Rh()-catalyzed site-selective hydroacylation of alkenyl-bearing allylic alcohols with non-chelating aldehydes controlled by generated carbonyl group

A rhodium( i )-catalyzed regioselective hydroacylation of alkenyl-bearing allylic alcohols with simple aldehydes for the preparation of diverse 1,5-diketones is described. Mechanistic investigation suggests that this transformation might proceed through redox isomerization of the allylic alcohol followed by hydroacylation of the resulting enone with aldehyde involving a stable six-membered rhodacycle intermediate. This protocol highlights the role of in situ generated carbonyl group in controlling the site-selectivity of the intramolecular alkene moiety. A rhodium( i )-catalyzed hydroacylation process allows the regioselective synthesis of 1,5-diketones from alkenyl-bearing allylic alcohols involving a stable six-membered rhodacycle intermediate.