This account summarizes representative contributions of Prof. Naomichi Furukawa to the field of heteroatom chemistry. Ligand-coupling reactions (LCRs) and ligand-exchange reactions (LERs) of chalcogen derivatives were developed from reactions of trivalent chalcogen species with organometallic reagents. Prof. Furukawa has also reported a large number of mono- and dicationic compounds generated via transannular and intermolecular interactions. Furthermore, the detection and isolation of hypercoordinated chalcogen species bearing only carbon ligands and an efficient method for the synthesis of thiophene S-oxides and their reactivity are described.
{"title":"Studies on diverse chemical species derived from chalcogen atoms ~ The Footprint of Professor Naomichi Furukawa in Heteroatom Chemistry ~","authors":"Soichi Sato","doi":"10.1002/hc.21475","DOIUrl":"10.1002/hc.21475","url":null,"abstract":"<p>This account summarizes representative contributions of Prof. Naomichi Furukawa to the field of heteroatom chemistry. Ligand-coupling reactions (LCRs) and ligand-exchange reactions (LERs) of chalcogen derivatives were developed from reactions of trivalent chalcogen species with organometallic reagents. Prof. Furukawa has also reported a large number of mono- and dicationic compounds generated via transannular and intermolecular interactions. Furthermore, the detection and isolation of hypercoordinated chalcogen species bearing only carbon ligands and an efficient method for the synthesis of thiophene <i>S</i>-oxides and their reactivity are described.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21475","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45632817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
When alkynes were treated with diphenyl diselenide under an atmosphere of nitric oxide and oxygen, nitroselenation of the carbon-carbon triple bond proceeded with a high regioselectivity to give the corresponding 1-nitro-2-phenylseleno alkenes. Similarly, the nitroselenation of alkynes proceeded by the reaction of the alkynes with nitrogen dioxide. The stirring of the 1,2-bis(phenylseleno) alkenes under an atmosphere of nitric oxide and oxygen also gave the corresponding 1-nitro-2-phenylseleno alkenes.
{"title":"Nitroselenation of carbon-carbon triple bond by PhSeSePh and NO/O2 or NO2","authors":"Yutaka Nishiyama, Mari Sumida, Noboru Sonoda","doi":"10.1002/hc.21480","DOIUrl":"10.1002/hc.21480","url":null,"abstract":"<p>When alkynes were treated with diphenyl diselenide under an atmosphere of nitric oxide and oxygen, nitroselenation of the carbon-carbon triple bond proceeded with a high regioselectivity to give the corresponding 1-nitro-2-phenylseleno alkenes. Similarly, the nitroselenation of alkynes proceeded by the reaction of the alkynes with nitrogen dioxide. The stirring of the 1,2-bis(phenylseleno) alkenes under an atmosphere of nitric oxide and oxygen also gave the corresponding 1-nitro-2-phenylseleno alkenes.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21480","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43669785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Christopher A. Dodds, Alan R. Kennedy, Mark D. Spicer
The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (1). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (2) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (3) are also reported. The discrete molecular structures of compounds 1 to 3 are comparable, with Ge-N bond lengths in the range 1.835-1.875 Å, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound 2 was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound 2 versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (1), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (4), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds 1 to 3 were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.
{"title":"N-Heterocyclic Germylenes: Structural Characterisation of Some Heavy Analogues of the Ubiquitous N-Heterocyclic Carbenes","authors":"Christopher A. Dodds, Alan R. Kennedy, Mark D. Spicer","doi":"10.1155/2019/9178371","DOIUrl":"10.1155/2019/9178371","url":null,"abstract":"<div>\u0000 <p>The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (<b>1</b>). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (<b>2</b>) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (<b>3</b>) are also reported. The discrete molecular structures of compounds <b>1</b> to <b>3</b> are comparable, with Ge-N bond lengths in the range 1.835-1.875 Å, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound <b>2</b> was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound <b>2</b> versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (<b>1</b>), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (<b>4</b>), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds <b>1</b> to <b>3</b> were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.</p>\u0000 </div>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"2019 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2019-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1155/2019/9178371","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41887215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bis (ethylenedioxy)-1,4,5,8-tetraselenanaphthalene (BEDO-TSeN) has been synthesized by the reaction of diselenolate with tetraiodoethylene or tetrabromoethylene. The structure of BEDO-TSeN was determined by X-ray analysis, and its π-donor property was estimated by MO calculations and determined by CV analysis.
{"title":"Synthesis and structure of bis(ethylenedioxy)-1,4,5,8-tetraselenanaphthalene","authors":"Ryoji Watanabe, Masashi Hasegawa, Masahiko Iyoda","doi":"10.1002/hc.21479","DOIUrl":"10.1002/hc.21479","url":null,"abstract":"<p>Bis (ethylenedioxy)-1,4,5,8-tetraselenanaphthalene (BEDO-TSeN) has been synthesized by the reaction of diselenolate with tetraiodoethylene or tetrabromoethylene. The structure of BEDO-TSeN was determined by X-ray analysis, and its π-donor property was estimated by MO calculations and determined by CV analysis.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21479","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43013393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ibrahim A. M. Saraireh, Mohammednoor Altarawneh, Jibril Alhawarin, Mansour H. Almatarneh
This contribution sets out to compute thermochemical and geometrical parameters of the complete series of chlorinated isomers of thiophene based on the accurate chemistry model of CBS-QB3. Herein, we compute standard entropies, standard enthalpies of formation, standard Gibbs free energies of formation, and heat capacities. Our calculated enthalpy values agree with available limited experimental values. The DFT-based reactivity descriptors were used to elucidate the site selectivity for the chlorination sequence of thiophene. The relative preference for chlorination was found to be in accord with the thermodynamic stability trends inferred based on the H scale. Calculated Fukui indices predict a chlorination sequence to ensue as follows: 2-chloro → 2,5-dichloro → 2,3,5-trichloro → 2,3,4,5-tetrachlorothiophene.
{"title":"A Thermochemical Parameters and Theoretical Study of the Chlorinated Compounds of Thiophene","authors":"Ibrahim A. M. Saraireh, Mohammednoor Altarawneh, Jibril Alhawarin, Mansour H. Almatarneh","doi":"10.1155/2019/7680264","DOIUrl":"10.1155/2019/7680264","url":null,"abstract":"<div>\u0000 <p>This contribution sets out to compute thermochemical and geometrical parameters of the complete series of chlorinated isomers of thiophene based on the accurate chemistry model of CBS-QB3. Herein, we compute standard entropies, standard enthalpies of formation, standard Gibbs free energies of formation, and heat capacities. Our calculated enthalpy values agree with available limited experimental values. The DFT-based reactivity descriptors were used to elucidate the site selectivity for the chlorination sequence of thiophene. The relative preference for chlorination was found to be in accord with the thermodynamic stability trends inferred based on the H scale. Calculated Fukui indices predict a chlorination sequence to ensue as follows: 2-chloro → 2,5-dichloro → 2,3,5-trichloro → 2,3,4,5-tetrachlorothiophene.</p>\u0000 </div>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"2019 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2019-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1155/2019/7680264","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43547706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A series of novel 9,9-dialkoxy-9-silafluorenes were synthesized, and their structures and reactivity were studied. Dehydrogenative alkoxylation of 9,9-dihydro-9-silafluorene with various alcohols in the presence of PdCl2 gave the corresponding dialkoxylated products in good yields. The structures of some of the novel 9,9-dialkoxy-9-silafluorenes were analyzed by X-ray crystallography. The 9,9-dialkoxy-9-silafluorenes show remarkably high reactivity toward phenylmagnesium bromide to afford substitution products.
{"title":"Synthesis, structures, and reactivity of 9,9-dialkoxy-9-silafluorenes","authors":"Ken-ichiro Kanno, Satoshi Hirose, Soichiro Kyushin","doi":"10.1002/hc.21478","DOIUrl":"10.1002/hc.21478","url":null,"abstract":"<p>A series of novel 9,9-dialkoxy-9-silafluorenes were synthesized, and their structures and reactivity were studied. Dehydrogenative alkoxylation of 9,9-dihydro-9-silafluorene with various alcohols in the presence of PdCl<sub>2</sub> gave the corresponding dialkoxylated products in good yields. The structures of some of the novel 9,9-dialkoxy-9-silafluorenes were analyzed by X-ray crystallography. The 9,9-dialkoxy-9-silafluorenes show remarkably high reactivity toward phenylmagnesium bromide to afford substitution products.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21478","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45015568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was studied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution (SH2) reaction with a phenyl radical generated from phenylhydrazine in the air, to afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthesis, a one-pot synthesis of unsymmetrical diaryl tellurides was developed by the SH2 reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The selectivity of mono-/di-substitution and the reactivity of arylhydrazines depend on the nature of the substituents on the arylhydrazines, that is, electron-donating or -withdrawing group.
{"title":"Reaction of arylhydrazines with diaryl ditellurides in the air: Insight into bimolecular homolytic substitution on tellurium via Aryl–Te bond cleavage","authors":"Yuki Yamamoto, Fumiya Sato, Shintaro Kodama, Akihiro Nomoto, Akiya Ogawa","doi":"10.1002/hc.21471","DOIUrl":"10.1002/hc.21471","url":null,"abstract":"<p>The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was studied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution (S<sub>H</sub>2) reaction with a phenyl radical generated from phenylhydrazine in the air, to afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthesis, a one-pot synthesis of unsymmetrical diaryl tellurides was developed by the S<sub>H</sub>2 reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The selectivity of mono-/di-substitution and the reactivity of arylhydrazines depend on the nature of the substituents on the arylhydrazines, that is, electron-donating or -withdrawing group.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21471","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48864556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We describe, herein, the synthesis, full characterization, and optical properties of four different ligands L1-L4 which associate an azo group, an imidazole unit, and a Schiff base fragment. The UV-visible absorption bands are characteristic of π → π⁎ and n → π⁎ transitions with an additional charge transfer between the azobenzene moiety and the imino group. Finally the determination of MIC80 values against pathogenic fungi such as S. apiospermum, A. fumigatus, and C. albicans revealed that these ligands have effective antifungal properties with highest activities (MIC80) on C. albicans for the azole based ligands L1-L3. DPPH radical scavenging of the studied ligands was also tested.
{"title":"Imidazole and Azo-Based Schiff Bases Ligands as Highly Active Antifungal and Antioxidant Components","authors":"Siham Slassi, Adeline Fix-Tailler, Gérald Larcher, Amina Amine, Abdelkrim El-Ghayoury","doi":"10.1155/2019/6862170","DOIUrl":"10.1155/2019/6862170","url":null,"abstract":"<div>\u0000 <p>We describe, herein, the synthesis, full characterization, and optical properties of four different ligands <b>L1-L4</b> which associate an azo group, an imidazole unit, and a Schiff base fragment. The UV-visible absorption bands are characteristic of <i>π</i> → <i>π</i>⁎ and <i>n</i> → <i>π</i>⁎ transitions with an additional charge transfer between the azobenzene moiety and the imino group. Finally the determination of MIC<sub>80</sub> values against pathogenic fungi such as <i>S. apiospermum</i>, <i>A. fumigatus,</i> and <i>C. albicans</i> revealed that these ligands have effective antifungal properties with highest activities (MIC<sub>80</sub>) on <i>C. albicans</i> for the azole based ligands <b>L1-L3</b>. DPPH radical scavenging of the studied ligands was also tested.</p>\u0000 </div>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"2019 1","pages":""},"PeriodicalIF":1.1,"publicationDate":"2019-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1155/2019/6862170","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44584392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jacek Chrzanowski, Dorota Krasowska, Jozef Drabowicz
The synthetic approaches for the preparation of non-racemic tertiary phosphine oxides with particular attention to the latest advances are discussed in this minireview.
本文综述了非消旋型叔膦氧化物的合成方法，并着重介绍了最新进展。
{"title":"Synthesis of optically active tertiary phosphine oxides: A historical overview and the latest advances","authors":"Jacek Chrzanowski, Dorota Krasowska, Jozef Drabowicz","doi":"10.1002/hc.21476","DOIUrl":"10.1002/hc.21476","url":null,"abstract":"<p>The synthetic approaches for the preparation of non-racemic tertiary phosphine oxides with particular attention to the latest advances are discussed in this minireview.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21476","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46856714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Leixing Chen, Shuai Wang, Patrick Werz, Zeyu Han, Derek P. Gates
We report the attempted synthesis of a “masked” phosphaalkene by treating MgA·3THF (A = anthracenide) with MesPCl(CH2Cl). Although the desired “masked” phosphaalkene could not be isolated, indirect evidence for its formation was obtained. The product of trapping MesP=CH2 with 1,3-cyclohexadiene was detected. In addition, the oxide MesPO(Me)A was isolated and crystallographically characterized from the MgA·3THF and MesPCl(CH2Cl) experiment described above. Finally, the attempted isolation of “masked” phoshaalkene afforded P-containing oligomers with a trimodal molecular weight distribution [Mn = 640, 1.7 × 103 and 7.4 × 103 Da].
{"title":"A “masked” source for the phosphaalkene MesP=CH2: Trapping, rearrangement, and oligomerization","authors":"Leixing Chen, Shuai Wang, Patrick Werz, Zeyu Han, Derek P. Gates","doi":"10.1002/hc.21474","DOIUrl":"10.1002/hc.21474","url":null,"abstract":"<p>We report the attempted synthesis of a “masked” phosphaalkene by treating MgA·3THF (A = anthracenide) with MesPCl(CH<sub>2</sub>Cl). Although the desired “masked” phosphaalkene could not be isolated, indirect evidence for its formation was obtained. The product of trapping MesP=CH<sub>2</sub> with 1,3-cyclohexadiene was detected. In addition, the oxide MesPO(Me)A was isolated and crystallographically characterized from the MgA·3THF and MesPCl(CH<sub>2</sub>Cl) experiment described above. Finally, the attempted isolation of “masked” phoshaalkene afforded P-containing oligomers with a trimodal molecular weight distribution [<i>M</i><sub>n</sub> = 640, 1.7 × 10<sup>3</sup> and 7.4 × 10<sup>3</sup> Da].</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":0.3,"publicationDate":"2019-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21474","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47856357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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