A new type of P - C and C - C bond cleavage reactions in .ALPHA.-trimethyl-silyloxy-.BETA.-oxo phosphonates and .ALPHA.-ethoxy-.BETA.-oxo phosphonates. The synthesis of unsymmetrical .ALPHA.-hydroxy ketones utilizing 1:1 carbonyl adducts of diethyl trimet
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概要
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α-Lithiated diethyl α-(trimethylsilyloxy)benzylphosphonate underwent facile acylation with various acylating agents to afford the corresponding α-acylated products in good yields. On treatment of the α-acylated products with 1 M NaOH–EtOH (1:1, v/v) the P–C bond was cleaved with elimination of diethyl phosphate to give α-hydroxy ketones predominantly. On the other hand, when diethyl α-acyl-α-ethoxybenzylphosphonates were treated under the same conditions, they were rather stable and recovered. However, the prolonged alkaline treatment or the use of 4 M NaOH–EtOH (1:1, v/v) resulted in the C–C bond cleavage giving carboxylic acids and diethyl α-ethoxybenzylphosphonate in quantitative yields, respectively. The mechanisms of the above two reactions were proposed and discussed in connection with the Perkow reaction and related reactions.
- 公益社団法人 日本化学会の論文
著者
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Sekine Mitsuo
Department Of Life Chemistry Tokyo Institute Of Technology
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Nakajima Masashi
Department Of Internal Medicine And Health Care Fukuoka University
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Hata Tsujiaki
Department of Chemistry Tokyo Institute of Technology
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