom-based nucleophiles to afford structurally diverse 1-alkenyl phosphorus compounds. Especially, when 1-alkynylphosphonates or phosphinates are used, intramolecular substitution reactions on P-atom might occur in some cases, which would result in the formation of P-based heterocycles. In addition, the existing triple bond makes them prone to go through addition reaction initiated cyclization reactions and [2+2], [2+3], [2+4], [2+5] and [2+2+2] cycloaddition reactions with other unsaturated bonds, which provides an efficient access to various P-based heterocycles and phosphorylated carbon- and heterocycles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142085538","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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