Copper(i)-catalyzed radical carboamination reaction of 8-aminoquinoline-oriented buteneamides with chloroform: synthesis of-β-lactams

Abstract

A novel Cu(CH3CN)4PF6-catalyzed carboamination reaction of 8-aminoquinoline-oriented buteneamides with chloroform to afford 4-(2,2,2-trichloroethyl)-β-lactams is described.

Divergent regioselective Heck-type reaction of unactivated alkenes and N-fluoro-sulfonamides

“…2). Of note, under reaction conditions C excluding the aforementioned promoting factors, the β-lactams 5 would dominate the product distribution through a reductive elimination of the high-valent copper intermediate 79 , a process previously observed independently by Zhao 80,81 , He/Chen/Wang 82,83 , and Quan/Liang/Wang 43 in alkylamination of unactivated alkenes. As demonstrated in Fig.…”

“…The resultant amidyl radical II is a highenergy species 77,91,92 , which undergoes an intramolecular HAT with remote δ-C(sp 3 )−H bond to form a carbon-centered radical IV 93 . Radical addition of IV to the olefin moiety of Cu(II) intermediate III results in the formation of a secondary carbon-centered radical, which can rapidly recombine with the nearby Cu(II) center to produce the key Cu(III) intermediate V 34,41,43,45,46,49,50,53,[80][81][82][83] . At this point, there are three potential reaction pathways from V to provide different products depending on the choice of external additives.…”

Directed Copper-Catalyzed Tandem Radical Cyclization Reaction of Alkyl Bromides and Unactivated Olefins

“…In 2018, Fu’s group developed the first copper-catalyzed Heck-type reaction of alkyl halides and unactivated olefins (Scheme a) . After that, Zhao’s group reported a copper-catalyzed cascade reaction for constructing various β-lactam backbones (Scheme b) . Nevertheless, despite the obvious attractiveness of research on unactivated olefins, certain challenges remain for the retention of active double bonds and the introduction of new small active ring skeletons in double bonds.…”