84537-35-9Relevant articles and documents
Palladium-Catalyzed Allylic Alkylation of 2-Aryl-1,3-Dithianes, an Umpolung Synthesis of β,γ-Unsaturated Ketones
Trongsiriwat, Nisalak,Li, Minyan,Pascual-Escudero, Ana,Yucel, Baris,Walsh, Patrick J.
, p. 502 - 509 (2019)
Palladium-catalyzed allylic alkylation of 2-aryl-1,3-dithianes at room temperature is described. A variety of cyclic and acyclic electrophiles successfully coupled with in-situ generated 2-sodio-1,3-dithiane nucleophiles to afford the allylated products in good to excellent yields (25 examples). Deprotection of these products leads to valuable β,γ-unsaturated ketones. Direct synthesis of such β,γ-unsaturated ketones via a one-pot allylation-oxidation protocol is also presented. Investigation into the stereochemistry of the allylation reaction revealed that the 2-sodio-1,3-dithiane nucleophile behaves as a “soft” nucleophile, which underwent external attack on the π-allyl palladium complex to provide retention of stereochemistry (double inversion pathway). Additionally, the utility of this method was demonstrated through a sequential one-pot allylation-Heck cyclization to produce asterogynin derivatives, which are important bioactive compounds in medicinal chemistry. (Figure presented.).
Sulfur-directed olefin oxidations: Observation of divergent reaction mechanisms in the palladium-mediated acetoxylation of unsaturated thioacetals
Mann, Sam E.,Aliev, Abil E.,Tizzard, Graham J.,Sheppard, Tom D.
scheme or table, p. 1772 - 1775 (2011/06/22)
The Pd-mediated oxidation of unsaturated thioacetals gives either allyl or vinyl esters, depending on the substrate structure. We report the characterization of a range of sulfur-stabilized palladium intermediates via a combined computational and experime
