Carbanions 27. Rearrangements of (9-alkyl-9-fluorenyl)-methyllithium (or cesium) and 2,2-diphenyl-3,3-dimethyl-butyllithium
作者:Erling Grovenstein、Jagvir Singh、Bhalchandra B. Patil、Don VanDerveer
DOI:10.1016/s0040-4020(01)90451-x
日期:1994.1
with some 9-neopentylphenanthrene which becomes the major product in diethyl ether solution at 35 °C. 2,2-Diphenyl-3,3-dimethylbutyllithium undergoes predominantly [1,2]-phenyl migration in THF at 0 °C. From an x-ray crystal study upon 9-tert-butyl-9-(chloromethyl)fluorene and 9-neopentyl-9-(chloromethyl)fluorene, it is concluded that steric acceleration is responsible for the unusual reactions of
已经对将各种(9-烷基-9-芴基)甲基锂(或铯)化合物在THF中加热到接近0°C,然后进行碳化的产品进行了研究。当9-烷基为乙基时,结果主要是质子化产物(9-烷基-9-芴基)甲烷;当9-烷基为1-降冰片基时,显然会形成类似的产物。当9-烷基是叔丁基时,次要产物是叔[1,2]迁移引起的9-新戊基芴-9-羧酸。-氘基,而主要产物是分子内消除的9-甲基芴-9-羧酸,如氘标记所示。当9-烷基是新戊基时,主要产物是9-新戊基-9,10-二氢菲-9羧酸以及一些9-新戊基菲,其在35℃的乙醚溶液中成为主要产物。2,2-二苯基-3,3-二甲基丁基锂在0°C下主要在THF中经历[1,2]-苯基迁移。根据对9-叔丁基-9-(氯甲基)芴和9-新戊基-9-(氯甲基)芴的X射线晶体研究,可以得出结论,空间加速是导致(9-烷基-当9-烷基为叔丁基和新戊基时的9-芴基)甲基锂。