光学活性アミノ酸を利用した革新的分子変換

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概要

• 論文の詳細を見る

• Some methods for innovative molecular transformations using optically active α-amino acids have been exploited. 1) The non-Kolbe reaction of the N-benzoyloxazoline derivative 1 derived from L-serine gave the optically active N,O-acetal 2 when graphite was used an anode material. This reaction represents the first example of “memory of chirality” in the carbenium ion chemistry. 2) The optically active pipecolic acid derivative 13, prepared from L-lysine by using electrochemical oxidation, was cyclopropanated with high diastereoselectivity (96.6%de), and the product 14 was transformed into (2S,3R)-metanopipecolic acid (7). 3) An enantiomerically pure 1,2-dihydropyridine 23 was prepared from L-lysine using electrochemical oxidation as a key step and was utilized as a chiral diene synthon in the Diels-Alder reaction. That is, in the presence of AlCl3, the Diels-Alder reaction between 23 and N-acryloyloxazolidinone 24 gave a cycloadduct with high stereoselectivity, which was converted to an optically active isoquinuclidine derivative 26 (96.8%ee). 4) The Hofmann rearrangement of the L-glutamine derivative 27 to the enantiomerically pure 2-aminobutyric acid derivative 28 was successfully achieved with an electrochemical method using a trifluoroethanol-MeCN solvent system. 5) Some types of N-formyl cyclic amine derivatives were found to be effective activators of trichlorosilane to reduce ketones and imines. Namely, the reduction of ketones and imines by trichlorosilane with a catalytic amount of L-proline derivatives 30 and 32 gave enantiomerically enriched sec-alcohols and amines, respectively, to some extent of optical yields.

• 日本薬学会の論文
• 2002-11-01

著者

• 尾野村 治

  長崎大学 大学院医歯薬学総合研究科生命薬科学専攻

• 尾野村 治

  長崎大 大学院医歯薬学総合研究科 生命薬科学専攻

• 尾野村 治

  長崎大学大学院医歯薬学総合研究科

関連論文

• 有機電解合成における不斉反応の新展開
• 1,2-ジオール分子認識に基づく選択的分子変換反応
• 1-アルコキシ-2,2,2-トリフロロエチル基で保護したL-プロリノール誘導体の電極酸化
• 光学活性アミノ酸を利用した革新的分子変換
• 研究開発情報 トリクロロシランの触媒的活性化法の開発と還元反応への応用

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