105018-90-4Relevant articles and documents
Photolytic Cleavage of Remote Functional Groups in Polyfunctional Molecules. Activation of a γ C-Cl Bond in the endo- and exo-Benzobicycloocten-3-yl Chlorides
Morrison, Harry,Muthuramu, Kayambu,Severance, Daniel
, p. 4681 - 4687 (2007/10/02)
The aryl-induced photolytic cleavage of a distal C-Cl bond, earlier reported for a β-substituent benzobicyclo (eq 1) and - (eq 2) substrates, has been extended to the γ position in the title compounds (endo-BBOC and exo-BBOC).Photolyses of these compounds in methanolic solution using 254-nm light primarily lead to products derived from carbocation intermediates (eq 4 and 5) with quantum efficiencies for loss of starting material φdis = 8.1 * 10-2 and 7.6 * 10-3 (endo and exo, respectively).The greater reactivity of the endo isomer contrasts with that observed in the and series where large exo/endo rate ratios are the rule (Table III).This inverted reactivity pattern is attributed to the favorable aryl/chlorine relationship in the endo isomer (Figure 1), which compensates for the increased Ar-C3 separation otherwise characteristic of these γ functionalities.
