α-取代内酯的立体选择硝基乙烯化反应研究  

Stereoselective Nitroolefination of α-Substituted Lactones

作　　者：王锐[1] 杨晓武 刘大学 贾强[2] 

机构地区：[1]应用有机化学国家来点实验室,兰州730000 [2]兰州大学生物系,化学系,兰州730000

出　　处：《高等学校化学学报》1998年第1期56-60,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金!29442010;霍英东教育基金;国家教委优秀年轻教师基金;博士点专项科研基金

摘　　要：研究了α-取代内酯的立体选择硝基乙烯化反应.从金属离子对反应时间、温度及产率的影响实验中发现，Zn2+增加了反应活性．用1HNMR光谱确定了产物双键的立体构型，并初步探讨了反应历程．Nitroolefins are versatile intermediates in the synthesis of complex natural products because of their various functional group transformations. They can proceed Michael type additions, and Diels-Alder cyclic reactions. Furthermore, the--NO2 group can be converted to carbonyl group by reductive Nef reaction. Their synthetic potential should be greatly enhanced if they contain quaternary carbon centers. Here, we wish to describe stereoselective nitroolefination of α-substituted carbonyl compounds via addition-elimination on the basis of our previous research. The E stereochemistry of double bond was determined by 1H NMR data (chemical shift, the coupling constant). Studies on effects of different metal ions on reaction temperature, time and yields showed Zn2+ enhanced reactivity. A rational process of addition-elimination was proposed to elucidate the reaction mechanism.

关 键 词：硝基乙烯内酯 季碳中心 α-取代内酯 

分 类 号：O626[理学—有机化学]