Divergent and Modular Synthesis of Terpenoid Scaffolds via a AuI 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.

Single-Electron Transfer from Dimsyl Anion in the Alkylation of Phenols.

While attempting to synthesize biaryl ethers we discovered the inadvertent formation of a methylsulfoxylmethyl ether byproduct. Formation of this unexpected byproduct presented an opportunity to streamline the synthesis of methylsulfoxylmethyl ethers. Mechanistic studies suggest a radical pathway with dimsyl potassium as a reducing agent.

Functional primary amines and diamines from alpha-aminoacids. a concise route to substituted 2-aminotetralins.

S-Phthalimidomethyl xanthates derived from various alpha-amino acids add efficiently to a range of unactivated alkenes to give a variety of highly functionalized, protected amines. In the case of phenylalanine and tyrosine derived xanthates, the adducts can be further converted into the rare 4-substituted 2-aminotetralines by a radical ring closure onto the aromatic ring.

A convergent radical-based route to biaryls.

A route to biaryl-3-carboxylate esters involving a radical 1,2-aryl migration has been developed. This strategy hinges on the radical addition of xanthate 2 to olefin 1 causing a 1,2-aryl shift leading to alpha,beta-unsaturated ester 5, which is then converted into biaryl 10 by treatment with DBU under microwave heating.