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

Abstract

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...

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

“…Encouraged by zhang's work on the hydroacylation of vinyl cyclobutanol, [20] we achieved the regioselective hydroacylation of alkenyl‐substituted allylic alcohols 52 with simple aromatic aldehydes 51 to furnish a variety of 1,5‐diketones ( 53 and 54 ) under the rhodium catalysis (Scheme 9). [54] A number of allylic alcohols substituted with aryl, heteroaryl, and alkyl groups are suitable substrates for the coupling reaction, providing the desired diketones ( 53 a – 53 e ) in moderate to good yields. It should be noteworthy that the reaction of homoallyl‐substituted allylic alcohol gave a branched product 54 , which provides some clues to the possible pathway.…”