4,5-dehydro- and 4,5,15,16-bis(dehydro)octafluoro[2.2]paracyclophanes: facile generation and extraordinary Diels-Alder reactivity

J Org Chem. 2003 Apr 18;68(8):3078-83. doi: 10.1021/jo0268815.

Abstract

Dehydroiodination of 4-iodo- and 4,15-diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane by treatment with KO(t)Bu in the presence of benzene, naphthalene, anthracene, and [2.2]paracyclophane affords each of the corresponding Diels-Alder mono- and bis-cycloadducts derived from the presumed aryne intermediates in high yield. Monoadducts of t-butylbenzene and furan are also obtained in excellent yield. All of the products were characterized by their NMR spectra, with four of them also being confirmed by X-ray crystallography. The extraordinary selectivity/reactivity of the aryne intermediate is discussed.