Stability of 2-oxo and 2-methylene bridgehead carbocations in solvolysis: further evidence for the unimportance of .pi.-conjugative stabilization in tertiary .alpha.-keto cations

Evaluation of the π-conjugative effect o

Evaluation of the π-conjugative effect of the 2-methylene and the 2-oxo substituent on the stability of carbocations in the solvolysis of bicyclic bridgehead derivatives

✍ Ken'ichi Takeuchi; Fumio Akiyama; Keizo Ikai; Tadashi Shibata; Midori Kato 📂 Article 📅 1988 🏛 Elsevier Science 🌐 French ⚖ 280 KB

The cyano and carbonyl groups are strongly electron withdrawing (-I). However. in recent years considerable experimental and theoretical efforts have been made in evaluating the ITconjugative electron donation (+M) of these substituents toward cationic carbon (schemes 1 and 2).' As for the effect of