UC Irvine

Chapter 1. Described herein is a study on the functional group tolerance of the gold/palladium dual catalyzed synthesis of 4-allylisocoumarins. A number of motifs commonly found in compounds with biological activity and intermediates towards such compounds were prepared and tested. The effect of silver on the product distribution was determined.

Chapter 2. A kinetic study of the alkoxyboration reaction showed the reaction is second order overall: first order with respect to both IPrAuTFA and NaTFA. NaTFA was determined to be both a Lewis base, by enhancing the nucleophilicity the B–O σ bond, and as a reagent needed to decrease the amount of IPrAuTFA converted to the catalytically inactive IPrAuCl. Increasing the amount of trifluoroacetate eventually lead to a decrease in the reaction rate. This effect is attributed to over addition of the Lewis base into the borate ester that is formed after the cyclization step. The rate-determining step was determined to be the transmetalation step.