20633-40-3Relevant academic research and scientific papers
TYPE II PHOTOREACTIONS OF α-ALKYL β-OXOESTERS. NEIGHBORING GROUP EFFECT ON 1,4-BIRADICAL REACTIONS AND EFFECTIVE INTERNAL FILTER EFFECT BY THE TYPE II PHOTOPRODUCT
Hasegawa, Tadashi,Arata, Yoshiaki,Endoh, Masaru,Yoshioka, Michikazu
, p. 1667 - 1674 (1985)
The α-alkyl β-oxoesters 1 undergo type II photoreactions.The process of back hydrogen transfer in the 1,4-biradical intermediate to revert to the starting ester is suppressed because of the intramolecular hydrogen bonding between the hydroxyl and carboalkoxyl groups in the biradical intermediate.The hydrogen bonding determines the stereochemistry of 1,4-biradical cyclization.The cyclobutanols having the hydroxyl group cis to the carboalkoxyl group are formed exclusively from the α-alkyl β-oxoesters 1.The enol form of the type II elimination product, the benzoylacetate 2, acts as an effective internal filter for the photoreaction of the α-alkyl β-oxoester 1.
Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (-)-Aspewentins A, B, and C
Liu, Yiyang,Virgil, Scott C.,Grubbs, Robert H.,Stoltz, Brian M.
supporting information, p. 11800 - 11803 (2015/10/05)
The direct α-vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that δ-oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium-catalyzed decarbonylative dehydr
