Remote Substituent Effects on Allylic and Benzylic Bond Dissociation Energies. Effects on Stabilization of Parent Molecules and Radicals

• Published in: Journal of organic chemistry 2007-09, Vol.72 (19), p.7091-7101
• Main Authors: Zavitsas, Andreas A, Rogers, Donald W, Matsunaga, Nikita
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Free radicals chemistry; Organic chemistry; Reactivity and mechanisms
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0707129

The effect of remote substituents on bond dissociation energies (BDE) is examined by investigating allylic C−F and C−H BDE, as influenced by Y substituents in trans-YCHCHCH2−F and trans-YCHCHCH2−H. Theoretical calculations at the full G3 level model chemistry are reported. The interplay of stabilization energies of the parent molecules (MSE) and of the radicals formed by homolytic bond cleavage (RSE) and their effect on BDE are established. MSE values of allyl fluorides yield an excellent linear free energy relationship with the electron-donating or -withdrawing ability of Y and decrease by 4.2 kcal mol-1 from Y = (CH3)2N to O2N. RSE values do not follow a consistent pattern and are of the order of 1−2 kcal mol-1. A decrease of 4.1 kcal mol-1 is found in BDE[C−F] from Y = CH3O to NC. BDE[YCHCHCH2−H] generally increases with decreasing electron-donating ability of Y for electron-donating groups and does not follow a consistent pattern with electron-withdrawing groups, the largest change being an increase of 3.6 kcal mol-1 from Y = (CH3)2N to CF3. The G3 results are an indicator of benzylic BDE in p-YC6H4CH2−F and p-YC6H4CH2−H, via the principle of vinylogy, demonstrated by correlating MSE of the allylic compounds with physical properties of their benzylic analogues.