fatemeh doraghi, Parsa Baghershahi, Farzad Gilaninezhad, Negar Mehdi zadeh Darban, Navid Dastyafteh, Milad Noori, Mohammad Mahdavi
Owing to multiple reactive sites, such as an acidic α‐carbon and an isocyano group, isocyanide esters can successfully participate in the synthesis of various five‐ and six‐membered N‐heterocycles through the cycloaddition reactions under metal‐catalyzed systems. Considering the unique and versatile functionality of this synthon, in this review, we have highlighted silver and copper‐catalyzed cycloadditions of isocyanide esters over the last decade.
{"title":"Silver and Copper‐Catalyzed Cycloaddition Reactions of Isocyanide Esters","authors":"fatemeh doraghi, Parsa Baghershahi, Farzad Gilaninezhad, Negar Mehdi zadeh Darban, Navid Dastyafteh, Milad Noori, Mohammad Mahdavi","doi":"10.1002/adsc.202400994","DOIUrl":"https://doi.org/10.1002/adsc.202400994","url":null,"abstract":"Owing to multiple reactive sites, such as an acidic α‐carbon and an isocyano group, isocyanide esters can successfully participate in the synthesis of various five‐ and six‐membered N‐heterocycles through the cycloaddition reactions under metal‐catalyzed systems. Considering the unique and versatile functionality of this synthon, in this review, we have highlighted silver and copper‐catalyzed cycloadditions of isocyanide esters over the last decade.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415740","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 stepwise copper-catalyzed boracarboxylation then palladium-catalyzed Suzuki-Miyaura cross-coupling methodology was developed to access 2,3-diarylpropionic acid derivatives regioselectively by pre-setting the position of the carboxylic acid in the boracarboxylation reaction. This method provides access to a wide range of aryl and heteroaryl products in up to 80% isolated yield. Pharmaceutical potential was demonstrated by synthesizing a glucagon receptor antagonist drug in 3-steps (31% overall yield) from commercially available 4-tert-butylstyrene.
{"title":"Methodology to Control the Regioselective Installation of a Carboxylic Acid for the Synthesis of 2,3-Diarylpropionic Acids","authors":"Mason Hamilton, Trina M. Perrone, Brian Popp","doi":"10.1002/adsc.202400952","DOIUrl":"https://doi.org/10.1002/adsc.202400952","url":null,"abstract":"A stepwise copper-catalyzed boracarboxylation then palladium-catalyzed Suzuki-Miyaura cross-coupling methodology was developed to access 2,3-diarylpropionic acid derivatives regioselectively by pre-setting the position of the carboxylic acid in the boracarboxylation reaction. This method provides access to a wide range of aryl and heteroaryl products in up to 80% isolated yield. Pharmaceutical potential was demonstrated by synthesizing a glucagon receptor antagonist drug in 3-steps (31% overall yield) from commercially available 4-tert-butylstyrene.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"108 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398613","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}
Benzofluorenes are an important class of polycyclic aromatic hydrocarbons (PAHs), which are widely used in materials science for light-sensitive electronic components. In addition, the benzofluorene skeleton also serves as a key structural unit in various natural products. Therefore, the development of synthetic strategies for the construction of benzofluorenes has been a prominent research topic in synthetic chemistry. Over the past few decades, numerous efforts have been made for the construction of benzofluorenes via cascade cyclization of alkyne units. This review aims to summarize recent advances in the cascade cyclization of alkyne units for the construction of Based on the different reaction mechanisms underlying these transformations, this review can be divided into four categories: (1) thermal-induced cascade cyclization of alkyne units for the construction of benzofluorenes, (2) metal-catalyzed cascade cyclization of alkyne units for the construction of benzofluorenes, (3) acid-promoted/catalyzed cyclization of alkyne units for the construction of benzofluorenes, and (4) base-promoted cascade cyclization of alkyne units for the construction of benzofluorenes.
{"title":"Recent Advances in the Cascade Cyclization of Alkyne Units for the Construction of Benzofluorenes","authors":"Shimin Jiang, Ruchun Yang, Xian-Rong Song, qiang xiao","doi":"10.1002/adsc.202401047","DOIUrl":"https://doi.org/10.1002/adsc.202401047","url":null,"abstract":"Benzofluorenes are an important class of polycyclic aromatic hydrocarbons (PAHs), which are widely used in materials science for light-sensitive electronic components. In addition, the benzofluorene skeleton also serves as a key structural unit in various natural products. Therefore, the development of synthetic strategies for the construction of benzofluorenes has been a prominent research topic in synthetic chemistry. Over the past few decades, numerous efforts have been made for the construction of benzofluorenes via cascade cyclization of alkyne units. This review aims to summarize recent advances in the cascade cyclization of alkyne units for the construction of Based on the different reaction mechanisms underlying these transformations, this review can be divided into four categories: (1) thermal-induced cascade cyclization of alkyne units for the construction of benzofluorenes, (2) metal-catalyzed cascade cyclization of alkyne units for the construction of benzofluorenes, (3) acid-promoted/catalyzed cyclization of alkyne units for the construction of benzofluorenes, and (4) base-promoted cascade cyclization of alkyne units for the construction of benzofluorenes.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398607","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}
We herein report that the combination of Fe(OTf)3 and triphenylphosphate (TPP, (PhO)3PO) has proven to be an effective catalyst for the intramolecular hydroamination of amino-1,3-dienes with an efficiency and scope superior to previously reported methods. This catalytic system demonstrated consistent performance with diverse aminodienes as well as aminoolefins, providing five- to seven-membered N-heterocycles. We propose a Lewis/Brønsted acid cocatalysis mechanism involving proton transfer through hydrogen bonding with TPP. Catalyst system consisting of inexpensive and nontoxic iron salt and phosphate additive, relatively low loading and recyclability of catalyst, and rapid and high-yielding reaction are the advantages of this protocol.
{"title":"Fe(III)-Catalyzed Intramolecular Hydroamination of 1,3-Dienes Improved by Using Triphenylphosphate as an Additive","authors":"Ye Jin Kim, Dong Bin Kim, So Won Youn","doi":"10.1002/adsc.202401180","DOIUrl":"https://doi.org/10.1002/adsc.202401180","url":null,"abstract":"We herein report that the combination of Fe(OTf)3 and triphenylphosphate (TPP, (PhO)3PO) has proven to be an effective catalyst for the intramolecular hydroamination of amino-1,3-dienes with an efficiency and scope superior to previously reported methods. This catalytic system demonstrated consistent performance with diverse aminodienes as well as aminoolefins, providing five- to seven-membered N-heterocycles. We propose a Lewis/Brønsted acid cocatalysis mechanism involving proton transfer through hydrogen bonding with TPP. Catalyst system consisting of inexpensive and nontoxic iron salt and phosphate additive, relatively low loading and recyclability of catalyst, and rapid and high-yielding reaction are the advantages of this protocol.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398610","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}
María Trinidad Martín, Celia Maya, Agustin Galindo, M Carmen Nicasio
We report the Ni-catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 º or 50 ºC) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.
{"title":"Ni-Catalyzed [2+2+2] Cycloaddition of Alkynes to Form Arenes and Pyridines at Low Catalyst Loadings","authors":"María Trinidad Martín, Celia Maya, Agustin Galindo, M Carmen Nicasio","doi":"10.1002/adsc.202400765","DOIUrl":"https://doi.org/10.1002/adsc.202400765","url":null,"abstract":"We report the Ni-catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 º or 50 ºC) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"43 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398093","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}
This work describes gold-catalyzed annulations of 1-(2-(dimethoxymethyl)phenyl)-1-prop-2-yn-1-yl acetate substrates with α-diazo esters and anilines, respectively yielding substituted naphthoates and indeno[1,2-b]quinoline derivatives. Our mechanistic analysis indicates 1-methoxy-2-carbonyl-1H-indenes as their common intermediates. In the formation of naphthoates, α-diazo ester attacks at gold-bound intermediate via a SN2 pathway to enable a allylic methoxy substitution. For indeno[1,2-b]quinoline derivatives, there are two main reactions, including (i) a reversible formation between intermediate and a double amine addition product and (ii) an arylation reaction of intermediate. Species N-(phenyl((2E)-1-(phenylimino)-1,3-dihydro-2H-inden-2-ylidene)methyl)aniline was converted to indeno[1,2-b]quinoline in the presence of gold catalyst.
这项工作描述了金催化 1-(2-(二甲氧基甲基)苯基)-1-丙-2-炔-1-基乙酸酯底物与 α-重氮酯和苯胺的环化反应，分别生成取代的萘酸盐和茚并[1,2-b]喹啉衍生物。我们的机理分析表明，1-甲氧基-2-羰基-1H-茚是它们的共同中间体。在萘酸盐的形成过程中，α-重氮酯通过 SN2 途径攻击与金结合的中间体，从而实现烯丙基甲氧基取代。对于茚并[1,2-b]喹啉衍生物，主要有两个反应，包括 (i) 中间体与双胺加成产物之间的可逆生成，以及 (ii) 中间体的芳基化反应。在金催化剂存在下，N-(苯基((2E)-1-(苯基亚氨基)-1,3-二氢-2H-茚-2-亚基)甲基)苯胺被转化为茚并[1,2-b]喹啉。
{"title":"Gold-catalyzed Annulation between 1-[2-(Dimethoxymethyl)phenyl]prop-2-yn-1-yl Acetates and α-Diazoesters or Anilines to Form Substituted Naphthoates and Indeno[1,2-b]quinoline, Respectively.","authors":"Rai-Shung Liu, Akshay Suresh Kshirsagar","doi":"10.1002/adsc.202400968","DOIUrl":"https://doi.org/10.1002/adsc.202400968","url":null,"abstract":"This work describes gold-catalyzed annulations of 1-(2-(dimethoxymethyl)phenyl)-1-prop-2-yn-1-yl acetate substrates with α-diazo esters and anilines, respectively yielding substituted naphthoates and indeno[1,2-b]quinoline derivatives. Our mechanistic analysis indicates 1-methoxy-2-carbonyl-1H-indenes as their common intermediates. In the formation of naphthoates, α-diazo ester attacks at gold-bound intermediate via a SN2 pathway to enable a allylic methoxy substitution. For indeno[1,2-b]quinoline derivatives, there are two main reactions, including (i) a reversible formation between intermediate and a double amine addition product and (ii) an arylation reaction of intermediate. Species N-(phenyl((2E)-1-(phenylimino)-1,3-dihydro-2H-inden-2-ylidene)methyl)aniline was converted to indeno[1,2-b]quinoline in the presence of gold catalyst.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398551","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}
Wen-Jun Han, Fang-Long Yang, Zhiyuan Hu, Wenxia Chen, Shun Liu, Ke Guo, Xin-Yuan Yang, Bin Cheng
The copper powder-mediated tandem hydroamination cyclization-hydrocyanation of alkyne-tethered ketoximes is described by using TMSCN as the commercially available cyanating reagent. This methodology provides an alternative strategy for the synthesis of a series of structurally important cyano-substituted cyclic nitrones. The hydrocyanation process exhibits distinct regioselectivity depending on the substituent pattern of the alkyne moiety. Moreover, the synthesized products were shown to be capable of undergoing various derivatization reactions.
{"title":"Copper Powder-Mediated Tandem Hydroamination Cyclization-Hydrocyanation of Alkyne-Tethered Ketoximes toward Cyano-Featured Cyclic Nitrones","authors":"Wen-Jun Han, Fang-Long Yang, Zhiyuan Hu, Wenxia Chen, Shun Liu, Ke Guo, Xin-Yuan Yang, Bin Cheng","doi":"10.1002/adsc.202401049","DOIUrl":"https://doi.org/10.1002/adsc.202401049","url":null,"abstract":"The copper powder-mediated tandem hydroamination cyclization-hydrocyanation of alkyne-tethered ketoximes is described by using TMSCN as the commercially available cyanating reagent. This methodology provides an alternative strategy for the synthesis of a series of structurally important cyano-substituted cyclic nitrones. The hydrocyanation process exhibits distinct regioselectivity depending on the substituent pattern of the alkyne moiety. Moreover, the synthesized products were shown to be capable of undergoing various derivatization reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398094","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 synthesis of unsymmetrical bis(indolyl)methanes (BIMs) using simple indoles and readily available alcohols as the coupling partners under both heat and 390–400 nm light conditions was developed. Detailed research of the mechanism demonstrated that the diaryliodonium salt-mediated transformation undergoes a nucleophilic hydroxymethyl radical formation process. Moreover, the diaryliodonium salt-mediated method is also applicable for synthesizing symmetrical BIMs.
{"title":"Diaryliodonium Salt-Mediated Radical Transformation of Indoles with Alcohols for the Synthesis of Unsymmetrical Bis(indolyl)methanes","authors":"Hongzhen Wang, Haohao Jiang, Shuizhen Lin, Shuoshuo Zhang, Xiaolei Huang","doi":"10.1002/adsc.202400827","DOIUrl":"https://doi.org/10.1002/adsc.202400827","url":null,"abstract":"A method for the synthesis of unsymmetrical bis(indolyl)methanes (BIMs) using simple indoles and readily available alcohols as the coupling partners under both heat and 390–400 nm light conditions was developed. Detailed research of the mechanism demonstrated that the diaryliodonium salt-mediated transformation undergoes a nucleophilic hydroxymethyl radical formation process. Moreover, the diaryliodonium salt-mediated method is also applicable for synthesizing symmetrical BIMs.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"210 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398095","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}
Zhihua Wang, Wang-Fu Liang, Xinglei He, Jingheng Li, Keyin Ye
Herein, we reported the straightforward synthesis of thiomethylnaphthalenes via the reaction of propargyl alcohols with DMSO/SOCl2, which also provided easy access to deuterated thiomethyl and other thioalkyl scaffolds when deuterated dimethyl sulfoxide and dialkyl sulfoxides were used, respectively. In addition, the thiomethyl group can be readily derivatized to the corresponding sulfoxide, sulfone, and sulfoximine of interesting photophysical properties.
{"title":"DMSO/SOCl2‐Mediated Synthesis of Thiomethylnaphthalenes from Propargyl Alcohols","authors":"Zhihua Wang, Wang-Fu Liang, Xinglei He, Jingheng Li, Keyin Ye","doi":"10.1002/adsc.202401025","DOIUrl":"https://doi.org/10.1002/adsc.202401025","url":null,"abstract":"Herein, we reported the straightforward synthesis of thiomethylnaphthalenes via the reaction of propargyl alcohols with DMSO/SOCl2, which also provided easy access to deuterated thiomethyl and other thioalkyl scaffolds when deuterated dimethyl sulfoxide and dialkyl sulfoxides were used, respectively. In addition, the thiomethyl group can be readily derivatized to the corresponding sulfoxide, sulfone, and sulfoximine of interesting photophysical properties.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385450","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}
Adam Cieśliński, Artur Przydacz, Lesław Sieroń, Anna Skrzyńska, Łukasz Albrecht
[10+2]-Hetero-higher-order cycloaddition between tropone hydrazides (acting as 10π-components) and 3-alkylidene oxindoles (acting as 2π-components) has been established. Under Brønsted base catalysis the reaction proceeded in a fully peri- and diastereoselective manner with the stereochemical outcome governed mainly by electronic interactions. Following such a strategy, a series of structurally diverse tetrahydropyridazines were prepared in 30-70% yields. Furthermore, the potential of the obtained cycloadducts has been confirmed in selected chemoselective transformations.
{"title":"Tropone hydrazides in [10+2]-hetero-higher-order cycloaddition for the synthesis of tetrahydropyridazine derivatives","authors":"Adam Cieśliński, Artur Przydacz, Lesław Sieroń, Anna Skrzyńska, Łukasz Albrecht","doi":"10.1002/adsc.202401033","DOIUrl":"https://doi.org/10.1002/adsc.202401033","url":null,"abstract":"[10+2]-Hetero-higher-order cycloaddition between tropone hydrazides (acting as 10π-components) and 3-alkylidene oxindoles (acting as 2π-components) has been established. Under Brønsted base catalysis the reaction proceeded in a fully peri- and diastereoselective manner with the stereochemical outcome governed mainly by electronic interactions. Following such a strategy, a series of structurally diverse tetrahydropyridazines were prepared in 30-70% yields. Furthermore, the potential of the obtained cycloadducts has been confirmed in selected chemoselective transformations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385066","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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