Photochemical Studies on 5-Methylbicyclo[1.1.1]pentane Derivatives： p-Orbital Overlap Controlled Enantioselectivity  

作　　者：马满玲 杨超 李冰 邵玉田 赵国磊 夏吾炯 

机构地区：[1]State Key Laboratory of Urban Water Resource and Environment,Academy of Fundamental and Interdisciplinary Sciences,Harbin Institute of Technology,Harbin,Heilongjiang 150080 [2]State Key Laboratory of Applied Organic Chemistry,Lanzhou University,Lanzhou,Gansu 730000

出　　处：《Chinese Journal of Chemistry》2012年第1期91-95,共5页中国化学（英文版）

基　　金：We are grateful to the financial supports from the National Natural Science Foundation of China （Nos. 20802013, 21002018, 21072038）, the Natural Scientific Research Innovation Foundation in Harbin institute of Technology （Nos. 01107866, 01107986） and the Wenzhou Science and Technology Program （No. G20100056）.

摘　　要：The first example of the p-orbital overlap controlled enantioselectivity of Norrish type II photocyclization reaction was described. Irradiation of 5-methyl bicyclo[l. 1.1 ]pentanyl ketone with UV in the solid state as well as in the acetonitrile solution afforded the Norrish/Yang photocyclization compound as the sole product. Solid-state asymmetric photochemical studies using ionic chiral auxiliary technique led to the enantioselectivity as high as 60%. The results were rationalized by Xray single crystal structure.The first example of the p-orbital overlap controlled enantioselectivity of Norrish type II photocyclization reaction was described. Irradiation of 5-methyl bicyclo[l. 1.1 ]pentanyl ketone with UV in the solid state as well as in the acetonitrile solution afforded the Norrish/Yang photocyclization compound as the sole product. Solid-state asymmetric photochemical studies using ionic chiral auxiliary technique led to the enantioselectivity as high as 60%. The results were rationalized by Xray single crystal structure.

关 键 词：ENANTIOSELECTIVITY porbital overlap solid state Norrish type 11 photoreaction ionic chiral auxiliary 

分 类 号：O6-1[理学—化学] O629.711