The asymmetric total synthesis of (+)-geniposide via phosphine-catalyzed [3+2] cycloaddition

The iridoids are a large family of monoterpenoid natural products that possess a wide range of biological activities. A great deal of research has already been done in the field of iridoid total synthesis, but limitations still remain. Specifically, few syntheses of iridoid β-glycosides have been reported. This work describes the 14 step asymmetric total synthesis of the iridoid β-glycoside (+)-geniposide utilizing a phosphine-catalyzed [3+2] cycloaddition as the key step. Other noteworthy steps in the synthesis include a palladium-catalyzed kinetic resolution and a previously unutilized method for iridoid glycosidation. In addition to describing the synthesis of (+)-geniposide, this dissertation will also review 1) phosphine-catalyzed cycloaddition reactions and 2) previous enantioselective total syntheses of iridoid glycosides.