京都大学 · 材料科学
小池大一教授の研究室は、遷移金属を用いた新しい有機合成反応の開発を柱としています。特に、アルキン誘導体を用いたサイクロアロマティゼーションや、金属を介したバルェンス異性化反応、およびフェイス・オキシカルベニウム型中間体を経る酸化カルベニウム錯体の生成反応に注力しています。これらの反応は、天然物合成や機能性化合物の効率的合成に応用可能な、高選択的で実用的な手法を提供しています。
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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNucleophilic substitution at the central allyl carbon atom of a (.pi.-allyl)platinum complexKouichi Ohe, Hideki Matsuda, Tsumoru Morimoto, Sensuke Ogoshi, Naoto Chatani, and Shinji MuraiCite this: J. Am. Chem. Soc. 1994, 116, 9, 4125–4126Publication Date (Print):May 1, 1994Publication History Published online1 May 2002Published inissue 1 May 1994https://pubs.acs.org/doi/10.1021/ja00088a077https://doi.org/10.1021/ja00088a077research-articleACS Publicati
The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cyc
A transition metal catalyst can trigger the cycloaromatization of an enediyne. A coordinatively unsaturated rhodium complex catalyzes the cyclization of the acyclic enediyne 1 to produce 3. The cyclization, which is similar to the Myers reaction, proceeds via a vinylidene–rhodium intermediate and the 1,4-organorhodium diradical 2. Rh = [RhCl(iPr3P)2].
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSodium arenetellurolate-catalyzed selective conversion of nitro aromatics to aromatic azoxy or azo compounds and its application for facile preparation of 3,3'- and 4,4'-bis[.beta.-(aryltelluro)vinyl]azobenzenes from (3- and 4-nitrophenyl)acetylenesKouichi Ohe, Sakae Uemura, Nobuyuki Sugita, Hideki Masuda, and Toru TagaCite this: J. Org. Chem. 1989, 54, 17, 4169–4174Publication Date (Print):August 1, 1989Publication History Published online1 May 2002Pu
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-catalyzed reaction of 5-methylene-1,3-dioxolan-2-ones. A new access to and reactivity of oxatrimethylenemethane-palladiumKouichi Ohe, Hideki Matsuda, Toshihisa Ishihara, Sensuke Ogoshi, Naoto Chatani, and Shinji MuraiCite this: J. Org. Chem. 1993, 58, 5, 1173–1177Publication Date (Print):February 1, 1993Publication History Published online1 May 2002Published inissue 1 February 1993https://pubs.acs.org/doi/10.1021/jo00057a033https://doi.org/10
The reaction of conjugated enyne−carbonyl compounds such as 1-(alkoxycarbonyl)-2-ethynylcycloalkenes and 1-carbamoyl-2-ethynylcycloalkenes with Mo(CO)5·NEt3 and W(CO)5·THF gave the corresponding 6-alkoxy- and 6-amino-2H-pyranylidene−molybdenum and −tungsten complexes, respectively. The cycloisomerization reaction of the conjugated vinylidene−ene−carbonyl complexes generated from 1-(alkoxycarbonyl)- or 1-carbamoyl-2-ethynylcycloalkenes and metals is a key route to these Fischer-type oxacarbene co
The ruthenium-catalyzed isomerization of diynes and triynes involving propargyl carboxylate moieties affords dienynes and dienediynes, respectively. The [1,n]-metallotropic shift (n = 3, 5) (carbene walk) of in situ generated alkynyl carbene complexes has been proposed for the catalytic isomerization reaction.
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