Redox-Neutral Multicatalytic Cerium Photoredox-Enabled Cleavage of O-H Bearing Substrates.

The need for synthetic methodologies capable of rapidly altering molecular structure are in high demand. Most existing methods to modify scaffolds rely on net exothermicity to drive the desired transformation. We sought to develop a general strategy for the cleavage of C-C bonds β to hydroxyl groups independent of inherent substrate strain.

Formal Synthesis of (±)-Salvinorin A via Gold(I) Catalysis.

The formal synthesis of (±)-salvinorin A is presented. Our approach utilizes two distinct gold(I) catalytic processes. The combination of a gold(I)-catalyzed reaction with an intermolecular Diels-Alder reaction followed by a gold(I)-catalyzed photoredox reaction generated in eight steps the framework of the natural product with high diastereoselectivity.

Total Synthesis of Ginkgolide C and Formal Syntheses of Ginkgolides A and B.

Ginkgolides are diterpenes isolated from that exhibit strong anti-inflammatory and neuroprotective properties. The highly complex molecular architecture of ginkgolides, combined with their remarkable biological profile, provides a unique platform for the development of new strategies and methods. Herein, we reported the first total synthesis of ginkgolide C and the formal syntheses of ginkgolides A and B.

Divergent and Modular Synthesis of Terpenoid Scaffolds via a Au Catalyzed One-Pot Cascade.

A one-pot cascade sequence to generate synthetically challenging polycyclic scaffolds is reported utilizing a novel Lewis acid gold catalyst for the key cyclization step, enabling the divergent synthesis of both 6,6,5-tricyclic and 6,6,6,5-tetracyclic cores through both ligand and reaction condition control. We have combined the intrinsic complexity and stereoselectivity of cycloadditions with the electronic and steric properties of gold complexes to selectively generate complex polycyclic scaffolds in a single operation.

Formal Bromine Atom Transfer Radical Addition of Nonactivated Bromoalkanes Using Photoredox Gold Catalysis.

Organic transformations mediated by photoredox catalysis have been at the forefront of reaction discovery. Recently, it has been demonstrated that binuclear Au(I) bisphosphine complexes, such as [Au(μ-dppm)]X, are capable of mediating electron transfer to nonactivated bromoalkanes for the generation of a variety of alkyl radicals. The transfer reactions of bromine, derived from nonactivated bromoalkanes, are largely unknown.