Chemoselectivity of Pinacol Rearrangement Originate by Different Hexafluoroantimonate Oxidant.

Using 1,1,2‐triphenylethane‐1,2‐diol, AgSbF6, and NOSbF6, two different carbonyl products of rearrangement were synthesized: neutral ketone compound 1,2,2‐triphenylethanone (1) from NOSbF6 and coordination complex of Ag ion and aldehyde product ([Ag·22]+SbF6–) from AgSbF6. Single crystal X‐ray analyses reveal the different structure generated by different salt. UV/Vis absorption spectra and calculation demonstrate the formation of both compounds. It provides an example of chemoselectivity of Wagner–Meerwein 1,2‐shifts in pinacol rearrangement that depends upon different oxidant. [ABSTRACT FROM AUTHOR]