60th Annual Report on Research 2015

The no-cost extension for this grant was intended to enable us to keep up a few items that could not be completed in the allotted time due to change in personnel. I am pleased to report we were able to complete them. The primary body of work that was funded by this grant was focused on the development of an orgaocatalyzed, bi-functional catalyst of the construction of all-carbon quaternary centers. This grant paved the way for the Carter laboratory to secure a NSF award in this general area. Additionally, this grant is acknowledged for support on a submitted manuscript entitled Construction of Stereogenic alpha,alpha-Disubstituted Cycloalkanones Via Primary Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses. This manuscript is currently under review with ACS Catalysis. The output of this work was the development of an organocatalyzed, asymmetric Pfau d'Angelo reaction has been developed by exploiting a bifunctional primary amine thiourea catalyst system. Notable breadth in substrate scope was demonstrated on both the cyclic ketone moiety and the alpha,beta-unsaturated electrophile. Exploration into the matched and mismatched selectivity of this process with a ketone containing pre-existing stereocenters has been demonstrated. In addition, an important collaboration between the Carter laboratory and the Paul Ha-Yeon Cheong laboratory (Oregon State University) was nurtured through this grant. It specifically enabled us to work with them to conduct the computational analyses of this reaction mechanism. In concert with KIE experiments, these computational results provide a detailed understanding of the likely mechanism, including the aspects of the organocatalyst scaffold that are critical for stereoselectivity. In addition, this same collaboration spurned a new project focused on understanding another organocatalyzed process on desymmetrizing diol moieties. A manuscript of this work is currently in preparation.