Palladium-catalyzed direct β-arylation of ketones with diaryliodonium salts: a stoichiometric heavy metal-free and user-friendly approach

Abstract

A user-friendly protocol for the Pd-catalyzed direct β-arylation of ketones is described, which avoids the use of stoichiometric heavy metals.

Palladium-Catalyzed Aerobic Dehydrogenation of Cyclic Hydrocarbons for the Synthesis of Substituted Aromatics and Other Unsaturated Products

“…Additional synthetic opportunities have been realized through the use of Pd-catalyzed α,β-dehydrogenations of carbonyl compounds in tandem reactions, representative examples of which include dehydrogenation/Heck-type reactions of acyclic aldehydes and ketones 25 , chromanones, 26 and cyclic carbonyl compounds. 27 …”

Palladium‐Catalyzed Direct β‐C−H Arylation of Ketones with Arylboronic Acids in Water

“…In the latter case, electrophilic aryl iodides are employed in a palladium‐catalyzed β‐C−H arylation of ketones via a successive dehydrogenative oxidation and conjugate addition at elevated temperature (Scheme b‐1) . To avoid the stoichiometric silver‐based oxidant and air‐sensitive P( i ‐Pr) 3 ligand, hypervalent diaryliodonium salts were proven effective alternatives as both the oxidant and the aryl source (Scheme b‐2), although additional steps are required to synthesize diaryliodonium salts from aryl iodides or arylboronic acids…”

Allyl‐Palladium‐Catalyzed Ketone Dehydrogenation Enables Telescoping with Enone α,β‐Vicinal Difunctionalization

“…Instead, methods to obtain cycloalkanones with the β‐position functionalized have either relied on multistep sequences or more recently by conversion of ketones to activated intermediates such as enamines that can undergo oxidation to an allylic radical species or enones that can undergo conjugate addition . Through the use of palladium catalysis, Dong and co‐workers were able to functionalize in situ generated enone intermediates with aryl halides or diaryliodonium salts to provide β‐arylated ketones (Figure a). Su and co‐workers reported the addition of latent, stabilized nucleophiles, including malonates and sulfonamides, to enone intermediates generated from propiophenone derivatives by a copper‐catalyzed oxidation (Figure b) .…”