prepared by the alkylation of fluorenyllithium with (−)-menthyltosylate, and the complex (+)-(pseudo-neomenthylfluorenyl)Co(COD) (6) was synthesized by the metathetic reaction of the corresponding lithium salt with (PPh3)3CoCl and COD, in which an inversion of the cyclohexane ring of the terpene moiety was observed upon complexation. The structures of the compounds 1, 2, 3, 4, 5, and 6 were determined by single-crystal
制备了几种旋光的(Cp R)Co(L)(L = 1,5-
环辛二烯,降
冰片二烯)配合物。通过在COD存在下用高反应性“原子”
钴直接处理(-)-薄荷基
环戊二烯,合成了(-)-(薄荷基Cp)Co(COD)(1)。通过将(-)-去质子化来制备(+)- pR-(1-
新薄荷烯基)Co(COD)(2)和(+)- pR-(1-
新薄荷烯基)Co(NBD)(3)。 3-新
萘与BuLi的反应以及相应的
锂盐与三(
三苯基膦)
钴(I)
氯化物的易位反应,然后替换PPh 3分别使用COD或NBD。络合物的非对映选择性高达74.5%de,色谱分离出主要的非对映异构体。从(+)-3-
新薄荷烯开始,类似地制备光学纯的配合物(-)- pS-(1-
新薄荷烯基)Co(COD)(4),主要非对映异构体的非对映异构体过量为74.4%de。通过将
芴基
锂与(-)-薄荷基
甲苯磺酸酯烷基化来制备(+)-
新薄荷基
芴5,并通过相应
锂的易位反应合成络