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KAKEN_24350050seika.pdf
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ハードな配位子を持つ後周期遷移金属ビニリデン種の発生を機軸とする新合成反応の開発
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ハードナ ハイイシ オ モツ コウシュウキ センイ キンゾク ビニリデンシュ ノ ハッセイ オ キジク ト スル シンゴウセイ ハンノウ ノ カイハツ
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Hadona haiishi o motsu koshuki seni kinzoku biniridenshu no hassei o kijiku to suru shingosei hanno no kaihatsu
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Development of catalytic reactions involving late transition-metal vinylidene species bearing hard ligands
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垣内, 史敏
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カキウチ, フミトシ
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Kakiuchi, Fumitoshi
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慶應義塾大学・理工学部・教授
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Research team head
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科研費研究者番号 : 70252591
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河内, 卓彌
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コウチ, タクヤ
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Kochi, Takuya
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慶應義塾大学・理工学部・専任講師
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Research team member
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科研費研究者番号 : 70396779
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2016
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科学研究費補助金研究成果報告書
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2015
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本研究では, ロジウムキノリノラト錯体がもつ特徴を使い, 新規触媒反応の開発を目指して検討した。その結果, 末端アセチレン2分子が活性メチレン化合物1分子と環化反応を起こしたシクロペンテン類を与える反応を見出した。さらに, 末端アルキンとアクリル酸エステルとの反応では, [2+2]型付加環化生成物を与える新規触媒反応の開発に成功した。キノリノラート配位子にホスフィン部位を導入したPNO型三座配位子をもつロジウム錯体の合成法の開発にも成功した。
Developments of new catalytic reactions using rhodium-quinolinolato complexes as catalysts have been investigated. We have developed the [Rh(Q)(cod)]-catalyzed 2:1 coupling reaction of terminal alkyne and active methylene compounds leading to cyclopentene derivatives. We found that the coupling of aliphatic alkynes with alkyl acrylates gave cyclobutene derivatives in regioselective manner in high yields. In addition, we synthesized PNO tridentate ligands bearing diphenylphosphinomethylene group at 2-position of the quinolinolate moiety and prepared new types of rhodium complexes having this PNO tridentate ligand.
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研究種目 : 基盤研究(B)(一般)
研究期間 : 2012～2015
課題番号 : 24350050
研究分野 : 有機合成化学
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