Diversity-oriented synthesis of fluoroalkylated amines via the palladium-catalyzed divergent fluoroalkylamination of 1,3-dienes

Abstract

Herein, we reported the first versatile and expeditious protocol for the diversity-oriented synthesis (DOS) of fluoroalkylated amines via the photoinduced palladium-catalyzed cross coupling of 1,3-dienes, amines and fluoroalkyl iodides, which...

Metal-free photosensitized radical relay 1,4-carboimination across two distinct olefins

“…5 Moreover, with the development of photochemistry, 6 modern visible light-mediated methods for 1,4-carboaminations have recently gradually emerged. 7–9 In a notable example, Sarlah and coworkers demonstrated an elegant strategy for the stepwise syn -1,4-carboamination of simple arenes by the combination of photoinduced cycloaddition and palladium-catalyzed ring-opening substitution. 7 Very recently, we have realized a palladium-catalyzed 1,4-carboimination of 1,3-dienes with alkylcarboxylic acid-derived bifunctional reagents through a single electron transfer (SET) approach mediated by visible light (Scheme 1B).…”

“… 8 Based on this strategy, the palladium-catalyzed three component 1,4-carboamination of 1,3-dienes with haloalkanes and nitrogen nucleophiles has been subsequently achieved by other groups and us. 9 Although these reactions are versatile, they require the use of transition metals (especially palladium), as catalysts. Moreover, the utilization of unstable 1,3-dienes as starting materials further restricts the general appeal of these protocols.…”

Regio-, Site-, and Stereoselective Three-Component Aminofluorination of 1,3-Dienes via Cooperative Silver Salt and Copper Catalysis

“…Compared to electronically activated aryl-1,3-dienes, the selective control of less reactive alkyl-1,3-dienes is more elusive due to dissymmetrical η 3 -π-allyl intermediates, , which would lead to the nonselective generation of 1,2- and 1,4-products, and E- / Z -isomers. − This phenomenon has been fully embodied in the intermolecular aminodifunctionalization of 1,3-dienes (Figure b). Despite encouraging progress in the last decade, most works have focused on either aryl-1,3-dienes − or two-component reactions of alkyl-1,3-dienes using dual-function amino reagents. − In comparison, only a few three-component aminodifunctionalization reactions of alkyl-1,3-dienes have been evaluated on account of low reaction efficiencies and selectivities. Bäckvall and co-workers took a seminal work on 1,4-diamination of butadiene and 1,3-cyclohexadiene via a stoichiometric π-allylpalladium complex .…”

Nickel-Catalyzed, Enantioselective Hydrofluoromethylation of Olefins: Access to Chiral α-Fluoromethylated Amides and Esters

“…Our group and others have used ICH 2 F in a variety of fluoromethylation reactions. With our continued interest in developing new fluoroalkylation methodalogies, we then further sought to employ the ICH 2 F system in combination with a suitable chiral nucleophile species to realize the enantioselective fluoromethylation. Hydrofluoromethylation is an appealing strategy for the enantioselective introduction of a fluoromethyl group to an olefin.…”