Yuka Iizuka, Koki Obata, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura
The first enantioselective reaction of acyclic α-ketiminoesters with thiols has been developed. Good yields and enantioselectivities were obtained using our original cinchona alkaloid amide/zinc(II) catalysts. The obtained products were converted into useful chiral thiazolidines. Based on experimental results and DFT calculation, transition states were proposed to explain the stereoselectivity of the reaction.
{"title":"Enantioselective Addition of Thiols to Acyclic Ketiminoesters Using Cinchona Alkaloid Amide/Zinc(II) Catalysts","authors":"Yuka Iizuka, Koki Obata, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura","doi":"10.1002/adsc.202400674","DOIUrl":"https://doi.org/10.1002/adsc.202400674","url":null,"abstract":"The first enantioselective reaction of acyclic α-ketiminoesters with thiols has been developed. Good yields and enantioselectivities were obtained using our original cinchona alkaloid amide/zinc(II) catalysts. The obtained products were converted into useful chiral thiazolidines. Based on experimental results and DFT calculation, transition states were proposed to explain the stereoselectivity of the reaction.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141899997","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 Palladium catalyzed C4- alkylation of indoles using epoxide as an alkylating agent and pivaloyl as a weak chelating group has been demonstrated. A variety of substituted epoxides and indoles furnished the desired β-indolylethylalcohols in 38% - 87% yields. Control experiments indicate that the C−H cleavage step is irreversible. The resultant hydroxyl group has been converted to various functional groups to demonstrate the synthetic utility of this protocol.
{"title":"Directing Group Guided Site−Selective Alkylation of Indoles by Epoxides: Synthesis of β-Indolylethyl Alcohol Derivatives","authors":"Ashfaq Ahmad, Mohit Kumar, Anushka Rastogi, Raziullah Khan, Manoj Kumar Gangwar, Dipankar Koley","doi":"10.1002/adsc.202400741","DOIUrl":"https://doi.org/10.1002/adsc.202400741","url":null,"abstract":"A Palladium catalyzed C4- alkylation of indoles using epoxide as an alkylating agent and pivaloyl as a weak chelating group has been demonstrated. A variety of substituted epoxides and indoles furnished the desired β-indolylethylalcohols in 38% - 87% yields. Control experiments indicate that the C−H cleavage step is irreversible. The resultant hydroxyl group has been converted to various functional groups to demonstrate the synthetic utility of this protocol.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141899941","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 route for the construction of benzofulvenes derivatives through 4‐Aminobenzotriazole (ABTA) directed Pd‐catalyzed cascade reactions of amides with inner alkynes was developed. This method afforded a diverse array of benzofulvene derivatives in yields ranging from 34% to 91%. The control experiments indicated that the substrate reacts with alkynes in tandem to synthesize 1,3‐diene intermediates, and ultimately 1,3‐diene underwent intramolecular cyclization to produce benzofulvene derivatives. Furthermore, the directing group can be removed.
{"title":"4‐Aminobenzotriazole (ABTA) Directed Palladium‐Catalyzed Cascade Reaction for Synthesis of Benzofulvenes through C‐H Bond Activation Involving Inner Alkynes","authors":"Chengqian Li, Zhuo Wang, Zhiguang Song","doi":"10.1002/adsc.202400616","DOIUrl":"https://doi.org/10.1002/adsc.202400616","url":null,"abstract":"A route for the construction of benzofulvenes derivatives through 4‐Aminobenzotriazole (ABTA) directed Pd‐catalyzed cascade reactions of amides with inner alkynes was developed. This method afforded a diverse array of benzofulvene derivatives in yields ranging from 34% to 91%. The control experiments indicated that the substrate reacts with alkynes in tandem to synthesize 1,3‐diene intermediates, and ultimately 1,3‐diene underwent intramolecular cyclization to produce benzofulvene derivatives. Furthermore, the directing group can be removed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141877521","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}
Jie Lin, Juan Ma, Liandi Wang, Ping Wu, Kaikai Wu, Yong-Gui Zhou, Zhengkun Yu
Palladium-catalyzed stereoselective olefinic C–H alkynylation of gem-diarylsubstituted ethylenes with propargylic alcohols was achieved to access diverse unsymmetrical 1,3-enynes. The regio- and stereoselectivities were established through a 1,4-palladium migration from aryl to vinyl in the presence of 2-FC<sub>6</sub>H<sub>4</sub>OH additive. Mechanistic investigations have suggested that cleavage of the olefinic C–H bond might not be involved in the rate-determining step throughout the catalytic process.
{"title":"Stereoselective Construction of Trisubstituted 1,3-Enynes via Aryl to Vinyl 1,4-Palladium Migration","authors":"Jie Lin, Juan Ma, Liandi Wang, Ping Wu, Kaikai Wu, Yong-Gui Zhou, Zhengkun Yu","doi":"10.1002/adsc.202400793","DOIUrl":"https://doi.org/10.1002/adsc.202400793","url":null,"abstract":"Palladium-catalyzed stereoselective olefinic C–H alkynylation of gem-diarylsubstituted ethylenes with propargylic alcohols was achieved to access diverse unsymmetrical 1,3-enynes. The regio- and stereoselectivities were established through a 1,4-palladium migration from aryl to vinyl in the presence of 2-FC<sub>6</sub>H<sub>4</sub>OH additive. Mechanistic investigations have suggested that cleavage of the olefinic C–H bond might not be involved in the rate-determining step throughout the catalytic process.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141877576","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}
Ning Zou, Yu-Zheng Wu, Xin-Yi Zhong, Cui Wei, Li-Min Liao, Dong-Liang Mo, Wen-Jun Zhou
We describe a chiral phosphoric acid (CPA) catalyzed asymmetric [3+3] cycloaddition of N‐viny oxindole nitrones with 2‐indolylmethanols to prepare various spirooxindole[1,2]oxazines in 43‐93% yields and 88:12‐97:3 enantiomeric ratios. Experimental results revealed that the addition of hexafluoroisopropanol (HFIP) played important roles to help CPA control the reaction reactivity and enantioselectivity. The present method features the construction of tetrasubstituted chiral carbon stereocenter and the example of N‐vinyl nitrones in asymmetric [3+3] cycloaddition.
{"title":"Asymmetric [3+3] Cycloaddition of N‐Vinyl Oxindole Nitrones with 2‐Indolylmethanols to Prepare Spirooxindole[1,2]oxazines","authors":"Ning Zou, Yu-Zheng Wu, Xin-Yi Zhong, Cui Wei, Li-Min Liao, Dong-Liang Mo, Wen-Jun Zhou","doi":"10.1002/adsc.202400533","DOIUrl":"https://doi.org/10.1002/adsc.202400533","url":null,"abstract":"We describe a chiral phosphoric acid (CPA) catalyzed asymmetric [3+3] cycloaddition of N‐viny oxindole nitrones with 2‐indolylmethanols to prepare various spirooxindole[1,2]oxazines in 43‐93% yields and 88:12‐97:3 enantiomeric ratios. Experimental results revealed that the addition of hexafluoroisopropanol (HFIP) played important roles to help CPA control the reaction reactivity and enantioselectivity. The present method features the construction of tetrasubstituted chiral carbon stereocenter and the example of N‐vinyl nitrones in asymmetric [3+3] cycloaddition.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141877522","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}
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}
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}
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