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Controlling the Reactivity of Ferrocenyl Carbocations: Routes to Enantiomerically Pure Chlorophosphites and Solid‐State Characterization of a Benzopentalene Dimer
Author(s) -
Nottingham Chris,
MüllerBunz Helge,
McGlinchey Michael J.,
Guiry Patrick J.
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201700430
Subject(s) - chemistry , enantiopure drug , carbocation , dimer , phosphoramidite , reactivity (psychology) , ferrocene , stereochemistry , organic chemistry , medicinal chemistry , catalysis , enantioselective synthesis , electrochemistry , oligonucleotide , medicine , dna , biochemistry , alternative medicine , electrode , pathology
A range of enantiopure ferrocenyl diols possessing a variety of electron‐withdrawing groups at the carbinol centre was investigated in the reaction with phosphorus trichloride. Subtle changes in the electronic properties of these groups led, after reaction with phosphorus trichloride, to distinctly different products: α‐substituted ferrocenes, (bis)phosphinic dichlorides, benzopentalene dimers or chlorophosphites. A mechanistic rationale was developed based upon the observed α‐ferrocenyl carbocation behaviour to account for the formation of such diverse products. Two benzopentalene dimers were isolated and successfully characterized by X‐ray crystallography, representing the first examples of such compounds in the solid‐state. The synthesis and characterization of an enantiopure ferrocenophane‐phosphoramidite‐gold(I) complex is also described.