{"title":"Proton-Conductive Crystals Based on Polyoxometalates","authors":"S. Uchida","doi":"10.4019/bjscc.79.106","DOIUrl":"https://doi.org/10.4019/bjscc.79.106","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48819457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Magnets for this Millennium Based Upon Coordination Compounds and New Coordination Chemistry","authors":"Joel S A Miller","doi":"10.4019/bjscc.79.38","DOIUrl":"https://doi.org/10.4019/bjscc.79.38","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46156198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biocatalysis has covered an increasingly important role in the synthesis and manufacturing of pharmaceuticals and other high value compounds. In the interest of expanding the range of synthetically useful reactions accessible via biocatalysts, our group has explored the potential and application of engineered myoglobins for 'abiological' carbene transfer catalysis. These transformations provide a direct route for the construction of new carbon-carbon and carbon-heteroatom bonds, including the synthesis of cyclopropane rings, which are key motifs and pharmacophores in many drugs and bioactive natural products. In this award article, we survey the progress made by our group toward the development of myoglobin-based catalysts for asymmetric intermolecular cyclopropanation reactions. The high stereoselectivity exhibited by these biocatalysts in these reactions, combined with their broad substrate scope, scalability, and robustness to high substrate loading and organic co-solvents, contribute to make these systems particularly useful for chemical synthesis and biocatalysis at the preparative scale. Extension of the scope of biocatalytic carbene transfer reactions to include different classes of carbene donor reagents has created new opportunities for the asymmetric synthesis of functionalized cyclopropanes. Furthermore, the integration of myoglobin-catalyzed stereoselective cyclopropanations with chemical diversification of the enzymatic products has furnished attractive chemoenzymatic strategies to access a diverse range of optically active cyclopropane scaffolds of high value for drug discovery, medicinal chemistry, and the synthesis of natural products.
{"title":"Engineered Myoglobin Catalysts for Asymmetric Intermolecular Cyclopropanation Reactions.","authors":"Mary G Siriboe, Rudi Fasan","doi":"10.4019/bjscc.80.4","DOIUrl":"https://doi.org/10.4019/bjscc.80.4","url":null,"abstract":"<p><p>Biocatalysis has covered an increasingly important role in the synthesis and manufacturing of pharmaceuticals and other high value compounds. In the interest of expanding the range of synthetically useful reactions accessible via biocatalysts, our group has explored the potential and application of engineered myoglobins for 'abiological' carbene transfer catalysis. These transformations provide a direct route for the construction of new carbon-carbon and carbon-heteroatom bonds, including the synthesis of cyclopropane rings, which are key motifs and pharmacophores in many drugs and bioactive natural products. In this award article, we survey the progress made by our group toward the development of myoglobin-based catalysts for asymmetric intermolecular cyclopropanation reactions. The high stereoselectivity exhibited by these biocatalysts in these reactions, combined with their broad substrate scope, scalability, and robustness to high substrate loading and organic co-solvents, contribute to make these systems particularly useful for chemical synthesis and biocatalysis at the preparative scale. Extension of the scope of biocatalytic carbene transfer reactions to include different classes of carbene donor reagents has created new opportunities for the asymmetric synthesis of functionalized cyclopropanes. Furthermore, the integration of myoglobin-catalyzed stereoselective cyclopropanations with chemical diversification of the enzymatic products has furnished attractive chemoenzymatic strategies to access a diverse range of optically active cyclopropane scaffolds of high value for drug discovery, medicinal chemistry, and the synthesis of natural products.</p>","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"80 ","pages":"4-13"},"PeriodicalIF":0.0,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10448740/pdf/nihms-1869406.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10095123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Exploring the Hidden Constraints that Control the Self-Assembly of Nanomolecular Inorganic Clusters","authors":"Leroy Cronin","doi":"10.4019/bjscc.78.11","DOIUrl":"https://doi.org/10.4019/bjscc.78.11","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42766749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Frontier Chemistry on Photofunctional Chromic Metal Complexes","authors":"Masako Kato","doi":"10.4019/bjscc.78.3","DOIUrl":"https://doi.org/10.4019/bjscc.78.3","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43183916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Construction of Highly Reactive Silanimine- and Phosphasilene-coordinated Complexes Composed of Silicon, Group 15 Elements, and Transition Metals","authors":"M. Okazaki","doi":"10.4019/bjscc.78.18","DOIUrl":"https://doi.org/10.4019/bjscc.78.18","url":null,"abstract":"","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47078610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
3 Bull. Jpn. Soc. Coord. Chem. Vol. 77 (2021) Post-Synthetic Coordination Modification of Robust PillaredRod Metal-Azolate Frameworks for Diversified Applications a MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China b School of Biotechnology and Health Science, Wuyi University, Jiangmen 529000, Guangdong, China Pei-Qin Liao and Xiao-Ming Chen*,a,b Received, March 9, 2021; Accepted, April 22, 2021; Published, May 31, 2021
{"title":"Post-Synthetic Coordination Modification of Robust Pillared-Rod Metal-Azolate Frameworks for Diversified Applications","authors":"Liao Pei-Qin, Cheng Xiao-ming","doi":"10.4019/bjscc.77.3","DOIUrl":"https://doi.org/10.4019/bjscc.77.3","url":null,"abstract":"3 Bull. Jpn. Soc. Coord. Chem. Vol. 77 (2021) Post-Synthetic Coordination Modification of Robust PillaredRod Metal-Azolate Frameworks for Diversified Applications a MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China b School of Biotechnology and Health Science, Wuyi University, Jiangmen 529000, Guangdong, China Pei-Qin Liao and Xiao-Ming Chen*,a,b Received, March 9, 2021; Accepted, April 22, 2021; Published, May 31, 2021","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46622584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
controlled mechanisms. In artificial supramolecular system, the recent advances have allowed numerous studies of molecular recognition behaviors and self-assembly processes. While they are generally thermodynamically controlled events, kinetic control of such processes is essential for the development of new supramolecular functional systems. Here we constructed kinetically controlled new supramolecular complexes based coordination chemistry. The guest uptake/release of host-guest system can be precisely controlled by the introduction of replaceable caps into the apertures of the macrocyclic metallohost. The kinetic study also unveiled the mechanism of host-gust binding where the metallohost uptakes the guest cation accompanied by the host reaction. By using a rigid bent ligand in which chelate coordination sites are introduced, we achieved the selective formation of kinetically-stable pentanuclear metallonanobelt by template-directed self-assembly.
{"title":"Development of Kinetically Controlled New Functional Supramolecular Complexes","authors":"Y. Sakata","doi":"10.4019/bjscc.77.26","DOIUrl":"https://doi.org/10.4019/bjscc.77.26","url":null,"abstract":"controlled mechanisms. In artificial supramolecular system, the recent advances have allowed numerous studies of molecular recognition behaviors and self-assembly processes. While they are generally thermodynamically controlled events, kinetic control of such processes is essential for the development of new supramolecular functional systems. Here we constructed kinetically controlled new supramolecular complexes based coordination chemistry. The guest uptake/release of host-guest system can be precisely controlled by the introduction of replaceable caps into the apertures of the macrocyclic metallohost. The kinetic study also unveiled the mechanism of host-gust binding where the metallohost uptakes the guest cation accompanied by the host reaction. By using a rigid bent ligand in which chelate coordination sites are introduced, we achieved the selective formation of kinetically-stable pentanuclear metallonanobelt by template-directed self-assembly.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43012489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrides of s-, p-, dand f-block metals are insoluble solid state materials. Currently, hydrides of highly electropositive metals (electronegativity < ≈ 1.6) such as MgH2, Ca(BH4)2, and LaNi5H6 are being considered as hydrogen storage materials to allow reversible hydrogen uptake and release. Metal hydrides could also become useful as inexpensive and non-toxic precursors for homogeneous catalyst, if they can be dissolved. By introducing ligands such as CO, phosphines, and N-heterocyclic carbenes (NHCs) homogeneous hydride catalyst precursors based on late transition metals such as Wilkinsonʼs catalyst became widely available. When early transition metals were considered, their more electropositive (oxophilic) character and large size required new types of more electron-rich ligands to saturate the low valence electron counts of these metals. Bis(h-cyclopentadienyl) ligand systems tremendously contributed to the rapid development of early transition metal compounds, including Brintzingertype ansa-zirconocene catalysts for stereoselective olefin hydrogenation and poly merization. Generally, when dealing with highly electropositive, large metal centers, the use of chelating ligands is preferred, to suppress intermolecular ligand exchange reactions during catalysis. TACD ligands, derived from the NNNN macrocycle cyclen (1,4,7,10-tetraazacyclododecane or [12]aneN4) were initially developed for group 3 metals as alternatives to the ubiquitous cyclopentadienyl ligand class (Fig. 1). Commercial success of gadolinium(III) complexes containing DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) ligands as MRI contrast agents inspired us to study simpler derivatives such as (Me3TACD)H, the N,N′,N′′ methylated ligand [12]aneN4. 7 Me3TACD acts as an amido triamine supporting ligand (7-electron L3X or 9-electron L4X-type ligand, depending on the presence of p-donation of the amido function). Originally, (Me3TACD)H was conceived as a surrogate for the 5-electron L2X-type cyclopentadienyl ligand to support large metal centers such as lanthanides. The neutral L4-type ligand N,N′,N′′,N′′′ methylated cyclen Me4TACD (Me4[12]aneN4) is similar to the crown ether 12-crown-4 but acts as a more kinetically inert ancillary ligand for metal ions with different size of the s-, p-, d-, and f-block.
{"title":"Macrocyclic Ligands for Molecular Hydrides of s-Block Metals","authors":"Priyabrata Ghana, J. Okuda","doi":"10.4019/bjscc.77.37","DOIUrl":"https://doi.org/10.4019/bjscc.77.37","url":null,"abstract":"Hydrides of s-, p-, dand f-block metals are insoluble solid state materials. Currently, hydrides of highly electropositive metals (electronegativity < ≈ 1.6) such as MgH2, Ca(BH4)2, and LaNi5H6 are being considered as hydrogen storage materials to allow reversible hydrogen uptake and release. Metal hydrides could also become useful as inexpensive and non-toxic precursors for homogeneous catalyst, if they can be dissolved. By introducing ligands such as CO, phosphines, and N-heterocyclic carbenes (NHCs) homogeneous hydride catalyst precursors based on late transition metals such as Wilkinsonʼs catalyst became widely available. When early transition metals were considered, their more electropositive (oxophilic) character and large size required new types of more electron-rich ligands to saturate the low valence electron counts of these metals. Bis(h-cyclopentadienyl) ligand systems tremendously contributed to the rapid development of early transition metal compounds, including Brintzingertype ansa-zirconocene catalysts for stereoselective olefin hydrogenation and poly merization. Generally, when dealing with highly electropositive, large metal centers, the use of chelating ligands is preferred, to suppress intermolecular ligand exchange reactions during catalysis. TACD ligands, derived from the NNNN macrocycle cyclen (1,4,7,10-tetraazacyclododecane or [12]aneN4) were initially developed for group 3 metals as alternatives to the ubiquitous cyclopentadienyl ligand class (Fig. 1). Commercial success of gadolinium(III) complexes containing DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) ligands as MRI contrast agents inspired us to study simpler derivatives such as (Me3TACD)H, the N,N′,N′′ methylated ligand [12]aneN4. 7 Me3TACD acts as an amido triamine supporting ligand (7-electron L3X or 9-electron L4X-type ligand, depending on the presence of p-donation of the amido function). Originally, (Me3TACD)H was conceived as a surrogate for the 5-electron L2X-type cyclopentadienyl ligand to support large metal centers such as lanthanides. The neutral L4-type ligand N,N′,N′′,N′′′ methylated cyclen Me4TACD (Me4[12]aneN4) is similar to the crown ether 12-crown-4 but acts as a more kinetically inert ancillary ligand for metal ions with different size of the s-, p-, d-, and f-block.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41638024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transition-metal-catalyzed C–C bond(s) formations are one of the most fundamental organic transformations, where the design of transition metal catalysts is the key of success. To activate two coupling partners simultaneously, we focused on the combination of a transition metal anion and a typical metal cation. The anionic transition metal center itself or own ligands are nucleophilically activated by the anionic charge, and the Lewis acidic typical metal cation activates the electrophilic counterpart. The synergy of these two metal centers located closely by electrostatic interaction enables cross-coupling and multicomponent coupling reactions. For instance, Co–Mg–Li system catalyzed cross-coupling reaction of alkyl halides with tertiary alkyl Grignard reagents to construct quaternary carbon center. The cross-coupling reaction of alkenyl ethers with aryl Grignard reagents via C– O bond cleavage could be achieved with Rh-Mg and Rh-Li combinations. The key catalytic active species containing Rh anion and Li cation was successfully isolated and characterized by X-ray crystallography to clarify a unique structure and reactivity of the Rh-Li complex. In addition, we successfully connected dimerizative transformation of 1,3-dienes promoted by a neutral Ni complex and a C–C bond formation with carbon electrophiles promoted by an anionic Ni complex in one catalytic cycle. The isolation of and structural insight into the anionic Ni complexes clarified the reaction mechanism and the origin of selectivity between multicomponent coupling reaction and competing cross-coupling reaction.
{"title":"Development of Catalytic Carbon–Carbon Bond Formations Based on Composite Metal Catalysts","authors":"T. Iwasaki","doi":"10.4019/bjscc.77.11","DOIUrl":"https://doi.org/10.4019/bjscc.77.11","url":null,"abstract":"Transition-metal-catalyzed C–C bond(s) formations are one of the most fundamental organic transformations, where the design of transition metal catalysts is the key of success. To activate two coupling partners simultaneously, we focused on the combination of a transition metal anion and a typical metal cation. The anionic transition metal center itself or own ligands are nucleophilically activated by the anionic charge, and the Lewis acidic typical metal cation activates the electrophilic counterpart. The synergy of these two metal centers located closely by electrostatic interaction enables cross-coupling and multicomponent coupling reactions. For instance, Co–Mg–Li system catalyzed cross-coupling reaction of alkyl halides with tertiary alkyl Grignard reagents to construct quaternary carbon center. The cross-coupling reaction of alkenyl ethers with aryl Grignard reagents via C– O bond cleavage could be achieved with Rh-Mg and Rh-Li combinations. The key catalytic active species containing Rh anion and Li cation was successfully isolated and characterized by X-ray crystallography to clarify a unique structure and reactivity of the Rh-Li complex. In addition, we successfully connected dimerizative transformation of 1,3-dienes promoted by a neutral Ni complex and a C–C bond formation with carbon electrophiles promoted by an anionic Ni complex in one catalytic cycle. The isolation of and structural insight into the anionic Ni complexes clarified the reaction mechanism and the origin of selectivity between multicomponent coupling reaction and competing cross-coupling reaction.","PeriodicalId":72479,"journal":{"name":"Bulletin of Japan Society of Coordination Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70514741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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