We disclose the intramolecular synthesis of 3-alkenyl-2<i>H</i>-indazoles from 2-alkynylazobenzenes promoted by a dual catalysis using AuCl3 and a ruthenium photocatalyst under irradiation with visible light. This reaction goes through a hydroamination of the alkynyl fragment. The yields are governed by the electronic factors. Control experiments and DFT calculations suggest that a radical and polar mechanisms are operating in parallel. This transformation goes through first formation and C-N bond and 1,2-hydride shift. Derivatization was also carried out to extend the versatility of this methodology.
{"title":"Combined Gold and Photoredox Catalysis: Synthesis of 3-Alkenyl-2H-Indazoles from 2-Alkynylazobenzenes","authors":"Clara Mañas, Estibaliz Merino","doi":"10.1002/adsc.202400990","DOIUrl":"https://doi.org/10.1002/adsc.202400990","url":null,"abstract":"We disclose the intramolecular synthesis of 3-alkenyl-2<i>H</i>-indazoles from 2-alkynylazobenzenes promoted by a dual catalysis using AuCl3 and a ruthenium photocatalyst under irradiation with visible light. This reaction goes through a hydroamination of the alkynyl fragment. The yields are governed by the electronic factors. Control experiments and DFT calculations suggest that a radical and polar mechanisms are operating in parallel. This transformation goes through first formation and C-N bond and 1,2-hydride shift. Derivatization was also carried out to extend the versatility of this methodology.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"79 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440406","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}
Nawel GOUAL, Stéphane Maisonneuve, Fabrizio Medici, pascal retailleau, Jean-Francois GALLARD, juan Xie, Vincent Gandon, Angela Marinetti, Arnaud Voituriez
This work discloses a strategy for the implementation of ON-ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on the regiodivergent reactivity of mono- and bimetallic gold complexes that result from π- vs σ,π-activations of alkynyl-substituted urea substrates, for the selective formation of either dihydroquinazolinone or indole-carboxamide products, via intramolecular hydroamidation.
{"title":"Divergent Reactivity of E/Z-Azobenzene-Based Phosphine-Gold Catalysts: Toward an ON-ON Catalytic Photoswitch Process","authors":"Nawel GOUAL, Stéphane Maisonneuve, Fabrizio Medici, pascal retailleau, Jean-Francois GALLARD, juan Xie, Vincent Gandon, Angela Marinetti, Arnaud Voituriez","doi":"10.1002/adsc.202401105","DOIUrl":"https://doi.org/10.1002/adsc.202401105","url":null,"abstract":"This work discloses a strategy for the implementation of ON-ON organometallic catalytic processes using photoresponsive phosphine ligands. The approach leverages on the regiodivergent reactivity of mono- and bimetallic gold complexes that result from π- vs σ,π-activations of alkynyl-substituted urea substrates, for the selective formation of either dihydroquinazolinone or indole-carboxamide products, via intramolecular hydroamidation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440407","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}
Junhao Ruan, Xi Cao, Yipeng Zhou, Xiaoyu Yang, Weijie Chen
Six-membered endocyclic benzyl/allyl enecarbamates undergo a Pd-catalyzed decarboxylation process to generate endocyclic 1-azaallyl anions and Pd–benzyl/allyl cations. The ion pair then react with each other followed by reduction to ultimately give unprotected -2-(hetero)aryl-3-benzylpiperidines and 2-(hetero)aryl-3-allylpiperidines in 31−91% yields as single cis-diastereomers. These reactions represent a strategy to form unprotected β-substituted piperidines, which generates elusive endocyclic 1-azaallyl anion intermediates by introducing the negative charge from the N-terminal.
{"title":"Palladium-Catalyzed Decarboxylative Benzylation and Allylation of Six-Membered Endocyclic Enecarbamates","authors":"Junhao Ruan, Xi Cao, Yipeng Zhou, Xiaoyu Yang, Weijie Chen","doi":"10.1002/adsc.202401140","DOIUrl":"https://doi.org/10.1002/adsc.202401140","url":null,"abstract":"Six-membered endocyclic benzyl/allyl enecarbamates undergo a Pd-catalyzed decarboxylation process to generate endocyclic 1-azaallyl anions and Pd–benzyl/allyl cations. The ion pair then react with each other followed by reduction to ultimately give unprotected -2-(hetero)aryl-3-benzylpiperidines and 2-(hetero)aryl-3-allylpiperidines in 31−91% yields as single cis-diastereomers. These reactions represent a strategy to form unprotected β-substituted piperidines, which generates elusive endocyclic 1-azaallyl anion intermediates by introducing the negative charge from the N-terminal.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"95 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439603","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}
Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development of carbon-germanium bond formation strategies, particularly those for more challenging C(sp3)-Ge bonds. This review systematically summarizes the recent advances in C(sp3)-Ge bond forming methodologies, with particular emphasis on (1) the versatility of transition-metals, including iron, nickel, copper, rhodium and palladium, as catalysts in broadening reaction scope and controlling selectivity; (2) the powerfulness of organic photocatalysis in achieving mild and selective bond formation, and (3) the sustainability of catalytic electrosynthesis in facilitating chemical oxidant-/reductant-free conversions. Additionally, examples of (4) non-catalytic strategies are also discussed. The representative scopes, as well as mechanistic proposals, of these protocols are highlighted. Through an overview on the current state of research, this review aims to offer insights into the catalytic construction of C(sp3)-Ge bonds, and provide perspectives on future research directions to address the current challenges.
{"title":"Catalytic Construction of C(sp3)-Ge Bonds: Recent Advances and Future Perspectives","authors":"Jia-Lin Tu, Binbin Huang","doi":"10.1002/adsc.202401069","DOIUrl":"https://doi.org/10.1002/adsc.202401069","url":null,"abstract":"Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development of carbon-germanium bond formation strategies, particularly those for more challenging C(sp3)-Ge bonds. This review systematically summarizes the recent advances in C(sp3)-Ge bond forming methodologies, with particular emphasis on (1) the versatility of transition-metals, including iron, nickel, copper, rhodium and palladium, as catalysts in broadening reaction scope and controlling selectivity; (2) the powerfulness of organic photocatalysis in achieving mild and selective bond formation, and (3) the sustainability of catalytic electrosynthesis in facilitating chemical oxidant-/reductant-free conversions. Additionally, examples of (4) non-catalytic strategies are also discussed. The representative scopes, as well as mechanistic proposals, of these protocols are highlighted. Through an overview on the current state of research, this review aims to offer insights into the catalytic construction of C(sp3)-Ge bonds, and provide perspectives on future research directions to address the current challenges.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439605","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}
Soni Devi, Madan Kumar, Manisha Lamba, Avijit Goswami
An efficient and operationally simple protocol to access N-(2,2,2-trifluoroethyl)amides/propiolamides and acrylamides via direct conversion of easily accessible nitriles (aryl/alkyl/alkynyl/vinyl) and in situ generated CF3CHN2 as trifluoroethylating reagent has been developed. The protocol offers broad functional group tolerance under mild reaction conditions. Furthermore, the conversion of trifluoroethylated propiolamide into its triazole analog via Ru-catalyzed [3+2] cycloadditions using BnN3 clearly indicates its versatility in the synthetic applications.
{"title":"Synthesis of CF3CH2-Amides/Propiolamides/Acrylamides: The TfOH Catalyzed Reactions of Nitrile Compounds with CF3CHN2","authors":"Soni Devi, Madan Kumar, Manisha Lamba, Avijit Goswami","doi":"10.1002/adsc.202401120","DOIUrl":"https://doi.org/10.1002/adsc.202401120","url":null,"abstract":"An efficient and operationally simple protocol to access N-(2,2,2-trifluoroethyl)amides/propiolamides and acrylamides via direct conversion of easily accessible nitriles (aryl/alkyl/alkynyl/vinyl) and in situ generated CF3CHN2 as trifluoroethylating reagent has been developed. The protocol offers broad functional group tolerance under mild reaction conditions. Furthermore, the conversion of trifluoroethylated propiolamide into its triazole analog via Ru-catalyzed [3+2] cycloadditions using BnN3 clearly indicates its versatility in the synthetic applications.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431869","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}
Hon Cheung Leung, Tsz Chun Lee, Wing-Tak Wong, Wai Chung Fu
The front cover features a Tarot-style card titled “THE FLOW”. A sage seated by a cascading stream (symbolizing a flow system) holds deuterium and hydrogen atoms and determines the reaction pathway for ClCF2H molecules in the sky. By varying the addition and mixing sequences within a flow system, ClCF2H gas can undergo an SN2 reaction with heteroatom anions to produce X-CF2H products, or be selectively converted into difluorocarbenes for a carbene-based fragment coupling, yielding X-CF2D products. More details can be found in Communication by Wai Chung Fu and co-workers (H. C. Leung, T. C. Lee, W.-T. Wong, W. C. Fu, Adv. Synth. Catal. 2024, 366, XXXX–XXXX; DOI: 10.1002/adsc.202400826)
封面是一张塔罗牌，名为 "流"。一位圣人坐在溪流边（象征流动系统），手持氘和氢原子，决定着天空中 ClCF2H 分子的反应路径。通过改变流动系统中的添加和混合顺序，ClCF2H 气体可以与杂原子阴离子发生 SN2 反应，生成 X-CF2H 产物，或者选择性地转化为二氟羰基，进行基于碳的片段耦合，生成 X-CF2D 产物。更多详情可参阅傅伟忠及其合作者的通讯（H. C. Leung, T. C. Lee, W.-T. Wong, W. C. Fu, 2009）。Wong, W. C. Fu, Adv.Catal.2024, 366, XXXX-XXXX; DOI: 10.1002/adsc.202400826)
{"title":"Rapid (Deuterio)difluoromethylation of Heteroatoms Using R-22 Gas: A Demonstration of Flow Chemistry in Suppressing Intrinsic Reaction Pathways.","authors":"Hon Cheung Leung, Tsz Chun Lee, Wing-Tak Wong, Wai Chung Fu","doi":"10.1002/adsc.202401083","DOIUrl":"https://doi.org/10.1002/adsc.202401083","url":null,"abstract":"The front cover features a Tarot-style card titled “THE FLOW”. A sage seated by a cascading stream (symbolizing a flow system) holds deuterium and hydrogen atoms and determines the reaction pathway for ClCF<sub>2</sub>H molecules in the sky. By varying the addition and mixing sequences within a flow system, ClCF<sub>2</sub>H gas can undergo an SN2 reaction with heteroatom anions to produce X-CF<sub>2</sub>H products, or be selectively converted into difluorocarbenes for a carbene-based fragment coupling, yielding X-CF<sub>2</sub>D products. More details can be found in Communication by Wai Chung Fu and co-workers (H. C. Leung, T. C. Lee, W.-T. Wong, W. C. Fu, <i>Adv. Synth. Catal</i>. <b>2024</b>, <i>366</i>, XXXX–XXXX; DOI: 10.1002/adsc.202400826)","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"123 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431488","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}
Shengfu Kang, Xiaohong Liu, Yi Zhang, Fang Fang, Wenjun Li, Pengfei Li
Organocatalytic dearomatization of β-naphthols has been achieved via an 1,6-conjugated addition of 2-naphthols to alkynyl 7-methylene-7H-indoles in situ generated from α-(7-indolyl)methanols. In the presence of racemic phosphoric acid, a series of tetrasubstituted allenes was obtained in high yields. Particularly, with the aid of chiral phosphoric acid, asymmetric dearomatization of β-naphthols was investigated, affording axially chiral tetrasubstituted allenes with moderate enantioselectivity.
{"title":"Organocatalytic Dearomatization of β-Naphthols through a 1,6-Conjugated Addition of Alkynyl 7-Methylene-7H-indoles Formed In Situ","authors":"Shengfu Kang, Xiaohong Liu, Yi Zhang, Fang Fang, Wenjun Li, Pengfei Li","doi":"10.1002/adsc.202401173","DOIUrl":"https://doi.org/10.1002/adsc.202401173","url":null,"abstract":"Organocatalytic dearomatization of β-naphthols has been achieved via an 1,6-conjugated addition of 2-naphthols to alkynyl 7-methylene-7H-indoles in situ generated from α-(7-indolyl)methanols. In the presence of racemic phosphoric acid, a series of tetrasubstituted allenes was obtained in high yields. Particularly, with the aid of chiral phosphoric acid, asymmetric dearomatization of β-naphthols was investigated, affording axially chiral tetrasubstituted allenes with moderate enantioselectivity.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431751","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}
Wenhui Cui, Fanjing Meng, Zengfeng Zhang, Zhuting Han, Yang Cao
An asymmetric 1,4-reduction of exocyclic α,β-unsaturated ketones leading to the formation of diverse optically active α-substituted tetralones has been realized by chiral SPINOL-derived boro-phosphate. The enantios-elctivity-determining step of the reaction is the protonation of a highly active boron enolates intermediate. The catalytic reduction system composed of chiral SPINOL-derived boro-phosphate and pinacolborane may be widely used in other asymmetric reduction reactions.
{"title":"Chiral SPINOL-derived Boro-phosphate-Catalyzed Asymmetric 1,4-Reduction of Exocyclic α,β-Unsaturated Ketones","authors":"Wenhui Cui, Fanjing Meng, Zengfeng Zhang, Zhuting Han, Yang Cao","doi":"10.1002/adsc.202401008","DOIUrl":"https://doi.org/10.1002/adsc.202401008","url":null,"abstract":"An asymmetric 1,4-reduction of exocyclic α,β-unsaturated ketones leading to the formation of diverse optically active α-substituted tetralones has been realized by chiral SPINOL-derived boro-phosphate. The enantios-elctivity-determining step of the reaction is the protonation of a highly active boron enolates intermediate. The catalytic reduction system composed of chiral SPINOL-derived boro-phosphate and pinacolborane may be widely used in other asymmetric reduction reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431886","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 Pérez, Thomas Wirth
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 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.
{"title":"Hydrofluoroether Synthesis through One-Pot Anodic Iodoalkoxylation of Alkenes","authors":"Martin Becerra-Ruiz, Bethan Winterson, Edwin Pérez, Thomas Wirth","doi":"10.1002/adsc.202401108","DOIUrl":"https://doi.org/10.1002/adsc.202401108","url":null,"abstract":"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 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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","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}
An expedient strategy for the construction of trifluoromethylselenolated spiro[5.5]trienones/spiro[4.5]trienones through a cascade electrophilic trifluoromethylselenolation cyclization and dearomatization has been developed. This sequential process was induced by N-trifluoromethylselenophthalimide (Phth-SeCF3), which was an efficient electrophilic trifluoromethylselenolation reagent. This approach has the feature of mild conditions, broad substrate scope, and high functional group tolerance.
{"title":"Synthesis of Trifluoromethylselenolated Spiro[5.5]trienones/Spiro[4.5]trienones via Electrophilic Trifluoromethylselenolation Cyclization and Dearomatization","authors":"Jia Wang, Jia-Qi Niu, Ming-Jiang Geng, Jia-Cheng Li, Yun-Hui Yan, Lixia Liu, Xuefang Shang, Shu-Jun Chao","doi":"10.1002/adsc.202401099","DOIUrl":"https://doi.org/10.1002/adsc.202401099","url":null,"abstract":"An expedient strategy for the construction of trifluoromethylselenolated spiro[5.5]trienones/spiro[4.5]trienones through a cascade electrophilic trifluoromethylselenolation cyclization and dearomatization has been developed. This sequential process was induced by N-trifluoromethylselenophthalimide (Phth-SeCF3), which was an efficient electrophilic trifluoromethylselenolation reagent. This approach has the feature of mild conditions, broad substrate scope, and high functional group tolerance.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"28 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431773","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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