NONCONJUGATED CHARGE DELOCALIZATION BY REMOTE PI-ELECTRONS VIA RELAY THROUGH A DOUBLE-BOND PROXIMATE TO A SOLVOLYSIS CENTER

Diene 1 is of considerable fundamental interest regarding our understanding of factors which influence chemical reactivity because of its remarkably high reaction rate in solvolysis. Comparison of 1 with the historic anti-7-norbornenyl and 7-norbornyl systems1 shows the relative rate ratio to be 1014:1011:l (at 25ΰC), respectively.2 The enormous reactivity of 1 was attributed to -electron participation of the remote C4C5 double bond by relay through the C9C10 double bond to give the extensively charge delocalized carbocation 2.2 Theoretical calculations agree with this and predict 2 to have considerable extra stabilization.3 However, it has been claimed by Paquette and Dunkin4 that, owing to leveling of the rate ratios, the three-carbon C9C10C11 network shown in 3 prevails and C4=C5 does not anchimerically assist ionization. © 1979, American Chemical Society. All rights reserved.