The reactions of aryl acrylates under Baylis-Hillman conditions

Baylis−Hillman Mechanism: A New Interpretation in Aprotic Solvents

“…[26][27][28][29] These byproducts result when hemiacetal intermediates 7 or 9 undergo intramolecular transesterification with the ester, forming a six-membered ring (Scheme 3). As expected, the dioxanone byproducts form only when the acrylate is an activated ester.…”

α‐exomethylene lactone possessing acetal–ester linkage: Polymerization and postpolymerization modification for water‐soluble polymer

“…According to the literature, DMDO was prepared through the Baylis–Hillman reaction between phenyl acrylate and acetaldehyde . Since the liberated phenol has similar polarity and boiling point with DMDO, however, the purification was found troublesome.…”

“…Along the line of this concept, herein, we have designed a new monomer; that is, an α‐functionalized acrylates which has a feature of EMLs possessing acetal–ester (A–E) linkage in its lactone skeleton. Among them, a simple example, 2,6‐dimethyl‐5‐methylene‐1,3‐dioxa‐4‐one (DMDO) can be synthesized via Bailys–Hilman reaction of phenyl acrylate, but no application in polymer chemistry are reported. As well known, A–E linkage is a dynamic covalent bond, which is readily converted to carboxyl and hydroxyl groups by acid hydrolysis, while the thermal decomposition affords a carboxylic acid and a vinyl ether .…”

A novel self-promoted Morita-Baylis-Hillman-like dimerization

“…Nucleophilic catalysts such as DABCO, DBU, and n-Bu 3 P are frequently employed [20]. Slow reaction rates [20], autocatalysis in the absence of proton donors [22], formation of dioxanones [26,27], and the rate acceleration observed in protic solvents [28][29][30][31][32] are intriguing aspects of the MBH reaction, and recent DFT studies have begun to provide useful mechanistic insights [33][34][35].Scheme 1 Morita-Baylis-Hillman (MBH) reaction. EWG: electronwithdrawing group.…”

“…Nucleophilic catalysts such as DABCO, DBU, and n-Bu 3 P are frequently employed [20]. Slow reaction rates [20], autocatalysis in the absence of proton donors [22], formation of dioxanones [26,27], and the rate acceleration observed in protic solvents [28][29][30][31][32] are intriguing aspects of the MBH reaction, and recent DFT studies have begun to provide useful mechanistic insights [33][34][35] A few examples of dimerization reactions have been reported, but they require a catalyst [36][37][38][39], or high temperature [39], or high pressure [40]. We report the unusual case of a self-promoted dimerization of a triarylphosphine-substituted vinylphenyl-ketone 1, which we have been exploring as a ligand in Pd-catalyzed reactions [41][42][43].…”