Extraannular Fluorinated Calixarenes:  Regiospecificity of the Deoxofluorination Reactions of Bis(spirodienol) Derivatives

A new route for the partial displacement of OH groups of p-tert-butylcalixarene via spirodienol derivatives is described. NaBH4 reduction of the bis(spirodienone) calixarene derivatives 2a−2c afforded the corresponding bis(spirodienols) 3a−3c in stereospecific fashion. 1H NMR NOESY spectroscopy indicated that in the case of 2a, the reaction proceeds by attack at the exo face of the two carbonyls (the face located anti to the spiro C−O bond). The spirodienols readily revert to p-tert-butylcalix[4]arene when heated. The reaction of 3a with the deoxofluorinating agent DAST (Et2NSF3) afforded a mixture of extraannular substituted calixarenes possessing one or two fluoro-substituted dehydroxylated rings. The bisfluorinated calixarene 6a adopts in the crystal a conformation (1,3-alternate) similar to that adopted in solution by the di-dehydroxylated calixarene 6b. An experiment conducted with a selectively deuterated spirodienol derivative indicated that the deoxofluorination reaction involves regiospecific nucleophilic attack at the γ position of the pentadienol subunit.