化学、位置、立体選択的な触媒的分子変換反応の開発
メンバー： 平野雅文、小峰伸之
分野： 基礎化学、複合化学、材料化学
所属： 工学研究院
キーワード： 分子触媒反応、有機金属化合物、分子活性化、鎖状交差二量化、不斉反応
ウェブサイト：
研究概要
後周期遷移金属化合物を触媒とする基質、位置、立体選択的な触媒的分子変換反応の開発をしています。①12電子０価ルテニウム化合物を鍵とする置換アルケンや共役ジエンの選択的鎖状交差二量化反応、②12電子０価パラジウム化合物を鍵とする電子不足アルケンの選択的ヒドロシリル化およびヒドロメタル化反応、③０価パラジウム化合物を鍵とする触媒的な炭素ー酸素／炭素ー水素結合の連続的活性化反応、④酸化的アレーンカップリング反応などを研究しています。
１）鎖状交差二量化反応によるヘテロ環状化合物と共役化合物の直接カップリング反応反応
２）不斉鎖状交差二量化反応
３）ポリエンの合成
４）フルオレン誘導体の炭素ー酸素／炭素ー水素結合の連続的切断による触媒的合成
５）電子不足アルケンに対するヒドロシリル化反応
６）電子不足アレーンを用いた酸素を酸化剤とする直接的アレーンカップリング
７）分子内求電子置換機構を利用した協奏的結合切断反応
主要論文・参考事項
(1) Nobuyuki Komine, Makoto Abe, Ryoko Suda, Masafumi Hirano, Markovnikov-Selective Hydrosilylation of Electron-Deficient Alkenes with Arylsilanes Catalyzed by Mono(phosphine)palladium(0), Organometallics, 34, 432-437 (2015).
(2) Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, and Masafumi Hirano, Regio- and Enantioselective Cross-Dimerization between Conjugated Dienes and Acrylates Catalyzed by New Ruthenium(0) Complexes, Organometallics, 33, 6604-6613 (2014).
(3) Masafumi Hirano, Sosuke Kawazu, Nobuyuki Komine, Direct Access to Fluorene by Successive C-O/C-H Bond Activations of 2-Phenylbenzyl Ester, Organometallics, 33, 1921-1924 (2014).
(4) Masafumi Hirano, Yasuto Yanagisawa, Endin Mulyadi, Nobuyuki Komine, Sanshiro Komiya, Multiple C-H Bond Cleavage of Alkyl Group in (2,6-Dialkylphenoxo)ruthenium(II) Complex, Organometallics, 33, 1235-1244 (2014).
(5) Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, and Masafumi Hirano, Asymmetric Cross-dimerization between Methyl Methacrylate and Substituted Alkenes by Ru(0)-Bicyclononadiene Complex, Org. Lett. 15, 2486-2489 (2013).
お問い合わせ先
東京農工大学・先端産学連携研究推進センター
urac[at]ml.tuat.ac.jp（[at]を@に変換してください）
Develpment of Chemo-, Regio- and Stereoselective Catalytic Transformations of Organic Molecules
Research members： Masafumi Hirano PhD., Dr. Nobuyuki Komine
Research fields： Basic chemistry, Applied chemistry, Materials chemistry
Departments： Faculty of Engineering
Keywords： Molecular Catalysis, Organometallic Compounds, Molecular Activation, Cross-dimerizations, Enantioselective Reactions
Web site：
Summary
Our team develops the substrate-, regio- and stereoselective catalytic molecular transformation mainly by late-transition metal compounds. The main current interests are (1) Selective linear cross-dimerizations using substituted alkenes or conjugated dienes catalyed by a formal 12-electron zerovalent ruthenium species, (2) Selective hydrosilylation and hydrometallations using electron-deficient alkenes and alkynes using a formal 12-electron zerovalent palladium species, (3) Successive C-O/C-H bond activations by zerovalent palladium compounds, (4) Oxidative arene coupling reactions by palladium compounds.
1) Direct coupling reactions between heterocyclic compounds with conjugated compounds by linear cross-dimerization reactions
2) Enantioselective cross-dimerization reactions
3) Synthesis of polyene compounds
4) Synthesis of fluorenes by successive C-O/C-H bond cleavage reactions
5) Hydrosilylations of electron-deficient alkenes/alkynes
6) Direct arene coupling reactions using oxygen as an oxidant
7) Concerted bond cleavage reactions by internal electrophilic substitution
Reference articles and patents
(1) Nobuyuki Komine, Makoto Abe, Ryoko Suda, Masafumi Hirano, Markovnikov-Selective Hydrosilylation of Electron-Deficient Alkenes with Arylsilanes Catalyzed by Mono(phosphine)palladium(0), Organometallics, 34, 432-437 (2015).
(2) Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, and Masafumi Hirano, Regio- and Enantioselective Cross-Dimerization between Conjugated Dienes and Acrylates Catalyzed by New Ruthenium(0) Complexes, Organometallics, 33, 6604-6613 (2014).
(3) Masafumi Hirano, Sosuke Kawazu, Nobuyuki Komine, Direct Access to Fluorene by Successive C-O/C-H Bond Activations of 2-Phenylbenzyl Ester, Organometallics, 33, 1921-1924 (2014).
(4) Masafumi Hirano, Yasuto Yanagisawa, Endin Mulyadi, Nobuyuki Komine, Sanshiro Komiya, Multiple C-H Bond Cleavage of Alkyl Group in (2,6-Dialkylphenoxo)ruthenium(II) Complex, Organometallics, 33, 1235-1244 (2014).
(5) Yuki Hiroi, Nobuyuki Komine, Sanshiro Komiya, and Masafumi Hirano, Asymmetric Cross-dimerization between Methyl Methacrylate and Substituted Alkenes by Ru(0)-Bicyclononadiene Complex, Org. Lett. 15, 2486-2489 (2013).
Contact
University Research Administration Center(URAC),
Tokyo University of Agriculture andTechnology
urac[at]ml.tuat.ac.jp
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