A new palladium‐catalyzed selective aminomethylation of conjugated 1,3‐dienes with aminals via double C—N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear α,β‐unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C—N bond to furnish a cascade double C—N bond activation, in which an allylic 1,3‐diamine and allylic 1,2‐diamine were initially formed as key intermediates through the palladium‐catalyzed C—N bond activation of aminal and the α,β‐unsaturated allylic amine was subsequently produced via palladium‐catalyzed C—N bond activation of the allylic diamines.
An efficient new formal insertion strategy via combination of reductive elimination and oxidative addition sequence was reported, in which the transient N-acyliminium ions formed via hydrocarbonylation function as key intermediates. This strategy has enabled a novel palladiumcatalyzed hydrocarbonylative cyclization of azaarene-tethered alkenes or dienes via sequential insertion of a CC bond, CO, and a CN bond into palladium−hydride bonds. This method provides a new and highly efficient synthetic approach to quinolizinones and its derivatives with extended π-conjugated systems, possessing tunable emission wavelengths and good photoluminescence capabilities.
Lewis acid enables the electrophilic carbooxygenative cyclization of alkynols with N,O-aminals. The new process proceeds efficiently under very mild conditions via a pathway that is opposite to classical carbo-metalation. These reactions exhibit broad substrate generality and functional group compatibility, leading to a wide variety of 5−8-membered oxacycles bearing diverse functional groups. The cyclization products can be elaborated via simple functional group transformations to generate synthetically useful oxacycles.
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