A remarkable [2.2.2]propellane

Yigang He; Christopher P Junk; John J Cawley; David M Lemal

doi:10.1021/ja030077y

A remarkable [2.2.2]propellane

J Am Chem Soc. 2003 May 14;125(19):5590-1. doi: 10.1021/ja030077y.

Authors

Yigang He¹, Christopher P Junk, John J Cawley, David M Lemal

Affiliation

¹ Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA. david.m.lemal@dartmouth.edu

PMID: 12733871
DOI: 10.1021/ja030077y

Abstract

To explore the effects of fluorine substitution on the highly strained [2.2.2]propellane skeleton, a new representative of this ring system, perfluorotricyclo[2.2.2.01,4]octan-2-one ethylene ketal, was prepared by a rapid and quantitative [2+2] cycloaddition to the strained alkene perfluorobicyclo[2.2.0]hex-1(4)-ene. The propellane displays impressive thermal stability, and the vulnerable C-C bond joining the bridgeheads is very resistant to attack by electrophilic reagents. On the other hand, that electron-deficient bond is cleaved quickly at room temperature by a variety of nucleophiles and mild reducing agents. The behavior of this compound contrasts dramatically with that of the only known [2.2.2]propellane lacking fluorine substituents.