Although arguably the most important reaction in glycoscience, chemical glycosylations are among the least well understood of organic chemical reactions, resulting in an unnecessarily high degree of empiricism and a brake on rational development in this critical area. To address this problem, primary (13)C kinetic isotope effects have now been determined… (More)
Persistent free radicals have become indispensable in the synthesis of organic materials through living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Here, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and… (More)
Calculations on the propagation steps in the radical chain oxidation of lipids (H-atom abstraction, O(2) addition) show that secondary orbital interactions play an important role in the structure and energetics of the transition states of these reactions.