Exploration of Aryl Phosphates in Palladium-Catalyzed Mono-α-arylation of Aryl and Heteroaryl Ketones

Abstract

This paper presents the first general examples of selective palladium-catalyzed mono-α-arylation of aryl and heteroaryl ketones with aryl phosphates. The catalyst system, consisting of [Pd(2-butenyl)Cl] 2 and MorDalPhos, exhibited high catalytic reactivity toward this reaction. A wide range of aryl phosphates were efficiently coupled with aryl and heteroaryl ketones with good selectivity. Excellent-to-good product yields were afforded. The gram-scale reaction was conducted smoothly. Reductive elimination or transmetalation might be a rate-determining step in this reaction.

Photocatalytic Coproduction of Deoxybenzoin and H2 through Tandem Redox Reactions

“…The process requires functionalization of phenylacetic acid to phenylacetyl chloride by stoichiometric PCl 3 or SOCl 2 prior to the C–C bond coupling. , Other reported methods required the prefunctionalization of starting molecules or use expensive substrates alternatively (Scheme S1). − Thus, it is desirable to develop processes for DOB production using readily available and environmentally benign feedstocks. Moreover, if H 2 is also produced in the conversion of BAL to DOB, the whole process will achieve the coproduction of a clean energy vector and a very high value-added product. − …”

Ligand Control of Palladium‐Catalyzed Site‐Selective α‐ and γ‐Arylation of α,β‐Unsaturated Ketones with (Hetero)aryl Halides

“…Based on these observations and our previous studies, we hypothesize that the garylation of a,b-unsaturated ketones, which is similar to the direct a-arylation of ketones, maybe also a Csp 2 -Csp 3 reductive elimination-demanding reaction. [10,12] From our and other authors previous works on a-arylation of ketones, [10,13] palladium complexes containing strong, electron-donating ancillary ligands (e.g., -PCy 2 ) tend to undergo Csp 2 -Csp 3 reductive elimination reaction more slowly than complexes containing weakly electron-donating ancillary ligands (e.g., -PPh 2 ). We believe that for ligand scaffold with an appropriate steric induced via the bottom ring, the alternation of electron density may provide a significant inference towards the regioselectivity and give the siteselective a-or g-arylated product.…”

Photocatalytic Pinacol C–C Coupling and Jet Fuel Precursor Production on ZnIn2S4 Nanosheets

“…Functionalization of phenylacetic acid to form phenylacetyl chloride is a prerequisite for this process and stoichiometric PCl 3 or SOCl 2 as the chlorine source is needed. Even though alternative processes have been reported, they typically require expensive reagents or complex pre-functionalization steps. − Hence, our photocatalytic C–C coupling for the one-step synthesis of benzoin and deoxybenzoin represents a great advance in their green production if high selectivity for each product could be achieved.…”