Jun Yan, Pascal Retailleau, Christine Tran, Abdallah Hamze
We developed a transition metal-free methodology for the construction of pyrazoloquinazolinone derivatives. The strategy involves a one-pot reaction wherein the N-tosylhydrazone and its corresponding diazo derivative are generated in situ, followed by an intramolecular 1,3-dipolar cycloaddition-ring expansion to provide the pyrazolo-[1,5-c]quinazolinone motif. This approach enables straightforward access to a diverse range of highly functionalized N-heterocyclic compounds in good yields (up to 92%).
{"title":"Leveraging <i>in situ N</i>-tosylhydrazones as diazo surrogates for efficient access to pyrazolo-[1,5-<i>c</i>]quinazolinone derivatives.","authors":"Jun Yan, Pascal Retailleau, Christine Tran, Abdallah Hamze","doi":"10.1039/d4ob00950a","DOIUrl":"https://doi.org/10.1039/d4ob00950a","url":null,"abstract":"<p><p>We developed a transition metal-free methodology for the construction of pyrazoloquinazolinone derivatives. The strategy involves a one-pot reaction wherein the <i>N</i>-tosylhydrazone and its corresponding diazo derivative are generated <i>in situ</i>, followed by an intramolecular 1,3-dipolar cycloaddition-ring expansion to provide the pyrazolo-[1,5-<i>c</i>]quinazolinone motif. This approach enables straightforward access to a diverse range of highly functionalized N-heterocyclic compounds in good yields (up to 92%).</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The palladium-catalysed regioselective C-H chalcogenation of benzoxazines with disulfides and diselenides in air has been described. In this protocol, palladium acetate serves as the catalyst in conjunction with copper as an oxidizing agent. Through this approach, a wide array of sulfenylation and selenylation reactions of benzomorpholines have been effected, yielding results ranging from good to excellent. Thus, the established procedure demonstrates superb regioselectivity and a strong tolerance towards various functional groups and is suitable for gram-scale synthesis. Additionally, this synthetic approach offers a practical and convenient pathway for late-stage functionalization leading to the Rosenmund-von Braun reaction.
{"title":"Expedient, regioselective C-H chalcogenation of 3,4-dihydro-1,4-benzoxazines using a palladium-copper catalyst.","authors":"Ram Sunil Kumar Lalji, Monika, Mohit Gupta, Sandeep Kumar, Ray J Butcher, Brajendra Kumar Singh","doi":"10.1039/d4ob00524d","DOIUrl":"https://doi.org/10.1039/d4ob00524d","url":null,"abstract":"<p><p>The palladium-catalysed regioselective C-H chalcogenation of benzoxazines with disulfides and diselenides in air has been described. In this protocol, palladium acetate serves as the catalyst in conjunction with copper as an oxidizing agent. Through this approach, a wide array of sulfenylation and selenylation reactions of benzomorpholines have been effected, yielding results ranging from good to excellent. Thus, the established procedure demonstrates superb regioselectivity and a strong tolerance towards various functional groups and is suitable for gram-scale synthesis. Additionally, this synthetic approach offers a practical and convenient pathway for late-stage functionalization leading to the Rosenmund-von Braun reaction.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Subhashini V Subramaniam, Badal Singh, Natarajan Pradeep, Saravanan Peruncheralathan
We present the PIFA-mediated intramolecular N-arylation of 2-aminoquinoxalines at room temperature for the first time. This method provides a wide range of indolo[2,3-b]quinoxalines in good to excellent yields within a short time. The C-H bond functionalization occurs without the need for an inert atmosphere or additives. Additionally, a double C-H bond functionalization was observed, where the first reaction forms a C-N bond (N-arylation) and the second forms a C-O bond, yielding an acetal-functionalized product. Mechanistic investigations suggest that the C-H bond functionalization proceeds through an ionic mechanism, whereas acetal functionalization follows a radical pathway. This method extends to the derivation of indoloquinoxalines, including the target compound BIQMCz.
{"title":"PIFA-mediated intramolecular <i>N</i>-arylation of 2-aminoquinoxalines to afford indolo[2,3-<i>b</i>]quinoxaline derivatives.","authors":"Subhashini V Subramaniam, Badal Singh, Natarajan Pradeep, Saravanan Peruncheralathan","doi":"10.1039/d4ob00812j","DOIUrl":"https://doi.org/10.1039/d4ob00812j","url":null,"abstract":"<p><p>We present the PIFA-mediated intramolecular <i>N</i>-arylation of 2-aminoquinoxalines at room temperature for the first time. This method provides a wide range of indolo[2,3-<i>b</i>]quinoxalines in good to excellent yields within a short time. The C-H bond functionalization occurs without the need for an inert atmosphere or additives. Additionally, a double C-H bond functionalization was observed, where the first reaction forms a C-N bond (<i>N</i>-arylation) and the second forms a C-O bond, yielding an acetal-functionalized product. Mechanistic investigations suggest that the C-H bond functionalization proceeds through an ionic mechanism, whereas acetal functionalization follows a radical pathway. This method extends to the derivation of indoloquinoxalines, including the target compound BIQMCz.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A practical and efficient synthesis of the C8-C23 fragment of antarlides A-H, incorporating six stereocenters and a conjugated diene, is reported. A strategic combination of synthetic methods, including CBS reduction, Evans' aldol reaction, Keck-Maruoka allylation, and enzymatic resolution, enabled the selective introduction of these stereocenters. Furthermore, the pivotal coupling of key fragments is successfully executed through a Julia-Kocienski olefination reaction, connecting the C8-C14 and C15-C23 subunits.
{"title":"Stereo flexible synthesis of the C8-C23 fragment of antarlides, androgen receptor antagonists.","authors":"Palash Ghosh, Pralay Das, Prathama S Mainkar, Thenkrishnan Kumaraguru, Rudrakshula Madhavachary, Srivari Chandrasekhar","doi":"10.1039/d4ob00852a","DOIUrl":"https://doi.org/10.1039/d4ob00852a","url":null,"abstract":"<p><p>A practical and efficient synthesis of the C8-C23 fragment of antarlides A-H, incorporating six stereocenters and a conjugated diene, is reported. A strategic combination of synthetic methods, including CBS reduction, Evans' aldol reaction, Keck-Maruoka allylation, and enzymatic resolution, enabled the selective introduction of these stereocenters. Furthermore, the pivotal coupling of key fragments is successfully executed through a Julia-Kocienski olefination reaction, connecting the C8-C14 and C15-C23 subunits.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel biomass-derived glucose-mediated one-pot multicomponent nitro-reductive cyclization method is presented for the direct synthesis of diverse pyrrole-fused heterocycles. The process involves two-component reactions of alkyl (NH)-pyrrole-2-carboxylates and 2-fluoronitroarenes, yielding pyrrolo[1,2-a]quinoxalin-4(5H)-ones, as well as three-component reactions utilizing (NH)-pyrroles, nitroarenes, and DMSO as carbon sources, resulting in various pyrrolo[1,2-a]quinoxaline derivatives. High yields were achieved with broad substrate scope and gram-scale synthesis capability, including pharmaceuticals featuring pyrroloquinoxaline scaffolds. The method's key innovation lies in enabling three or four reactions in a single-pot setup, previously unexplored in pyrrole chemistry. The simplicity of nitro group reduction by biomass-derived glucose ensures practical safety during scale-up, while mechanistic insights from control experiments reveal a new paradigm in pyrrole chemistry. The tandem process demonstrates low PMI values and high step and atom economies, aligning well with green chemistry principles.
{"title":"Modular synthesis of pyrrole-fused heterocycles <i>via</i> glucose-mediated nitro-reductive cyclization.","authors":"Surabhi Panday, Amitava Hazra, Pankaj Gupta, Srimanta Manna, Joydev K Laha","doi":"10.1039/d4ob00741g","DOIUrl":"https://doi.org/10.1039/d4ob00741g","url":null,"abstract":"<p><p>A novel biomass-derived glucose-mediated one-pot multicomponent nitro-reductive cyclization method is presented for the direct synthesis of diverse pyrrole-fused heterocycles. The process involves two-component reactions of alkyl (NH)-pyrrole-2-carboxylates and 2-fluoronitroarenes, yielding pyrrolo[1,2-<i>a</i>]quinoxalin-4(5<i>H</i>)-ones, as well as three-component reactions utilizing (NH)-pyrroles, nitroarenes, and DMSO as carbon sources, resulting in various pyrrolo[1,2-<i>a</i>]quinoxaline derivatives. High yields were achieved with broad substrate scope and gram-scale synthesis capability, including pharmaceuticals featuring pyrroloquinoxaline scaffolds. The method's key innovation lies in enabling three or four reactions in a single-pot setup, previously unexplored in pyrrole chemistry. The simplicity of nitro group reduction by biomass-derived glucose ensures practical safety during scale-up, while mechanistic insights from control experiments reveal a new paradigm in pyrrole chemistry. The tandem process demonstrates low PMI values and high step and atom economies, aligning well with green chemistry principles.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aspergillus fumigatus is a saprophytic fungus and opportunistic pathogen often causing fatal infections in immunocompromised patients. Recently AfKDNAse, an exoglycosidase hydrolyzing 3-deoxy-D-galacto-D-glycero-nonulosonic acid (KDN), a rare sugar from the sialic acid family, was identified and characterized. The principal function of AfKDNAse is still unclear, but a study suggests a critical role in fungal cell wall morphology and virulence. Potent AfKDNAse inhibitors are required to better probe the enzyme's biological role and as potential antivirulence factors. In this work, we developed a set of AfKDNAse inhibitors based on enzymatically stable thio-KDN motifs. C2, C9-linked heterodi-KDN were designed to fit into unusually close KDN sugar binding pockets in the protein. A polymeric compound with an average of 54 KDN motifs was also designed by click chemistry. Inhibitory assays performed on recombinant AfKDNAse showed a moderate and strong enzymatic inhibition for the two classes of compounds, respectively. The poly-KDN showed more than a nine hundred fold improved inhibitory activity (IC50 = 1.52 ± 0.37 μM, 17-fold in a KDN molar basis) compared to a monovalent KDN reference, and is to our knowledge, the best synthetic inhibitor described for a KDNase. Multivalency appears to be a relevant strategy for the design of potent KDNase inhibitors. Importantly, poly-KDN was shown to strongly decrease filamentation when co-cultured with A. fumigatus at micromolar concentrations, opening interesting perspectives in the development of antivirulence factors.
{"title":"Multivalent inhibition of the <i>Aspergillus</i> fumigatus KDNase.","authors":"Mathieu Scalabrini, Denis Loquet, Camille Rochard, Mélyne Baudin Marie, Coralie Assailly, Yoan Brissonnet, Franck Daligault, Amélie Saumonneau, Annie Lambert, Cyrille Grandjean, David Deniaud, Paul Lottin, Sagrario Pascual, Laurent Fontaine, Viviane Balloy, Sébastien G Gouin","doi":"10.1039/d4ob00601a","DOIUrl":"https://doi.org/10.1039/d4ob00601a","url":null,"abstract":"<p><p><i>Aspergillus fumigatus</i> is a saprophytic fungus and opportunistic pathogen often causing fatal infections in immunocompromised patients. Recently <i>Af</i>KDNAse, an exoglycosidase hydrolyzing 3-deoxy-D-galacto-D-<i>glycero</i>-nonulosonic acid (KDN), a rare sugar from the sialic acid family, was identified and characterized. The principal function of <i>Af</i>KDNAse is still unclear, but a study suggests a critical role in fungal cell wall morphology and virulence. Potent <i>Af</i>KDNAse inhibitors are required to better probe the enzyme's biological role and as potential antivirulence factors. In this work, we developed a set of <i>Af</i>KDNAse inhibitors based on enzymatically stable thio-KDN motifs. C2, C9-linked heterodi-KDN were designed to fit into unusually close KDN sugar binding pockets in the protein. A polymeric compound with an average of 54 KDN motifs was also designed by click chemistry. Inhibitory assays performed on recombinant <i>Af</i>KDNAse showed a moderate and strong enzymatic inhibition for the two classes of compounds, respectively. The poly-KDN showed more than a nine hundred fold improved inhibitory activity (IC<sub>50</sub> = 1.52 ± 0.37 μM, 17-fold in a KDN molar basis) compared to a monovalent KDN reference, and is to our knowledge, the best synthetic inhibitor described for a KDNase. Multivalency appears to be a relevant strategy for the design of potent KDNase inhibitors. Importantly, poly-KDN was shown to strongly decrease filamentation when co-cultured with <i>A. fumigatus</i> at micromolar concentrations, opening interesting perspectives in the development of antivirulence factors.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuanyuan Jiang, Shichao Duan, Jiaming Li, Yanli Zhao, Jinsong Yang
Sialyl Lewisa (sLea), also known as cancer antigen 19-9, is a tumor-associated carbohydrate antigen. In this article, chemical and chemoenzymatic syntheses of a tetrasaccharide glycan 1 structurally derived from sLea are reported. Challenges involved in the chemical synthesis include the highly stereoselective construction of 1,2-cis-α-L-fucoside and α-D-sialoside, as well as the assembly of the 3,4-disubstituted N-acetylglucosamine subunit. Perbenzylated thiofucoside and N-acetyl-5-N,4-O-oxazolidinone protected sialic acid thioglycoside were employed as glycosyl donors, respectively, for the efficient preparation of the desired α-fucoside and α-sialoside. The 3,4-branched glucosamine backbone was established through a 3-O and then 4-O glycosylation sequence in which the 3-hydroxyl group of the glucosamine moiety was glycosylated first and then the 4-hydroxyl. A facile chemoenzymatic approach was also exploited to synthesize the target molecule. The chemically obtained free disaccharide 30 was sequentially sialylated and fucosylated in an enzyme-catalyzed regio- and stereospecific manner to form 1 in high yields. The linker appended 1 can be covalently attached to a carrier protein for further immunological studies.
{"title":"Chemical and chemoenzymatic syntheses of sialyl Lewis<sup>a</sup> tetrasaccharide antigen.","authors":"Yuanyuan Jiang, Shichao Duan, Jiaming Li, Yanli Zhao, Jinsong Yang","doi":"10.1039/d4ob00809j","DOIUrl":"https://doi.org/10.1039/d4ob00809j","url":null,"abstract":"<p><p>Sialyl Lewis<sup>a</sup> (sLe<sup>a</sup>), also known as cancer antigen 19-9, is a tumor-associated carbohydrate antigen. In this article, chemical and chemoenzymatic syntheses of a tetrasaccharide glycan 1 structurally derived from sLe<sup>a</sup> are reported. Challenges involved in the chemical synthesis include the highly stereoselective construction of 1,2-<i>cis</i>-α-L-fucoside and α-D-sialoside, as well as the assembly of the 3,4-disubstituted <i>N</i>-acetylglucosamine subunit. Perbenzylated thiofucoside and <i>N</i>-acetyl-5-<i>N</i>,4-<i>O</i>-oxazolidinone protected sialic acid thioglycoside were employed as glycosyl donors, respectively, for the efficient preparation of the desired α-fucoside and α-sialoside. The 3,4-branched glucosamine backbone was established through a 3-<i>O</i> and then 4-<i>O</i> glycosylation sequence in which the 3-hydroxyl group of the glucosamine moiety was glycosylated first and then the 4-hydroxyl. A facile chemoenzymatic approach was also exploited to synthesize the target molecule. The chemically obtained free disaccharide 30 was sequentially sialylated and fucosylated in an enzyme-catalyzed regio- and stereospecific manner to form 1 in high yields. The linker appended 1 can be covalently attached to a carrier protein for further immunological studies.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report herein a synthetically useful catalytic system for aliphatic C-H oxidation with a mononuclear nonheme cobalt(II) complex and m-chloroperbenzoic acid (m-CPBA). Preliminary mechanistic studies suggest that a high-valent cobalt-oxygen species (e.g., cobalt(IV)-oxo or cobalt(III)-oxyl) is the oxidant that effects C-H oxidation via a rate-determining hydrogen atom abstraction (HAA) step.
{"title":"A synthetically useful catalytic system for aliphatic C-H oxidation with a nonheme cobalt complex and <i>m</i>-CPBA.","authors":"Xiang Wen, Yidong Ma, Jie Chen, Bin Wang","doi":"10.1039/d4ob00807c","DOIUrl":"https://doi.org/10.1039/d4ob00807c","url":null,"abstract":"<p><p>We report herein a synthetically useful catalytic system for aliphatic C-H oxidation with a mononuclear nonheme cobalt(II) complex and <i>m</i>-chloroperbenzoic acid (<i>m</i>-CPBA). Preliminary mechanistic studies suggest that a high-valent cobalt-oxygen species (<i>e.g.</i>, cobalt(IV)-oxo or cobalt(III)-oxyl) is the oxidant that effects C-H oxidation <i>via</i> a rate-determining hydrogen atom abstraction (HAA) step.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhiyong Yin, Michael Maczka, Gregor Schnakenburg, Stefan Schulz, Jeroen S Dickschat
Synthetic routes to geosmin and its enantiomer are well established, but the enantioselective synthesis of stereoisomers of geosmin is unknown. Here a stereoselective synthesis of all stereoisomers of geosmin is reported, yielding all compounds in high enantiomeric purity. Furthermore, the stereoselective synthesis of a geosmin derivative isolated from a mangrove associated streptomycete was performed, establishing the absolute configuration of the natural product. Finally, a new side product of the geosmin synthase from Streptomyces ambofaciens was isolated and its structure was elucidated by NMR spectroscopy. The absolute configuration of this new compound was determined through a stereoselective synthesis.
{"title":"Enantioselective synthesis of all stereoisomers of geosmin and of biosynthetically related natural products.","authors":"Zhiyong Yin, Michael Maczka, Gregor Schnakenburg, Stefan Schulz, Jeroen S Dickschat","doi":"10.1039/d4ob00934g","DOIUrl":"https://doi.org/10.1039/d4ob00934g","url":null,"abstract":"<p><p>Synthetic routes to geosmin and its enantiomer are well established, but the enantioselective synthesis of stereoisomers of geosmin is unknown. Here a stereoselective synthesis of all stereoisomers of geosmin is reported, yielding all compounds in high enantiomeric purity. Furthermore, the stereoselective synthesis of a geosmin derivative isolated from a mangrove associated streptomycete was performed, establishing the absolute configuration of the natural product. Finally, a new side product of the geosmin synthase from <i>Streptomyces ambofaciens</i> was isolated and its structure was elucidated by NMR spectroscopy. The absolute configuration of this new compound was determined through a stereoselective synthesis.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jay Prakash Maurya, Subham S Swain, S S V Ramasastry
We describe the first phosphine-promoted intramolecular Rauhut-Currier reaction that triggers an intramolecular Wittig process assembling new classes of diquinanes. The one-pot strategy provides ready access to simple diquinanes and various (hetero)arene-fused diquinanes incorporated with up to two contiguous all-carbon quaternary centers under metal-free and neutral conditions. We showcased the generality of the method on a broad range of substrates and demonstrated its synthetic utility in accessing various advanced intermediates relevant to natural product synthesis and material science.
{"title":"Phosphine-promoted intramolecular Rauhut-Currier/Wittig reaction cascade to access (hetero)arene-fused diquinanes.","authors":"Jay Prakash Maurya, Subham S Swain, S S V Ramasastry","doi":"10.1039/d4ob00984c","DOIUrl":"https://doi.org/10.1039/d4ob00984c","url":null,"abstract":"<p><p>We describe the first phosphine-promoted intramolecular Rauhut-Currier reaction that triggers an intramolecular Wittig process assembling new classes of diquinanes. The one-pot strategy provides ready access to simple diquinanes and various (hetero)arene-fused diquinanes incorporated with up to two contiguous all-carbon quaternary centers under metal-free and neutral conditions. We showcased the generality of the method on a broad range of substrates and demonstrated its synthetic utility in accessing various advanced intermediates relevant to natural product synthesis and material science.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}