Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1081
Takuya Hashimoto
Carbon-nitrogen bond formation with ammonia or its equivalent has been a major research field in organic chemistry since the discovery of Wöhler’s urea synthesis. Given the versatility of nitrogen-doped organic molecules in natural products, pharmaceuticals, agrochemicals and materials, many such transformations have been conceived during the last 200 years. While the focus has shifted more and more to developing new catalysts rather than reagents to achieve this goal, over the last couple of years we have been intrigued by the possibility of inventing new ammonia equivalents which suit modern catalytic synthesis. We review herein our recent study triggered by this renewed interest in reagent design, which has led to the discovery and application of N-(fluorosulfonyl)carbamates as a new class of aminating reagents.
{"title":"Nitrogen Functionalization with <i>N</i>-(Fluorosulfonyl)carbamates","authors":"Takuya Hashimoto","doi":"10.5059/yukigoseikyokaishi.81.1081","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1081","url":null,"abstract":"Carbon-nitrogen bond formation with ammonia or its equivalent has been a major research field in organic chemistry since the discovery of Wöhler’s urea synthesis. Given the versatility of nitrogen-doped organic molecules in natural products, pharmaceuticals, agrochemicals and materials, many such transformations have been conceived during the last 200 years. While the focus has shifted more and more to developing new catalysts rather than reagents to achieve this goal, over the last couple of years we have been intrigued by the possibility of inventing new ammonia equivalents which suit modern catalytic synthesis. We review herein our recent study triggered by this renewed interest in reagent design, which has led to the discovery and application of N-(fluorosulfonyl)carbamates as a new class of aminating reagents.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565175","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1089
Masayoshi Higuchi
This paper introduces our recent research on metallo-supramolecular polymers (MSPs) and the electrochromic (EC) device fabrication, including (1) control of metal sequence in one-dimensional (1D) MSPs, (2) design of two-dimensional (2D) MSPs, (3) three-dimensional (3D) hyperbranched MSPs, (4) EC devices (ECDs) with MSPs and (5) our trial for ECD applications. MSPs are a kind of coordination polymers and obtained by complexation of metal ions with multitopic organic ligands. MSPs show EC properties in the film state, activated by the electrochemical redox of the metal ions. The EC changes are caused by the reversible appearance and disappearance of the metal-to-ligand charge transfer (MLCT) absorption in the metal complex moieties of MSPs. ECDs with MSPs have great potential for the future’s smart window applications and spreading.
{"title":"Recent Progress on Metallo-Supramolecular Polymers and the Electrochromic Devices Fabrication","authors":"Masayoshi Higuchi","doi":"10.5059/yukigoseikyokaishi.81.1089","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1089","url":null,"abstract":"This paper introduces our recent research on metallo-supramolecular polymers (MSPs) and the electrochromic (EC) device fabrication, including (1) control of metal sequence in one-dimensional (1D) MSPs, (2) design of two-dimensional (2D) MSPs, (3) three-dimensional (3D) hyperbranched MSPs, (4) EC devices (ECDs) with MSPs and (5) our trial for ECD applications. MSPs are a kind of coordination polymers and obtained by complexation of metal ions with multitopic organic ligands. MSPs show EC properties in the film state, activated by the electrochemical redox of the metal ions. The EC changes are caused by the reversible appearance and disappearance of the metal-to-ligand charge transfer (MLCT) absorption in the metal complex moieties of MSPs. ECDs with MSPs have great potential for the future’s smart window applications and spreading.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565171","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1096
Keiichi Hirano, Masanobu Uchiyama
In recent years, the use of various elements has been attracting large attention in drug discovery and materials science. Particularly, organoborons and organosilicons are promising candidates owing to their high stability and relatively low toxicity. However, there are still limitations in the available chemical structures and hence development of novel skeletal-constructing methods is an urgent task in synthetic chemistry. Based on precise designs of boron and silicon ate complexes through an integration of theoretical and experimental chemistry, we have developed novel boration and silylation reactions.
{"title":"Synthetic Element Chemistry based on Precise Designs of Reagents and Transition States","authors":"Keiichi Hirano, Masanobu Uchiyama","doi":"10.5059/yukigoseikyokaishi.81.1096","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1096","url":null,"abstract":"In recent years, the use of various elements has been attracting large attention in drug discovery and materials science. Particularly, organoborons and organosilicons are promising candidates owing to their high stability and relatively low toxicity. However, there are still limitations in the available chemical structures and hence development of novel skeletal-constructing methods is an urgent task in synthetic chemistry. Based on precise designs of boron and silicon ate complexes through an integration of theoretical and experimental chemistry, we have developed novel boration and silylation reactions.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135564309","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1028
Goh Sennari, Richmond Sarpong
Carbon-hydrogen (C-H) bonds are ubiquitous in complex natural products. Over the past three decades, many methods to convert C-H bonds distal from functional groups, which were generally considered inert, have been developed. These advances now enable selective peripheral functionalizations at a late-stage. The direct engagement of traditionally unreactive C-H bonds in reactions expands chemical space by reducing functional group interconversions. As such, C-H functionalization serves as a powerful tool in medicinal and agrocultural chemistry as well as in the total synthesis of natural products where diversification to a broad array of compounds from a common intermediate is often desired. In this Account, we detail the thought processes and design principles that relied on emerging methods for C-H functionalization to prepare a wide range of bridged, polycyclic, natural products in the cephalotane and longibornane families from a common intermediate in each case.
{"title":"Use of Emerging C-H Functionalization Methods to Implement Strategies for the Divergent Total Syntheses of Bridged Polycyclic Natural Products","authors":"Goh Sennari, Richmond Sarpong","doi":"10.5059/yukigoseikyokaishi.81.1028","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1028","url":null,"abstract":"Carbon-hydrogen (C-H) bonds are ubiquitous in complex natural products. Over the past three decades, many methods to convert C-H bonds distal from functional groups, which were generally considered inert, have been developed. These advances now enable selective peripheral functionalizations at a late-stage. The direct engagement of traditionally unreactive C-H bonds in reactions expands chemical space by reducing functional group interconversions. As such, C-H functionalization serves as a powerful tool in medicinal and agrocultural chemistry as well as in the total synthesis of natural products where diversification to a broad array of compounds from a common intermediate is often desired. In this Account, we detail the thought processes and design principles that relied on emerging methods for C-H functionalization to prepare a wide range of bridged, polycyclic, natural products in the cephalotane and longibornane families from a common intermediate in each case.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565160","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1062
Tienan Jin, Masahiro Terada
The impressive structural diversity of polycyclic arenes (PCAs) comprised of pentagon, hexagon, heptagon, and octagon rings has continued to drum up interest in the fields of synthetic chemistry and materials science owing to their tunable electronic properties in relation to their unique planar, twisted, and curved π-surface conformations. Although an array of synthetic strategies have been developed to construct both known and new PCA scaffolds in the past decades, flexible and expedient strategies for creating PCAs with differently sized rings embedded are rare. We describe herein our recent studies on the tandem oxidative ring expansion (TORE) strategy for the construction of structurally diverse PCAs involving intra- and intermolecular TORE reactions for hexagon-embedded PCAs, and intramolecular TORE reactions for O- or S-incorporated heptagon-embedded PCAs and octagon-embedded PCAs.
{"title":"Synthesis of Structurally Diverse Polycyclic Arenes Using Tandem Oxidative Ring Expansion Strategy","authors":"Tienan Jin, Masahiro Terada","doi":"10.5059/yukigoseikyokaishi.81.1062","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1062","url":null,"abstract":"The impressive structural diversity of polycyclic arenes (PCAs) comprised of pentagon, hexagon, heptagon, and octagon rings has continued to drum up interest in the fields of synthetic chemistry and materials science owing to their tunable electronic properties in relation to their unique planar, twisted, and curved π-surface conformations. Although an array of synthetic strategies have been developed to construct both known and new PCA scaffolds in the past decades, flexible and expedient strategies for creating PCAs with differently sized rings embedded are rare. We describe herein our recent studies on the tandem oxidative ring expansion (TORE) strategy for the construction of structurally diverse PCAs involving intra- and intermolecular TORE reactions for hexagon-embedded PCAs, and intramolecular TORE reactions for O- or S-incorporated heptagon-embedded PCAs and octagon-embedded PCAs.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565164","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1040
Osamu Ogata, Wataru Kuriyama
Development and applications of the Ru-MACHO family of ruthenium complexes are described. The parent Ru-MACHO was originally developed for catalytic reduction of esters by molecular hydrogen, which not only provides an environmentally benign and safe protocol, but also achieves a wide range of substrate scope. The reaction with methyl lactate was demonstrated on an industrial scale, producing 2,200 kg of 1,2-propanediol with high optical purity. In addition to hydrogenation of esters, the Ru-MACHO family catalyzes a variety of reactions, including hydrogenation of nitriles and sugars, dehydrogenation of alcohols, N-monomethylation of aromatic amines, and formal deoxygenative hydrogenation of lactams.
{"title":"Development of Homogeneous PNP-Ruthenium Complexes (Ru-MACHO Family) for Hydrogenation of Esters and Beyond","authors":"Osamu Ogata, Wataru Kuriyama","doi":"10.5059/yukigoseikyokaishi.81.1040","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1040","url":null,"abstract":"Development and applications of the Ru-MACHO family of ruthenium complexes are described. The parent Ru-MACHO was originally developed for catalytic reduction of esters by molecular hydrogen, which not only provides an environmentally benign and safe protocol, but also achieves a wide range of substrate scope. The reaction with methyl lactate was demonstrated on an industrial scale, producing 2,200 kg of 1,2-propanediol with high optical purity. In addition to hydrogenation of esters, the Ru-MACHO family catalyzes a variety of reactions, including hydrogenation of nitriles and sugars, dehydrogenation of alcohols, N-monomethylation of aromatic amines, and formal deoxygenative hydrogenation of lactams.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565176","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1020
Yu Kawamata, Phil S. Baran
Electrosynthesis, driven by renewable energy, is a powerful method for accessing useful chemical reactivity in a sustainable fashion. Typically, electrochemical reactions have been carried out using direct current (DC), where electrons flow in a single direction. In contrast, utilization of alternating current (AC) has been largely unexplored in synthetic electrochemistry despite its wide applications in our daily life. This could stem from a historical perception regarding the lack of unique reactivity/selectivity that would result from using such a waveform, as well as the absence of readily available instrumentation to remove the engineering barrier for mass adoption. A breakthrough in this area is the introduction of rapid alternating polarity (rAP), which alternates the polarity of an electrode in the millisecond timescale. This mode of current delivery, now implemented in the widely employed potentiostat, ElectraSyn2.0, enables access to unique reactivity and selectivity in organic synthesis that are challenging or currently impossible to achieve by any known method (chemical or electrochemical). The remarkable chemoselectivity and simplicity of rAP open new vistas in modern synthetic electrochemistry.
{"title":"Rapid Alternating Polarity as a Unique Tool for Synthetic Electrochemistry","authors":"Yu Kawamata, Phil S. Baran","doi":"10.5059/yukigoseikyokaishi.81.1020","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1020","url":null,"abstract":"Electrosynthesis, driven by renewable energy, is a powerful method for accessing useful chemical reactivity in a sustainable fashion. Typically, electrochemical reactions have been carried out using direct current (DC), where electrons flow in a single direction. In contrast, utilization of alternating current (AC) has been largely unexplored in synthetic electrochemistry despite its wide applications in our daily life. This could stem from a historical perception regarding the lack of unique reactivity/selectivity that would result from using such a waveform, as well as the absence of readily available instrumentation to remove the engineering barrier for mass adoption. A breakthrough in this area is the introduction of rapid alternating polarity (rAP), which alternates the polarity of an electrode in the millisecond timescale. This mode of current delivery, now implemented in the widely employed potentiostat, ElectraSyn2.0, enables access to unique reactivity and selectivity in organic synthesis that are challenging or currently impossible to achieve by any known method (chemical or electrochemical). The remarkable chemoselectivity and simplicity of rAP open new vistas in modern synthetic electrochemistry.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565161","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1050
Yota Sakakibara, Kenichiro Itami, Kei Murakami
Carboxylic acids are one of the most important functional groups found in various feedstocks. Their significance lies in their pivotal role as key intermediates in selective transformations during organic synthesis. Despite the existence of various decarboxylative transformation reactions such as Kolbe dimerization, these methods still exhibit certain limitations that present opportunities for further improvement. In this account, we present our recent studies on the application of photocatalytic decarboxylative transformation that allows the divergent transformation of carboxylic acids.
{"title":"Divergent Transformation of Carboxylic Acids through Photocatalytic Decarboxylation with Hypervalent Iodine Reagents","authors":"Yota Sakakibara, Kenichiro Itami, Kei Murakami","doi":"10.5059/yukigoseikyokaishi.81.1050","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1050","url":null,"abstract":"Carboxylic acids are one of the most important functional groups found in various feedstocks. Their significance lies in their pivotal role as key intermediates in selective transformations during organic synthesis. Despite the existence of various decarboxylative transformation reactions such as Kolbe dimerization, these methods still exhibit certain limitations that present opportunities for further improvement. In this account, we present our recent studies on the application of photocatalytic decarboxylative transformation that allows the divergent transformation of carboxylic acids.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565167","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1103
Ayami Matsushima
Bisphenol A (BPA) is a component used in the manufacture of polycarbonate plastics and epoxy resins around the world; however, it is also well-known as one of the most notorious endocrine-disrupting chemicals. To avoid using BPA as an ingredient, various BPA derivatives and related compounds have been synthesized and the use of these for making polymers has grown significantly; however, the safety of these BPA derivatives, also known as next-generation bisphenols, has not been fully evaluated. We hypothesized that the bisphenol moiety is a privileged structure for binding to nuclear receptors. Here, we summarize the binding ability of next-generation bisphenols to estrogen receptors and show that halogen-containing bisphenols act as coactivator binding inhibitors for estrogen receptor β.
{"title":"Novel Estrogen Receptor Inhibitory Mechanism for Halogen-containing Endocrine-disrupting Chemicals Discovered by Computer Simulation","authors":"Ayami Matsushima","doi":"10.5059/yukigoseikyokaishi.81.1103","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1103","url":null,"abstract":"Bisphenol A (BPA) is a component used in the manufacture of polycarbonate plastics and epoxy resins around the world; however, it is also well-known as one of the most notorious endocrine-disrupting chemicals. To avoid using BPA as an ingredient, various BPA derivatives and related compounds have been synthesized and the use of these for making polymers has grown significantly; however, the safety of these BPA derivatives, also known as next-generation bisphenols, has not been fully evaluated. We hypothesized that the bisphenol moiety is a privileged structure for binding to nuclear receptors. Here, we summarize the binding ability of next-generation bisphenols to estrogen receptors and show that halogen-containing bisphenols act as coactivator binding inhibitors for estrogen receptor β.","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565172","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}
Pub Date : 2023-11-01DOI: 10.5059/yukigoseikyokaishi.81.1019
Benjamin List
{"title":"Enthusiasm, Guiding the Way to Universal Catalysts?","authors":"Benjamin List","doi":"10.5059/yukigoseikyokaishi.81.1019","DOIUrl":"https://doi.org/10.5059/yukigoseikyokaishi.81.1019","url":null,"abstract":"","PeriodicalId":17123,"journal":{"name":"Journal of Synthetic Organic Chemistry Japan","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135565174","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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