| The first total synthesis of lactodehydrothyrsiferol, a selective inhibitor of protein phosphatase 2A, was accomplished through the application of our electron-transfer-initiated cyclization reaction. Other highlights of our synthetic strategy include a novel method for the formation of 1,1-disubstuted vinyl iodides from a terminal alkyne, a Suzuki-Miyaura cross coupling reaction on a iodinated allylic carbonate, a one pot diepoxidation of a diene to generate two epoxides with opposite stereochemical identities, an asymmetric Nozaki-Hiyama-Kishi reaction, and the selective deoxygenation of a triol. This document will focus on the key epoxide cascade and completion of the synthesis.;An oxidative method to form Carbon--Carbon bonds through Carbon--Hydrogen bond cleavage is described herein. Chromene and isochromene both form aromatically stabilized oxocarbenium ions in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The reactivity of these cations was explored with a variety of nucleophiles. In addition, the electronic properties were altered on the benzopyran ring system to elucidate the substrate scope for this transformation.;An oxidative method to form Carbon--Carbon bonds through Carbon--Hydrogen bond cleavage is described herein. Chromene and isochromene both form aromatically stabilized oxocarbenium ions in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The reactivity of these cations was explored with a variety of nucleophiles. In addition, the electronic properties were altered on the benzopyran ring system to elucidate the substrate scope for this transformation. |
