L-2(10)-蒎烯四醋酸铅氧化产生扩环产物的结构

Structures of Ring-Enlargement Products from Oxidation of L-2(10)-Pinene with Lead Tetraacetate

在四醋酸铅氧化L-2(10)-蒎烯的产物中,首次分离得到三种扩环产物2、3、4,经HR-MS、EI-MS、NMR(~1H、^(13)C、H-H COSY、H-C COSY)、IR等波谱方法确定,分别为(1S,6S)-7,7-二甲基双环[4.1.1]-3-辛烷酮及其异构体(1R,6S)-7,7-二甲基双环[4.1.1]-2-辛烷酮和(4S)-4-异丙烯基环庚烷酮,文中还讨论了反应机理。

Three ring-expanding products 2,3 and 4 were isolated for the first time from the lead tetraacetate oxidation products of L-2(10)-pinene . Their structures, (1S,6S)-7,7-dimethyl-bicyclo [4, 1. 1]-3-octanone, (1R,6S)-7,7-dimethylbicyclo[4. 1. 1]-2-octanone, and (4S)-4-iso-propenylheptanone, were respectively established on the basis of spectroscopic data (EI-MS,HR-MS, IR,1H-NMR,13C-NMR,H-H and C-H COSY,etc. )- Possible reaction pathways for the formation of these new compounds involving novel ring-enlargement are discussed.