Development of a Dual-Catalysis Approach to Olefin Carbo-Difunctionalization using tert-Alkyl Hemioxalates

University Of California-Irvine, Irvine CA

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Abstract

Project Summary/Abstract Quaternary stereocenters are prevalent structural motifs that are found in countless molecules of biological importance. For example, quaternary carbons are salient features of valuable therapeutic classes such as steroid hormones and opioid analgesics, embodied by the medicinally useful natural products cortisone and morphine, respectively. Despite the significance of quaternary stereocenters in medicines, there are few methods that allow efficient access to these moieties. Thus, methodologies that furnish one or more quaternary carbons are highly sought after, especially those that unite multiple complex fragments in a single chemical step. The proposed research aims to synergistically utilize visible light photoredox catalysis and group 10 metal catalysis for the carbo-difunctionalization of electron-deficient olefins, forging two new carbon? carbon bonds and at least one quaternary center in a single transformation. Although photoredox catalysis has been employed to generate tertiary radicals from readily available tert-alkyl hemioxalates, allowing for subsequent conjugate addition reactions, this reactivity paradigm has never been employed in a dual catalysis manifold. Realization of such a reactivity platform should permit the generation of polyfunctionalized products containing multiple quaternary centers. Moreover, it is envisioned that the proposed dual catalysis system could be utilized as a key step in the total synthesis of the complex ent-kaurene diterpenoid, sculponeatin N.