Thermal Cyclization of Copper Carbenoid of α‐Dizao α‐Phosphorylacetate: Unexpected and Novel Access to Oxaphosphirane |
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| Authors: | Jr‐Yun Shie Jia‐Liang Zhu Yung‐Peng Wu |
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| Affiliation: | 1. Department of Chemistry, National Dong Hwa University, Hualien 974, Taiwan, R.O.C. Tel: +886‐3‐8633583;2. Fax: +886‐3‐8633570 |
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| Abstract: | Under the catalysis of Cu(OTf)2 in refluxing CH2Cl2, ethyl α‐dizao α‐(diethylphosphoryl)acetate was shown to undergo a new cyclization reaction to afford a pentacovalent oxaphosphirane product. The reaction is proposed to occur through the addition of the P=O double bond to the copper carbenoid, followed by the hydrolysis of the ylide intermediate. Our finding represents the first example on producing oxaphosphiranes from dizao phosphoryl compounds. On the other hand, the corresponding rhodium carbenoid displayed the different reactivity under the same thermal conditions, to produce the β‐propiolactone through the well‐recognized C‐H insertion pathway. |
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| Keywords: | α ‐Dizao α ‐phosphorylesters Carbenoids Oxaphosphiranes Intramolecular cyclization Copper‐catalysis |
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