Kinetic resolution in rhodium-catalyzed [5+2] cycloisomerization

This thesis demonstrates the ability of a rhodium(I)-phosphoramidite catalyst to effect the first examples of kinetic resolution in [5+2] cycloisomerization (Scheme i). This methodology was applied to a range of diversely substituted enyne substrates, including a novel chiral silane tether. Depending on the substrate, either a classical resolution, or a diastereodivergent resolution was achieved, both with exceptional selectivity. Furthermore, this methodology was applied to the asymmetric synthesis of the natural product (+)- dictamnol, a trinorguaiane sesquiterpene isolated from the roots of Dictamnus dascarpus TURCZ, with diastereodivergent resolution of an allene vinylcyclopropane as the key step.