1225222-52-5Relevant articles and documents
Delineating origins of stereocontrol in asymmetric Pd-catalyzed α-hydroxylation of 1,3-ketoesters
Smith, Alexander M. R.,Rzepa, Henry S.,White, Andrew J. P.,Billen, Denis,Hii, King Kuok
supporting information; experimental part, p. 3085 - 3096 (2010/07/17)
Systematic studies of reaction conditions and subsequent optimization led to the identification of important parameters for stereoselectivity in the asymmetric α-hydroxylation reaction of 1,3-ketoesters. Enantioselectivities of up to 98% can be achieved for cyclic substrates and 88% for acyclic ketoesters. Subsequently, the combination of cyclic/acyclic ketoester, catalyst, and oxidant was found to have a profound effect on reaction rates and turnover-limiting steps. The stereochemistry of the reaction contradicts that observed for other similar electrophilic substitution reactions. This was rationalized by transition-state modeling, which revealed a number of cooperative weak interactions between oxidant, ligand, and counterion, together with C-H/π interactions that cumulatively account for the unusual stereoselectivity.
