Novel Reactivity in Hypervalent Iodine-Mediated Arylations and Vinylations

WEBINAR

The lecture will focus on our recently developed diarylation cascade methodology yielding diaryl ethers, diarylamines and triarylamines with excellent atom economy. In this reaction, both aryl groups in diaryliodonium salts are efficiently transferred to amines and water under mild and transition metal-free conditions. The reaction follows a novel mechanistic pathway with initial nucleophilic aromatic substitution and a subsequent intramolecular aryl transfer.

The chemistry of our recently discovered hypervalent iodine(III) reagents vinylbenziodoxolones (VBX) will also be presented. This compound class is an efficient vinylating agent with various nucleophiles under mild conditions, without need for a transition metal catalyst or excess reagents. Interestingly, internal or terminal alkene products are regioselectively formed, depending on the nucleophile. Our results in the C-vinylation of nitroalkanes, P-vinylation of phosphine oxides and H-phosphinates and S-vinylation of thiols and mercaptothiazoles will be discussed, together with a mechanistic study to rationalize the regio- and stereoselectivity.

Learning points:

• Learn the chemistry of recently discovered hypervalent iodine(III) reagents vinylbenziodoxolones (VBX)
• Learn how the hypervalent Iodine (III) reagent perform in diarylation cascade methodology yielding diaryl ethers, diarylamines and triarylamines with excellent atom economy