Computational ligand design in enantio- and diastereoselective ynamide [5+2] cycloisomerization.

ABSTRACT: Transition metals can catalyse the stereoselective synthesis of cyclic organic molecules in a highly atom-efficient process called cycloisomerization. Many diastereoselective (substrate stereocontrol), and enantioselective (catalyst stereocontrol) cycloisomerizations have been developed. However, asymmetric cycloisomerizations where a chiral catalyst specifies the stereochemical outcome of the cyclization of a single enantiomer substrate--regardless of its inherent preference--are unknown. Here we show how a combined theoretical and experimental approach enables the design of a highly reactive rhodium catalyst for the stereoselective cycloisomerization of ynamide-vinylcyclopropanes to [5.3.0]-azabicycles. We first establish highly diastereoselective cycloisomerizations using an achiral cat

SUBMITTER: Straker RN 

PROVIDER: S-EPMC4728367 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature