Controlling the Reactivity of Ferrocenyl Carbocations: Routes to Enantiomerically Pure Chlorophosphites and Solid‐State Characterization of a Benzopentalene Dimer
作者： Chris Nottingham , Helge Müller-Bunz , Michael J. McGlinchey , Patrick J. Guiry
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摘要: A range of enantiopure ferrocenyl diols possessing a variety electron-withdrawing groups at the carbinol centre was investigated in reaction with phosphorus trichloride. Subtle changes electronic properties these led, after trichloride, to distinctly different products: alpha-substituted ferrocenes, (bis)phosphinic dichlorides, benzopentalene dimers or chlorophosphites. mechanistic rationale developed based upon observed alpha-ferrocenyl carbocation behaviour account for formation such diverse products. Two dimmers were isolated and successfully characterized by X-ray crystallography, representing first examples compounds solid-state. The synthesis, characterization an ferrocenophane-phosphoramidite-gold(I) complex is also described.
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