Cyclopentadienyliron-mediated introduction of functionalized alkyl or alkynyl groups to arenes in an addition—demetallation sequence
作者:Ronald G. Sutherland、Chunhao Zhang、Adam Piórko
DOI:10.1016/0022-328x(91)80248-i
日期:1991.1
cyanomethyl, and phenylethynyl anions add selectively ortho to arenes containing electron-witdrawing groups and complexed with cyclopentadienyliron. Under similar reaction conditions anions such as alkyl, dichloromethyl and trichloromethyl add in a non-selective way. Addition of the trichloromethyl anion is thermodynamically controlled at extended reaction times and, due to the size of the anion, the
硝基甲基,氰基甲基和苯基乙炔基阴离子选择性地将邻位添加到含有吸电子基团并与环戊二烯基铁络合的芳烃上。在相似的反应条件下,阴离子如烷基,二氯甲基和三氯甲基以非选择性方式添加。的三氯甲基阴离子的加成在延长反应时间是热力学控制的,并且由于阴离子的大小,元加成产物是有利的。加合物的脱金属导致邻位-硝基甲基化,氰基甲基化或苯基乙炔化的芳烃。对于对称的芳烃配合物,加成-脱金属顺序导致将三氯甲基基团引入芳烃环,从而产生单一产物。从合适的环戊二烯基铁络合物开始的一锅法二烷基芳烃的三氯甲基化可以良好的产率得到β-三氯甲基化的二烷基芳烃。