Regio- and Chemoselective Double Allylic Substitution of Alkenyl vic-Diols.

Double allylic substitution is an attractive approach to building molecular complexity from simple starting materials by creating two new bonds in one pot. However, this type of reaction has been doomed by chemoselectivity and regioselectivity issues. In this letter, we describe a new approach to introduce a-la-carte two new C-C, C-N, C-O, or C-S bonds in a chemo- and regioselective fashion. The reaction relies on sequential dual catalysis with a Lewis acid and palladium. The scope is remarkably broad, and the reaction can be diastereoselective by using secondary alcohols as the first nucleophile.

Copper-Catalyzed Regio- and Stereoselective Hydrothiolation of Allenamides, Enamides, and Ynamides.

We report a simple protocol for the copper-catalyzed hydrothiolation of N-unsaturated precursors, i.e., allenamides, enamides, and ynamides, under mild conditions. This method proceeds with a low loading of a commercially available Cu(CH3CN)4PF6 catalyst and enables the room-temperature transformation of a wide range of aromatic and aliphatic thiols into allylic or vinylic thioethers, 1,3-dithioethers, and thioaminals with good regio- and stereoselectivity.

Easy Access to Allylic Sulfones Through Transition-Metal-Free Hydrosulfonylation Of Allenes.

A Brønsted acid-mediated addition of (hetero)aryl and (cyclo)alkyl sodium sulfinates to N-allenyl derivatives, which proceeds in water, is described under very smooth conditions. This reaction provided a practical and efficient protocol for the regio- and stereoselective synthesis of allylic sulfones in an atom- and step-economic fashion.