Unexpected Oxidative Dimerisations of a Cyclopentadienyl‐Phosphane – Formation of Unprecedented, Structurally Remarkable Phosphacyclic Compounds
作者:Crispin Lichtenberg、Michael Elfferding、Jörg Sundermeyer
DOI:10.1002/ejic.200901267
日期:2010.7
4 ) with Ph 3 PCH 2 X + X - (X = Cl, Br, I) and diiodomethane as potential electrophiles have been investigated. Unexpectedly, in all four cases unprecedented oxidative dimerisations of the cyclopentadienylphosphane 1 have been observed. In the reactions with the phosphonium salts, an ionic group 15 analogue of octamethyl-tetrahydro-s-indacene with different counterions X - has been obtained (5-7) as
已经研究了 Me 2 PCp # (1) (Cp # = C 5 HMe 4 ) 与 Ph 3 PCH 2 X + X - (X = Cl, Br, I) 和二碘甲烷作为潜在亲电试剂的反应。出乎意料的是,在所有四种情况下,都观察到了环戊二烯基膦 1 前所未有的氧化二聚反应。在与鏻盐的反应中,由于 X + 转移和 H + 消除,获得了具有不同抗衡离子 X - 的八甲基-四氢-s-茚的离子基团 15 类似物 (5-7)。在 1 与二碘甲烷的反应中,形成了具有两个直接连接的螺碳中心的四重芳环化、部分不饱和、杂环化合物 9,这可能是碘自由基转移的结果。两种新型磷杂环均已通过单晶 XRD 分析表征。