研究者総覧
岩井 健人IWAI Kentoイワイ ケント
| ■所属部署名 | 研究院自然科学系化学領域 | |||
| ■職名 | 助教 | |||
Last Updated :2024/05/17
researchmap
プロフィール情報
姓
岩井, イワイ名
健人, ケント
学位
研究キーワード
研究分野
経歴
- 2024年04月, 9999年, 奈良女子大学, 研究院 自然科学系, 助教
- 2023年04月, 2024年03月, 高知工科大学, 理工学群, 助教, （学群名変更による）
- 2021年04月, 2023年03月, 高知工科大学, 環境理工学群, 助教
- 2020年04月, 2021年03月, 独立行政法人日本学術振興会, 特別研究員（DC2）
学歴
- 2018年04月, 2021年03月, 京都大学, 大学院理学研究科, 化学専攻
- 2016年04月, 2018年03月, 高知工科大学, 大学院工学研究科, 基盤工学専攻
- 2012年04月, 2016年03月, 高知工科大学, 環境理工学群, 化学・生命科学専攻
- 2009年04月, 2012年03月, 高知県立幡多農業高校, 園芸システム科
所属学協会
学術貢献活動
Ⅱ．研究活動実績
論文
- その他, RSC Advances, Highly electron-deficient 1-propyl-3,5-dinitropyridinium: evaluation of electron-accepting ability and application as an oxidative quencher for metal complexes, Akitaka Ito; Yasuyuki Kuroda; Kento Iwai; Soichi Yokoyama; Nagatoshi Nishiwaki, 2024年, 研究論文（学術雑誌）, 10.1039/D4RA00845F
- 英語, Chemistry – An Asian Journal, Cationic Iridium‐Catalyzed Decarboxylation of Aromatic Carboxylic Acids, Reina Nonami; Yu Kishino; Tomokazu Yamasaki; Kazuya Kanemoto; Kento Iwai; Nagatoshi Nishiwaki; Kazutaka Shibatomi; Tomohiko Shirai, Practical synthetic applications of catalytic decarboxylation in producing useful molecules are limited. We report herein the cationic Ir-catalyzed decarboxylations of various electron-rich and -poor aromatic carboxylic acids to produce hydrocarbons in good yield (up to >99%). Additionally, this reaction is applicable in decarboxylative hydroarylation of bicyclic alkenes and decarboxylative fluorination, indicating the potential utility of this catalytic decarboxylation in synthetic chemistry., 2023年09月, 18, 17, e202300533, 研究論文（学術雑誌）, 国際誌, 10.1002/asia.202300533
- その他, European Journal of Inorganic Chemistry, Solid‐state Chromism of Zwitterionic Triarylmethylium Salts, Kento Iwai; Yoshiyuki Mizuhata; Tomoya Nakamura; Masato Goto; Atsushi Wakamiya; Yuichi Shimakawa; Norihiro Tokitoh, Zwitterionic triarylmethylium dyes 1 and 2 were synthesized by using a synthetic unit of a tetraarylborate. The zwitterionic structure of 1 and 2 exhibits varied molecular assembly and induces charge transfer transition. These properties gave them specific optical features such as solvatochromism and mechanochromism in the solid state, that is, the green solid of 2 changes to yellow or red solid by dissolution & evaporation or grinding, respectively. The three colors were reproduced independently in different crystal forms, which were prepared from different recrystallization conditions. The diffuse reflectance measurement and powder X-ray diffraction demonstrated the correlation between the colors and the solid-state structures. The single crystal X-ray analysis revealed face-to-face dimeric assembly in each crystal. Among the crystal structures, the intermolecular distances and packing patterns were notable differences. Based on these results, it can be suggested that unique color change of zwitterionic triarylmethylium dyes originates from the alternation of intermolecular interactions., 2023年07月24日, 研究論文（学術雑誌）, 10.1002/ejic.202300337
- 英語, The Journal of Organic Chemistry, Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups, Kento Iwai; Noa Nishiguchi; Nagatoshi Nishiwaki, The naphthalene ring is distorted due to steric repulsion between iodo groups at the peri-positions. Due to the distortion, 1,8-diiodonaphthalene underwent a halo-Jacobsen rearrangement when treated with trifluoromethanesulfonic acid, producing 1,5-diiodonaphthalene and 1,4-diiodonaphthalene. In this reaction, acid-induced dehalogenative homocoupling also proceeded to form 4,4'-diiodo-1,1'-binaphthyl. The reaction selectivity could be controlled by varying the reaction temperature. DFT calculations and some control experiments revealed that these compounds were formed by different pathways., 2023年07月07日, 88, 13, 9409, 9412, 研究論文（学術雑誌）, 国際誌, 10.1021/acs.joc.3c00165
- その他, Molecules, A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring, Annisa Indah Reza; Kento Iwai; Nagatoshi Nishiwaki, A systematic study on the distortion of a naphthalene ring was performed using steric repulsion between peri-substituents at the 1- and 8-positions. The introduction of bromo groups into the methyl groups of the 1,8-dimethylnaphthalene enhanced the steric repulsion to distort the naphthalene ring. X-ray crystallography revealed that 1,8-bis(bromomethyl)naphthalene had a vertical distortion with a 11.0° dihedral angle (α) between peri-substituents which disturbed the coplanarity of the naphthalene ring. On the other hand, the dihedral angle of 1,8-bis(dibromomethyl)naphthalene was smaller (α = 8.3°) despite the bulkier substituents. In this case, horizontal distortion of the naphthalene ring increased. These distortions should non-electronically activate the naphthalene framework. In order to evaluate their reactivity, nitration and hydrogenation were carried out; however, the 1,8-bis(dibromomethyl)naphthalene was intact under the employed conditions. A DFT calculation suggested that the inertness of the 1,8-bis(dibromomethyl)naphthalene is presumably due to the negative hyperconjugation of the (dibromo)methyl group., 2023年07月, 28, 14, 研究論文（学術雑誌）, 10.3390/molecules28145343
- その他, Journal of Photochemistry and Photobiology, 2-Azafluorenone derivatives: Photocatalyst for oxygenation of toluene via electron transfer and hydrogen-atom transfer, Haruyasu Asahara; Yurie Horikawa; Kento Iwai; Nagatoshi Nishiwaki; Kei Ohkubo, 2-Aza-9-fluorenone derivatives were synthesized and their optical properties were investigated. The UV–visible absrption spectra revealed λmax values in the range of 350–380 nm, with a shift to the longer wavelength when an electron-donating group was substituted on the aryl group at the 3-position adjacent to the nitrogen in the azafluorenone. N-Methyl-2-azafluorenone was synthesized by methylating the nitrogen of azafluorenone. The N-methyl derivative was found to have a maximum absorption at 426 nm from UV-Vis spectral measurements, and electrochemical measurements revealed that it has a lower first reduction potential and higher electron-accepting ability than azafluorenone. In addition, the application of azafluorenone as a photocatalyst was investigated, focusing on its structural and electronic features. Oxidation of toluene with azafluorenone as a photocatalyst yielded benzoic acid in high yield. Electron-transfer dynamics analysis using nanosecond time-resolved laser flash photolysis suggests that azafluorenone and N-methylazafluorenone act as hydrogen transfer and electron transfer catalysts, respectively., 2023年06月, 15, 研究論文（学術雑誌）, 10.1016/j.jpap.2023.100184
- その他, The Journal of Organic Chemistry, Synthesis of Bis(functionalized) Aminals via Successive Nucleophilic Amidation and Amination, Kento Iwai; Akari Hikasa; Kotaro Yoshioka; Shinki Tani; Kazuto Umezu; Nagatoshi Nishiwaki, The central carbonyl group of diethyl mesoxalate (DEMO) exhibits high electrophilicity that allows it to be attacked by versatile nucleophiles. Even a less nucleophilic acid amide serves as a nucleophile to produce N,O-acetal upon treatment with DEMO in the presence of acetic anhydride. When the obtained N,O-acetal was treated with a base, the elimination of acetic acid generated N-acylimine in situ. N-Acylimine is also highly electrophilic, allowing it to accept the second nucleophilic addition by an amine, resulting in α,α-bis(functionalized) aminals. This protocol facilitates the modification of the two different amino groups by altering nucleophiles, resulting in the production of tetra-functionalized methane derivatives on demand. The ring closure between the amide moiety and the amino group was achieved using the structural features to form a six-membered ring., 2023年02月17日, 88, 4, 2207, 2213, 研究論文（学術雑誌）, 10.1021/acs.joc.2c02647
- 英語, Beilstein journal of organic chemistry, First synthesis of acylated nitrocyclopropanes., Kento Iwai; Rikiya Kamidate; Khimiya Wada; Haruyasu Asahara; Nagatoshi Nishiwaki, Although nitrocyclopropanedicarboxylic acid esters are widely used in organic syntheses, nitrocyclopropanes with an acyl group have not yet been synthesized. When adducts of β-nitrostyrene and 1,3-dicarbonyl compounds are treated with (diacetoxyiodo)benzene and tetrabutylammonium iodide, iodination occurs at the α-position of the nitro group, and the subsequent O-attack of the enol moiety leads to 2,3-dihydrofuran. Cyclopropane was successfully synthesized through C-attack as the acyl group became bulkier. The obtained nitrocyclopropane was transformed into furan upon treatment with tin(II) chloride via a ring-opening/ring-closure process., 2023年, 19, 892, 900, 研究論文（学術雑誌）, 国際誌, 10.3762/bjoc.19.67
- その他, ACS Omega, Synthesis of Unsymmetrical Ketones Using Chelation-Controlled Sequential Substitution of N-Triazinylamide/Weinreb Amide by Organometallic Reagents, Shotaro Hirao; Rumi Saeki; Toru Takahashi; Kento Iwai; Nagatoshi Nishiwaki; Yasushi Ohga, N-(2,4-Dimethoxy-1,3,5-triazinyl)amide was found to exhibit similar behavior to N-methoxy-N-methylamide (Weinreb amide) but higher reactivity for nucleophilic substitution by organometallic reagents. Triazinylamide suppresses overaddition, leading to the formation of a tertiary alcohol by the chelating ability of the triazinyl and carbonyl groups. Ureas possessing both triazinylamino and methoxy(methyl)amino groups underwent sequential nucleophilic substitution with different organometallic reagents, which furnished unsymmetrical ketones without any detectable tertiary alcohols., 2022年12月27日, 7, 51, 48476, 48483, 研究論文（学術雑誌）, 10.1021/acsomega.2c06756
- その他, The Chemical Record, Recent Advances in Synthesis of Multiply Arylated/Alkylated Pyridines, Annisa Indah Reza; Kento Iwai; Nagatoshi Nishiwaki, Multiply aryl/alkyl-substituted pyridines are some of the untapped synthetic targets because of the challenge in regioselectively introducing less polar aryl/alkyl groups at the desired positions in the pyridine framework. Interestingly, the importance of this family of compounds has increased annually, particularly in biological and materials engineering applications. The syntheses of such pyridines have been extensively reported, but there is a lack of comprehensive review articles. Hence, this review discusses recent advances by grouping reaction patterns that generally deliver tri-, tetra-, and penta-aryl/alkyl pyridines., 2022年09月, 研究論文（学術雑誌）, 10.1002/tcr.202200099
- その他, Tetrahedron Letters, Efficient synthesis of α-Nitro-β-Dialdimine ligands via Equilibrium–Controlling approach, Mahiro Nakabayashi; Nagatoshi Nishiwaki; Akitaka Ito; Shotaro Hayashi; Kento Iwai, Reactions of β-formyl-β-nitroenamine with anilines afforded N,N’-diaryl-α-nitro-β-dialdimines; however, only small amounts of dialdimines were obtained when anilines possessing an electron-withdrawing group were employed. This disadvantage was overcome by adding anilinium salts to control the equilibrium, which resulted in the formation of dialdimines in considerably improved yields. This method facilitated to introduce less nucleophilic 5-bromopyrid-2-yl groups that are expected to be a precursor for various frameworks. The prepared dialdimines served as a ligand which formed the nickel(II) complex with a distorted tetrahedral structure., 2022年07月20日, 102, 研究論文（学術雑誌）, 10.1016/j.tetlet.2022.153948
- その他, Molecules, Unusual Reactivities of ortho-Hydroxy-β-nitrostyrene, Kento Iwai; Khimiya Wada; Nagatoshi Nishiwaki, Nitrostyrene derivatives are widely used in organic syntheses as a substrate for Michael addition, photoisomerization and cycloaddition. In contrast, ortho-hydroxy derivatives exhibit unusual behaviors in these reactions. Conjugate addition proceeded upon treatment of the ortho-hydroxy-β-nitrostyrene with an amine; however, subsequent C–C bond cleavage readily occurred to afford the corresponding imine. Moreover, conversion of the trans-isomer to a cis-isomer did not occur efficiently, even when UV light was irradiated. We studied these unusual behaviors of β-nitrostyrene, focusing on the role of the ortho-hydroxy group., 2022年07月, 27, 15, 研究論文（学術雑誌）, 10.3390/molecules27154804
- その他, Synthesis, FeCl3-Promoted Facile Synthesis of Multiply Arylated Nicotinonitriles, Kento Iwai; Nagatoshi Nishiwaki; Haruka Yamauchi; Soichi Yokoyama, Many biologically active nicotinonitriles have been reported to date. Consequently, the development of synthetic methods for multiply arylated/alkylated nicotinonitriles remains a sought-after field of research. In the present work, a new synthetic strategy for multi-substituted nicotinonitriles is described. A FeCl3-promoted condensation cyclization reaction of an enamino nitrile and α,β-unsaturated ketones proceeded efficiently with a wide range of substrates. It is noteworthy that this method facilitates access to fully and differently substituted nicotinonitriles, including tetra-arylated nicotinonitriles, in only three steps. Using the functionality of the cyano group, the copper-catalyzed annulation reaction of the nicotinonitrile was achieved to yield benzo[c][2,7]naphthyridin-5(6H)-one., 2022年05月, 54, 10, 2480, 2486, 研究論文（学術雑誌）, 10.1055/a-1731-9464
- その他, Journal of Oleo Science, A Mechanistic Study for Aziridination of Nitroalkenes Mediated by N-Chlorosuccinimide, Kento Iwai; Khimiya Wada; Feiyue Hao; Haruyasu Asahara; Nagatoshi Nishiwaki, Direct aziridination of a nitrostyrene is achieved upon treatment with an alkylamine and N-chlorosuccinimide. The reaction is initiated by the Michael addition of amine to nitroalkene. Subsequent N-chlorination and nucleophilic substitution at the nitrogen atom afford 1-alkyl-2-nitroaziridine diastereoselectively. This reaction mechanism was clarified by NMR studies., 2022年, 71, 6, 897, 903, 研究論文（学術雑誌）, 10.5650/jos.ess21406
- その他, Organic & Biomolecular Chemistry, A new approach to 10-arylated 5H-dibenzo[b,f]azepines using syn-selective hydrohalogenation of ethynylaniline, Kento Iwai; Yusuke Mukaijo; Haruyasu Asahara; Nagatoshi Nishiwaki, A new synthetic method for 10-arylated dibenzo[b,f]azepines was developed. The pseudo-intramolecular hydrohalogenation of 2-(2′-bromophenyl)ethynylaniline, which proceeded in a syn-selective manner without forming any detectable over-addition product, was a crucial step. All attempts of subsequent arylation via Suzuki-Miyaura cross coupling and construction of a seven membered ring via Ullmann-type intramolecular coupling were unsuccessful because of dehydrohalogenation or other side reactions. This problem was overcome by the N-acetylation of the amino group, which facilitated the abovementioned coupling reactions to afford the desired 10-arylated dibenzoazepines., 2022年, 20, 28, 5543, 5550, 研究論文（学術雑誌）, 10.1039/D2OB00950A
- その他, Organic & Biomolecular Chemistry, Development of a synthetic equivalent of α,α-dicationic acetic acid leading to unnatural amino acid derivatives via tetrafunctionalized methanes, Haruyasu Asahara; Atsushi Bonkohara; Masaya Takagi; Kento Iwai; Akitaka Ito; Kotaro Yoshioka; Shinki Tani; Kazuto Umezu; Nagatoshi Nishiwaki, Diethyl mesoxalate (DEMO) exhibits high electrophilicity and accepts the nucleophilic addition of a less nucleophilic acid amide to afford N,O-hemiacetal. However, our research showed that elimination of the amide moiety proceeded more easily than dehydration upon treatment with a base. This problem was overcome by reacting DEMO with an acid amide in the presence of acetic anhydride to efficiently obtain N,O-acetal. Acetic acid was eliminated leading to the formation of N-acylimine in situ upon treatment with the base. N-Acylimine is also electrophilic, accepting the second nucleophilic addition by pyrrole or indole to form α,α-disubstituted malonates. Subsequent hydrolysis followed by decarboxylation resulted in (α-indolyl-α-acylamino)acetic acid formation; homologs of tryptophan. Through this process, DEMO serves as a synthetic equivalent of α,α-dicationic acetic acid to facilitate nucleophilic introduction of the two substituents., 2022年, 20, 11, 2282, 2292, 研究論文（学術雑誌）, 10.1039/D1OB02482E
- その他, European Journal of Organic Chemistry, Metal‐Free and syn‐Selective Hydrohalogenation of Alkynes through a Pseudo‐Intramolecular Process, Haruyasu Asahara; Yusuke Mukaijo; Kengo Muragishi; Kento Iwai; Akitaka Ito; Nagatoshi Nishiwaki, A new metal-free hydrohalogenation method for alkynes has been developed, which proceeds through a pseudo-intramolecular process. In this reaction, ethynylaniline serves as a substrate to quantitatively form an anilinium salt upon treatment with hydrochloric acid. The spatial proximity facilitates the efficient electrophilic addition of HCl to the ethynyl group in syn-mode, affording the corresponding chloroalkene without overaddition. This protocol was applied to HBr and HI, and the corresponding bromo- and iodoalkenes were obtained, respectively. The obtained chloroalkene was converted to tri-substituted alkenes possessing different aryl/alkynyl groups through Pd-catalyzed cross-coupling reactions., 2021年11月15日, 2021, 42, 5747, 5755, 研究論文（学術雑誌）, 10.1002/ejoc.202101134
- その他, Organometallics, Alkali-Metal-Ion-Centered Sandwich Structures of 4-Bromophenyl[tris(pentafluorophenyl)]borates and Their Synthetic Utility, Kento Iwai; Yoshiyuki Mizuhata; Norihiro Tokitoh, Fluorinated tetraarylborates (FTABs) are known as one of the best partners of reactive cations and radical cations. In addition, fascinating effects of ionic substituents have recently gathered much attention from organic chemists. In view of these backgrounds, we newly designed alkali-metal 4-bromophenyl[tris(pentafluorophenyl)]borates 1[ML] (M = Li, Na, K, Cs, MgBr; L = coordinating solvents) as synthetic units to explore reactive cations as zwitterionic compounds. Through this work, unique alkali-metal-centered sandwich structures of 1[ML] were revealed by X-ray crystallographic analysis. It should be noted that these are the first examples of the sandwich structure of alkali-metal borates. Their sandwich structures were induced by the M-Fortho coordination and the cation-πinteraction of the p-phenylene moiety, which constructed a cation-capturing pocket. As a synthetic utility of 1[KC6H6], we have demonstrated that the lithium-bromine exchange reaction of 1 afforded the corresponding dianionic species 2, which can be converted to boranuidyltriphenylmethanol 3[KDME] (DME = 1,2-dimethoxyethane) by the successive addition of benzophenone., 2021年03月08日, 40, 5, 570, 577, 研究論文（学術雑誌）, 10.1021/acs.organomet.0c00711
- 英語, IUCrData, 2,2-Bis[3,5-bis(dimethylamino)phenyl]-1,1,1,3,3,3-hexamethyltrisilane, Yoshiyuki Mizuhata; Kento Iwai; Norihiro Tokitoh, The title compound, C26H48N4Si3, was synthesized by the reaction of 2,2-di-chloro-tris-ilane with 3,5-bis-(di-methyl-amino)-phenyl-lithium. In the mol-ecule, the dihedral angle between the benzene rings is 57.57 (7)° and the Si-Si-Si bond angle is 110.08 (2)°. In the crystal, mol-ecules are linked via an SiC-H⋯π(ar-yl) inter-action, forming a chain along the c-axis direction., 2020年09月28日, 5, 9, x201299, 研究論文（学術雑誌）, 国際誌, 10.1107/S2414314620012997
- その他, Bulletin of the Chemical Society of Japan, Non-electronic aromatic ring activation by simple steric repulsion between substituents in 1-methylquinolinium salt systems, Kento Iwai; Soichi Yokoyama; Haruyasu Asahara; Nagatoshi Nishiwaki, A systematic study of non-electronic activation of an aromatic ring was performed using a series of 8-substituted 1-methylquinolinium salts. As the 8-substituent became bulkier, the quinoline framework was distorted by steric repulsion between substituents at the 1- A nd 8-positions. This was accompanied by lack of coplanarity, which brought about dearomatization. Consequently, quinolinium ions possessing a bulky 8-substituent exhibited high reactivity undergoing nucleophilic addition at the 2-position efficiently. We demonstrate that the activation was achieved sterically and not electronically., 2020年, 93, 1, 50, 57, 研究論文（学術雑誌）, 10.1246/bcsj.20190263
- その他, Chemical Communications, Development of a safely handleable synthetic equivalent of cyanonitrile oxide by 1,3-dipolar cycloaddition of nitroacetonitrile, Nagatoshi Nishiwaki; Yuta Kumegawa; Kento Iwai; Soichi Yokoyama, Dianionic cyano-aci-nitroacetate affords 3-cyanoisoxazol(in)es upon heating with a range of dipolarophiles in the presence of hydrochloric acid. In this reaction, nitroacetonitrile is formed as an intermediate active species, which serves as a synthetic equivalent of cyanonitrile oxide that can participate in a 1,3-dipolar cycloaddition reaction., 2019年, 55, 55, 7903, 7905, 研究論文（学術雑誌）, 10.1039/C9CC03875B
- その他, Bulletin of the Chemical Society of Japan, A direct synthesis of trisubstituted allenes from propargyl alcohols via oxaphosphetane intermediates, Kento Iwai; Soichi Yokoyama; Haruyasu Asahara; Nagatoshi Nishiwaki, A direct synthetic method for trisubstituted allenes from propargyl alcohol is provided; the synthesis proceeds via an oxaphosphetane intermediate. Functional groups such as for-myl and pyridyl exhibited a degree of tolerance during reaction without any protection. The alcohol dimethylated at the propargyl position afforded two structural isomers, allene and 1,3-diene. The product ratio was considerably influenced by the solvent. Allene was predominantly obtained when the reaction was conducted in cyclohexane, and the ratio was inverted by changing the solvent to dichloromethane. The prepared (2-pyridyl)allene served as a substrate for the copper(I) catalyzed cyclization reaction to afford 3,3-dimethylindolizine-2-one., 2018年, 91, 3, 337, 342, 研究論文（学術雑誌）, 10.1246/bcsj.20170372
- その他, Journal of Oleo Science, Phosphine induced dimerization of propargyl alcohols leading to allyl propargyl ethers, Kento Iwai; Soichi Yokoyama; Haruyasu Asahara; Nagatoshi Nishiwaki, A facile method for synthesizing allyl propargyl ethers (APEs) was developed based on the dimerization of propargyl alcohols. The reaction proceeded via an oxaphosphetane intermediate, which was generated without the use of a strong base, thus making this process a pseudo-Wittig reaction under mild reaction conditions. A wide variety of functional groups, including formyl and pyridyl groups were tolerated, thus yielding the corresponding functionalized APEs, which are otherwise not readily prepared via conventional methods. Moreover, a cross-reaction was found to occur when the reaction was conducted in the presence of alcohols that were more acidic than propargyl alcohol, which suggests that the proton transfer from the intermediately formed betaine to the second alcohol is crucial for undergoing the dimerization., 2018年, 67, 6, 773, 778, 研究論文（学術雑誌）, 10.5650/jos.ess17277
- その他, Journal of Organic Chemistry, Synthesis of Functionalized 3-Cyanoisoxazoles Using a Dianionic Reagent, Kento Iwai; Haruyasu Asahara; Nagatoshi Nishiwaki, A series of 5-acylated 3-cyanoisoxazoles were efficiently synthesized by the Michael addition of dianionic cyano-aci-nitroacetate to α-chloro-α,β-unsaturated ketones followed by intramolecular nucleophilic substitution of the nitronate ion intermediate. In this process, the dianionic reagent serves as the safe synthetic equivalent of the explosive nitroacetonitrile. The 3-cyano group is sufficiently reactive toward ethanolysis and 1,3-dipolar cycloaddition with an azide to afford ethyl ester and tetrazole, respectively. A pyridine ring between the 5-acyl and the 4-aryl group was also constructed. This led to the formation of the isoxazolo[5,4-c]quinoline derivative., 2017年05月19日, 82, 10, 5409, 5415, 研究論文（学術雑誌）, 10.1021/acs.joc.7b00811
MISC
- その他, Journal of Organic Chemistry, Nitroacetonitrile and Its Synthetic Equivalents, Kento Iwai; Nagatoshi Nishiwaki, Nitroacetonitrile (NAN) serves as a cyano(nitro)methylating agent facilitating the construction of polyfunctionalized compounds; however, its explosive property is a significant drawback in terms of practical handling. Alkali metal salts of NAN are thermally stable, but their insolubility in organic solvents restricts their use as a synthetic reagents. On the contrary, dipyrrolidinium cyano-aci-nitroacetate is soluble in common organic solvents and thermally stable, allowing for its use as an alternative synthetic equivalent of nitroacetonitrile for the construction of polyfunctionalized frameworks via cyano(nitro)methylation., 2021年10月01日, 86, 19, 13177, 13185, 書評論文,書評,文献紹介等, 10.1021/acs.joc.1c01515
受賞
共同研究・競争的資金等の研究課題
- 特別研究員奨励費, 2020年04月24日, 2022年03月31日, 20J12946, アニオン性置換基導入による高周期元素低配位化学種の酸化電位および構造の制御, 岩井 健人, 日本学術振興会, 科学研究費助成事業, 京都大学, 1700000, 1700000, 0, 申請者の2020年度における研究計画では、ボラヌイジル基を有する高周期典型元素低配位化学種を合成し、物性の評価を行なうことで、ボラヌイジル基の置換基効果を解明することを目標としていた。実際の研究では、ボラヌイジル基を有する双性イオン型トリアリールメチリウム塩やアクリジニウム塩およびケイ素化合物を新たに合成し、物性や反応性の評価を行なった。その結果、双性イオン型のトリアリールメチリウム塩が外部刺激に応答した色調の変化を示すことや、アクリジニウム塩が固体状態でのみ発光を示すことを明らかにした。これらの双性イオン型の色素について、単結晶X線構造解析など各種測定を行なったところ、ボラヌイジル基のイオン性相互作用に起因する特異な分子配列を示していることがわかった。この結果から、ボラヌイジル基の置換基効果として、分子内の電子的な効果のみならず、固体状態での分子間の集積構造を制御する効果があると考えられる。従って、ボラヌイジル基の新たな活用法として分子配列の制御が可能であることを示した点で本研究成果は意義深いといえる。 さらにボラヌイジル基を有する低配位ケイ素化学種の合成検討では、ボラヌイジル基を有するクロロシラン類にN-ヘテロ環状カルベン（NHC）を作用させると塩脱離を伴う求核置換反応が進行することを見出した。これは一般的なシラン類では見られない反応性であり、ボラヌイジル基を導入したことにより発現した新規な反応性であると考えられる。また、本置換反応により生成するイミダゾリオシランは更なる化学変換により多座配位性の配位場を有するアニオン性NHCへ変換できることを明らかにした。これらの一連の反応は近年注目を集めているアニオン性NHCの新規な合成法と見做せるため、合成化学的な観点から意義深い結果であると考えられる。, kaken