[摘要]：We report here that the monodentate complexation of Me2AlCl to an ester group significantly enhances the selectivity of hydrogen transfer on acyclic radicals flanked by both an ester functionality and a stereogenic center, leading to C-2,C-3-anti products with high diastereoselectivity. In certain cases improved ratios were obtained using bulkier aluminum Lewis acid such as MAD (methylaluminum-di(di-2,6-tert-butyl-4-methylphenoxide)). ESR studies on these acyclic radicals indicate that Lewis acid complexation leads to conformational changes in the radicals. The stereochem. of the preferred enolate radicals complexed with Lewis acids and their impact on the acyclic transition states involved are suggested.
