Stereochemical Studies. V. Intramolecular C-H Bond Insertion Reaction of Acyl Nitrene generated from optically Active Acyl Azide
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概要
- 論文の詳細を見る
In order to determine the spin state of the acyl nitrene (VII) which is thought to intervene in the insertion reaction at the intramolecular aliphatic C-H bond, optically active (R)-5-methyl-6-phenylhexanoyl azide ((R)-XVII) was synthesized from ((S) (+)-2-methyl-3-phenylpropionic acid ((S) (+)-XVIII), and submitted to photochemical decomposition in methylene dichloride solution. (S) (-)-6-Benzyl-6-methyl-2-piperidone ((S) (-)-XIX) was obtained as a reaction product in a 4.3% yield with 98% retention of configuration. These results show that the singlet state acyl nitrene (XXXVIII) produced from (R)-XVII by irradiation, had inserted into the intramolecular optically active C-H bond through the transition state (IL), as in the intramolecular insertion reaction of alkoxycarbonyl nitrene. Independent synthesis of (S) (-)-XIX from (R)-α-methylphenylalanine ethyl ester ((R) (+)-XX), and preliminary experiments on racemic compounds are also reported.
- 公益社団法人日本薬学会の論文
- 1970-06-25
著者
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山田 俊一
Faculty Of Pharmaceutical Sciences University Of Tokyo
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寺島 孜郎
(財)相模中央化学研究所
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奈良 宗彦
興和(株)東研
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寺島 孜郎
Faculty Of Pharmaceutical Sciences University Of Tokyo:(present Address)sagami Chemical Research Cen
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奈良 宗彦
Faculty of Pharmaceutical Sciences, University of Tokyo
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