71292-75-6Relevant academic research and scientific papers
A New Type of P-C and C-C Bond Cleavage Reactions in α-Trimethylsilyloxy-β-oxo Phosphonates and α-Ethoxy-β-oxo Phosphonates. The Synthesis of Unsymmetrical α-Hydroxy Ketones Utilizing 1:1 Carbonyl Adducts of Diethyl Trimethylsilyl Phosphite with Benzaldehyde
Sekine, Mitsuo,Nakajima, Masashi,Hata, Tsujiaki
, p. 218 - 223 (2007/10/02)
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 with 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.
Silyl Phosphites. 16. Mechanism of the Perkow Reaction and the Kukhtin-Ramirez Reaction. Elucidation by means of a New Type of Phosphoryl Rearrangements Utilizing Silyl Phosphites
Sekine, Mitsuo,Nakajima, Masashi,Hata, Tsujiaki
, p. 4030 - 4034 (2007/10/02)
Reactions of α-lithiated diethyl α-benzylphosphonate (4) with benzoyl chloride and chloroiodomethane afforded benzoylated and chloromethylated products (1 and 2) corresponding to the 1:1 carbonyl adducts of diethyl trimethylsilyl phosphite with benzil and phenacyl chloride which were not obtained by the reactions between the phosphite and benzil or phenacyl chloride.Pyrolysis of 1 and 2 afforded 1,3,2-dioxaphosphole (6) and enol phosphate (8).On the other hand, treatment of 1 and 2 with tetrabutylammonium fluoride afforded benzoin phosphate (7)and 1,2-epoxy phosphonate (14), respectively, as the main products.These results are also discussed in connection with the mechanism of the Perkow reaction and the Kukhtin-Ramirez reaction.
