| A NOVEL ACETYLENIC ESTER-VINYL ETHER REARRANGEMENT |
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| 作者姓名： | 黄耀曾 沈延昌 忻元康 傅桂香 徐永珍 |
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| 作者单位： | Shanghai Institute of Organic Chemistry，Academia Sinica，Shanghai Institute of Organic Chemistry，Academia Sinica，Shanghai Institute of Organic Chemistry，Academia Sinica，Shanghai Institute of Organic Chemistry，Academia Sinica，Shanghai Institute of Organic Chemistry，Academia Sinica |
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| 摘 要： | A novel acetylenic ester-vinyl ether rearrrangement takes place when perfluoroacetylenicester is subject to hydrolysis with aqueous sodium hydroxide. The rearrangement is highlystereoselective and the Z-isomer predominates to the extent of above 94% in all cases. Thecrossover experiments showed that this rearrangement proceeds predominately intramolecu-larly. By using ~(18)O labeling technique and on the basis of mass spectral study, it wasshown that the rearrangement most likely roceeds through an intramolecular 1, 3 shiftof the methoxy group to the β-carbon atom. A novel mechanism involving a cage reactionin the organic phase of a two-phase system is proposed.
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