Journal of Organic Chemistry p. 4681 - 4687 (1986)
Update date:2022-07-29
Topics:
Morrison, Harry
Muthuramu, Kayambu
Severance, Daniel
The aryl-induced photolytic cleavage of a distal C-Cl bond, earlier reported for a β-substituent benzobicyclo<2.2.1> (eq 1) and -<2.2.2> (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 <2.2.1> and <2.2.2> 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.
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