Stefan F. Kirsch, Bastian L. Springer, Kristina Holzschneider, Fabian Mohr
Abstract A new synthetic route for the synthesis of phenanthro[9,10‑d]imidazoles is described. Through aminolysis of easily accessible 10,10-diazidophenanthren-9(10H)-one with nucleophilic amines, a self-condensation is triggered that results in the formation of the target phenanthro[9,10‑d]imidazoles. The molecular structures were studied by X-ray single crystallography, and the optical properties of the material are described.
{"title":"Phenanthro[9,10‑d]imidazoles: An Unexpected Synthetic Route","authors":"Stefan F. Kirsch, Bastian L. Springer, Kristina Holzschneider, Fabian Mohr","doi":"10.1055/s-0042-1751493","DOIUrl":"https://doi.org/10.1055/s-0042-1751493","url":null,"abstract":"Abstract A new synthetic route for the synthesis of phenanthro[9,10‑d]imidazoles is described. Through aminolysis of easily accessible 10,10-diazidophenanthren-9(10H)-one with nucleophilic amines, a self-condensation is triggered that results in the formation of the target phenanthro[9,10‑d]imidazoles. The molecular structures were studied by X-ray single crystallography, and the optical properties of the material are described.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135483449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mengran Li, Peng Chen, Haoqi Liu, Jian Huang, Yang Chen
The biologic properties and synthetic effort of ferruginol as a classical abietane-type diterpenoid with an aromatic C ring are reviewed. A strategy overview from 1954 to 2023 toward the total synthesis of ferruginol may provide some references for future design and synthesis of new diterpenoids natural products.
{"title":"Review of total synthesis of aromatic abietane diterpenoid: Ferruginol","authors":"Mengran Li, Peng Chen, Haoqi Liu, Jian Huang, Yang Chen","doi":"10.1055/a-2186-7983","DOIUrl":"https://doi.org/10.1055/a-2186-7983","url":null,"abstract":"The biologic properties and synthetic effort of ferruginol as a classical abietane-type diterpenoid with an aromatic C ring are reviewed. A strategy overview from 1954 to 2023 toward the total synthesis of ferruginol may provide some references for future design and synthesis of new diterpenoids natural products.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135483332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cameron Massey, Timothy Scott Snowden, Michael P. Jennings
The preparation and TMSOTf-mediated catalytic carbocupration-silylation of allylic propiolates has been investigated, expanding on previous syntheses of a variety of β-alkyl- and β-aryl-substituted vinylsilanes from an ethyl propiolate precursor. With few exceptions, the series of synthesized O-allyl (E)-vinylsilanes has been isolated in high yields (61-89%) with exceptional diastereoselectivities (E/Z > 20:1). Additionally, we demonstrated a novel LDA-initiated, TMSCl-mediated Ireland-Claisen rearrangement of a representative allylic ester.
{"title":"Preparation and Carbocupration-Silylation of Allyl Propiolates: Vicinal Functionalization to Form Polysubstituted (E)-Vinylic Silanes","authors":"Cameron Massey, Timothy Scott Snowden, Michael P. Jennings","doi":"10.1055/a-2186-6964","DOIUrl":"https://doi.org/10.1055/a-2186-6964","url":null,"abstract":"The preparation and TMSOTf-mediated catalytic carbocupration-silylation of allylic propiolates has been investigated, expanding on previous syntheses of a variety of β-alkyl- and β-aryl-substituted vinylsilanes from an ethyl propiolate precursor. With few exceptions, the series of synthesized O-allyl (E)-vinylsilanes has been isolated in high yields (61-89%) with exceptional diastereoselectivities (E/Z > 20:1). Additionally, we demonstrated a novel LDA-initiated, TMSCl-mediated Ireland-Claisen rearrangement of a representative allylic ester.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135483712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract This review delves into recent advances and significant breakthroughs in the field of the catalytic Friedel–Crafts alkylation of targeted arenes or heteroarenes. Though a few earlier literatures are referenced, the main emphasis of this review focuses on the literature mainly published between 2015 and March 2023. 1 Introduction 2 History and Background 3 Alcohols as Alkylating Agents 4 Aldehydes and Ketones as Alkylating Agents 5 Alkyl Fluorides as Alkylating Agents 6 Epoxides as Alkylating Agents 7 Cyclopropanes as Alkylating Agents 8 Conclusion and Outlook
{"title":"Recent Advancements in Typical Friedel–Crafts Alkylation Reactions Focused on Targeting Arene Nucleophiles","authors":"Chinmoy K. Hazra, Sanjay Singh","doi":"10.1055/s-0042-1751492","DOIUrl":"https://doi.org/10.1055/s-0042-1751492","url":null,"abstract":"Abstract This review delves into recent advances and significant breakthroughs in the field of the catalytic Friedel–Crafts alkylation of targeted arenes or heteroarenes. Though a few earlier literatures are referenced, the main emphasis of this review focuses on the literature mainly published between 2015 and March 2023. 1 Introduction 2 History and Background 3 Alcohols as Alkylating Agents 4 Aldehydes and Ketones as Alkylating Agents 5 Alkyl Fluorides as Alkylating Agents 6 Epoxides as Alkylating Agents 7 Cyclopropanes as Alkylating Agents 8 Conclusion and Outlook","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135828403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nikita Vystavkin, Manuel Barday, Christopher Teskey
Abstract Photochemistry has become a key area of research in synthetic chemistry over the last few decades. More recently, interest has grown in merging this area with transition metal catalysis to develop new reactivity. One key photoinduced step in this context is ligand dissociation from transition metal complexes. This has been used to develop light-gated catalysis, allowing for on/off control over a reaction. However, this concept can only result in a single product outcome. Our group has focused on the development of cobalt-catalyzed reactivity switches, enabled by a simple photodissociation step, which promotes one mechanistic path or another. As such, we can use a single catalytic platform to yield two different outcomes depending on whether the reaction is irradiated with light or not. This short review will focus on works in this area by our group and others. 1 Introduction 2 Photocontrolled Hydroboration 3 Hydrogenation and Hydroformylation 4 Conclusion
{"title":"Discovery of divergent, light-controlled catalysis triggered by ligand photodissociation from cobalt complexes","authors":"Nikita Vystavkin, Manuel Barday, Christopher Teskey","doi":"10.1055/a-2183-4332","DOIUrl":"https://doi.org/10.1055/a-2183-4332","url":null,"abstract":"Abstract Photochemistry has become a key area of research in synthetic chemistry over the last few decades. More recently, interest has grown in merging this area with transition metal catalysis to develop new reactivity. One key photoinduced step in this context is ligand dissociation from transition metal complexes. This has been used to develop light-gated catalysis, allowing for on/off control over a reaction. However, this concept can only result in a single product outcome. Our group has focused on the development of cobalt-catalyzed reactivity switches, enabled by a simple photodissociation step, which promotes one mechanistic path or another. As such, we can use a single catalytic platform to yield two different outcomes depending on whether the reaction is irradiated with light or not. This short review will focus on works in this area by our group and others. 1 Introduction 2 Photocontrolled Hydroboration 3 Hydrogenation and Hydroformylation 4 Conclusion","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135385526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Itziar Guerrero, Eugene Yew Kun Tan, Yuliang Liu, Lee J. Edwards, Shunsuke Chiba
Abstract A photochemical protocol for the alkylation of diazines (pyrimidines, pyrazines, and pyridazines) with N-(acyloxy)phthalimides has been developed. The process is facilitated by the presence of triethylamine under irradiation with 427–390 nm light; this enables rapid cross-coupling reactions to construct a wide range of alkylated diazines.
{"title":"Photoinduced alkylation of diazines with N-(acyloxy)phthalimides in the presence of triethylamine","authors":"Itziar Guerrero, Eugene Yew Kun Tan, Yuliang Liu, Lee J. Edwards, Shunsuke Chiba","doi":"10.1055/a-2182-7416","DOIUrl":"https://doi.org/10.1055/a-2182-7416","url":null,"abstract":"Abstract A photochemical protocol for the alkylation of diazines (pyrimidines, pyrazines, and pyridazines) with N-(acyloxy)phthalimides has been developed. The process is facilitated by the presence of triethylamine under irradiation with 427–390 nm light; this enables rapid cross-coupling reactions to construct a wide range of alkylated diazines.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135478497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nicholas Forsythe, Emma Mize, Gustavo Kashiwagi, Alexei V Demchenko
Abstract Superarmed glycosyl donors have higher reactivity compared to their perbenzylated armed counterparts. Generally, the 2-O-benzoyl-3,4,6-tri-O-benzyl protecting group pattern gives rise to increased reactivity due to an O-2/O-5 cooperative effect. Despite having a high reactivity profile and applicability in many expeditious strategies for glycan synthesis, regioselective introduction of the superarming protecting group pattern is tedious for most sugar series. Reported herein is a streamlined synthetic route to yield superarmed glycosyl donors of the d-gluco and d-galacto series equipped with an ethylthio, phenylthio, p-tolylthio, benzoxazol-2-ylthio, O-allyl, or O-pentenyl anomeric leaving group. This streamlined approach was made possible due to the refinement of the oxidative thioglycosylation reaction of the respective glucal and galactal precursors. The applicability of this approach to the direct formation of disaccharides is also showcased.
超旋臂糖基供体与过苄基旋臂糖基供体相比具有更高的反应性。一般来说，2- o -苯甲酰-3,4,6-三- o -苯保护基模式由于O-2/O-5协同效应而提高了反应性。尽管具有很高的反应性，适用于许多快速的糖合成策略，但对于大多数糖系来说，区域选择性地引入超警戒保护基团模式是繁琐的。本文报道了一种流线型的合成路线，以生产具有乙基硫、苯硫、对甲基硫、苯并恶唑-2-基硫、o -烯丙基或o -戊基端粒离去基的d-葡萄糖和d-半乳糖系列的超臂糖基供体。由于各自的葡萄糖和半乳糖前体的氧化巯基化反应的改进，这种简化的方法成为可能。这种方法对直接形成双糖的适用性也得到了证明。
{"title":"Expedient synthesis of superarmed glycosyl donors via oxidative thioglycosidation of glycals","authors":"Nicholas Forsythe, Emma Mize, Gustavo Kashiwagi, Alexei V Demchenko","doi":"10.1055/a-2183-0175","DOIUrl":"https://doi.org/10.1055/a-2183-0175","url":null,"abstract":"Abstract Superarmed glycosyl donors have higher reactivity compared to their perbenzylated armed counterparts. Generally, the 2-O-benzoyl-3,4,6-tri-O-benzyl protecting group pattern gives rise to increased reactivity due to an O-2/O-5 cooperative effect. Despite having a high reactivity profile and applicability in many expeditious strategies for glycan synthesis, regioselective introduction of the superarming protecting group pattern is tedious for most sugar series. Reported herein is a streamlined synthetic route to yield superarmed glycosyl donors of the d-gluco and d-galacto series equipped with an ethylthio, phenylthio, p-tolylthio, benzoxazol-2-ylthio, O-allyl, or O-pentenyl anomeric leaving group. This streamlined approach was made possible due to the refinement of the oxidative thioglycosylation reaction of the respective glucal and galactal precursors. The applicability of this approach to the direct formation of disaccharides is also showcased.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135534669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract A novel series of pyrido[2,3-b]quinoxaline-3-carboxylate derivatives was synthesized in short reaction times and in moderate to good yields by using a palladium catalyst in a one-pot Buchwald amination/cyclization reaction.
{"title":"Novel Synthesis of Pyrido[2,3-b]quinoxaline-3-carboxylate Derivatives via One-pot Buchwald Amination-Cyclization","authors":"majdi Hajiri, Omar Khoumeri, Raoudha Abderrahim, Thierry Terme, Patrice Vanelle","doi":"10.1055/a-2183-0324","DOIUrl":"https://doi.org/10.1055/a-2183-0324","url":null,"abstract":"Abstract A novel series of pyrido[2,3-b]quinoxaline-3-carboxylate derivatives was synthesized in short reaction times and in moderate to good yields by using a palladium catalyst in a one-pot Buchwald amination/cyclization reaction.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135534482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seung Hyeon Yoon, Kye Sung Park, Jaehee Kim, Yonghoon Kwon
Abstract Lewis acid catalyzed 4π-electrocyclization of Donor–Acceptor Stenhouse Adducts (DASAs) has been developed. By employing catalytic quantities of Dy(OTf)3, a highly efficient transformation of acyclic DASAs into the corresponding cyclized isomers was achieved. Notably, this transformation exhibited exceptional yields, particularly in the case of first generation DASAs. In addition, Lewis acid catalysis enabled one-pot synthesis of the cyclopentenone product from the ‘donor’ and ‘acceptor’ components.
{"title":"Lewis Acid Catalyzed 4π-Electrocyclization of Donor-Acceptor Stenhouse Adducts","authors":"Seung Hyeon Yoon, Kye Sung Park, Jaehee Kim, Yonghoon Kwon","doi":"10.1055/a-2182-9098","DOIUrl":"https://doi.org/10.1055/a-2182-9098","url":null,"abstract":"Abstract Lewis acid catalyzed 4π-electrocyclization of Donor–Acceptor Stenhouse Adducts (DASAs) has been developed. By employing catalytic quantities of Dy(OTf)3, a highly efficient transformation of acyclic DASAs into the corresponding cyclized isomers was achieved. Notably, this transformation exhibited exceptional yields, particularly in the case of first generation DASAs. In addition, Lewis acid catalysis enabled one-pot synthesis of the cyclopentenone product from the ‘donor’ and ‘acceptor’ components.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135478503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A photo-induced intramolecular electron-aromatic-substitution (SEAr) of N-acyloxybenzozmide under 20 mol% FeCl3 at 1, 4-dioxane is reported for the synthesis of biologically interesting benzoxazin-3(4H)-ones. In the reaction, it is believed that blue LED facilitates the reaction, like reaction temperature serving as source of energy. The reaction SEAr pathway was ascribed to the electron effect in aryl ring of substrates. The reaction was also applicable for the synthesis of useful scaffolds possessing a quinolin-2-one core, such as anticancer reagent 4, brexipiprazole and cilostamide analogues.
{"title":"Photo-Induced Electrophilic Aromatic Substitution of Ferric Acyl Nitrene","authors":"Ming Hou, Zhide Zhang, Xiaojing Lai, Qianzhou Zong, Miaofeng Ren, Tianwen Bai, Guanyinsheng Qiu","doi":"10.1055/a-2183-0262","DOIUrl":"https://doi.org/10.1055/a-2183-0262","url":null,"abstract":"A photo-induced intramolecular electron-aromatic-substitution (SEAr) of N-acyloxybenzozmide under 20 mol% FeCl3 at 1, 4-dioxane is reported for the synthesis of biologically interesting benzoxazin-3(4H)-ones. In the reaction, it is believed that blue LED facilitates the reaction, like reaction temperature serving as source of energy. The reaction SEAr pathway was ascribed to the electron effect in aryl ring of substrates. The reaction was also applicable for the synthesis of useful scaffolds possessing a quinolin-2-one core, such as anticancer reagent 4, brexipiprazole and cilostamide analogues.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135534543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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