Diffusion Controlled Hydrogen Atom Abstraction from Tertiary Amines by the Benzyloxyl Radical. The Importance of C-H/N Hydrogen Bonding

作者：Salamone Michela; Anastasi Gloria; Bietti Massimo^*; DiLabio Gino A

来源：Organic Letters, 2011, 13(2): 260-263.

DOI：10.1021/ol102690u

The rate constants for H-atom abstraction (k(H)) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO(center dot)) and benzyloxyl (BnO center dot) radicals were measured. Comparable k(H) values for the two radicals were obtained in their reactions with CHD and TIBA whereas large increases in k(H) for TEA and DABCO were found on going from CumO(center dot) to BnO center dot. These differences are attributed to the rate-determining formation of BnO center dot C-H/amine N lone-pair H-bonded complexes.

• 出版日期2011-1-21