We report anew visible-light-mediated carbonylative amidation of aryl, heteroaryl, and alkyl halides.Atandem catalytic cycle of [Ir(ppy) 2 (dtb-bpy)] + generates ap otent iridium photoreductant through as econd catalytic cycle in the presence of DIPEA, whichp roductively engages aryl bromides,i odides,a nd even chlorides as well as primary, secondary,a nd tertiary alkyli odides.T he versatile in situ generated catalyst is compatible with aliphatic and aromatic amines,shows high functional-group tolerance,and enables the late-stage amidation of complex natural products.

An efficient nitro-Mannich type direct α-C(sp(3))-H functionalisation of N-aryl-1,2,3,4-tetrahydroisoquinolines catalysed by simple iron salts in combination with O2 as the terminal oxidant is described. The use of a Teflon AF-2400 membrane Tube-in-Tube reactor under continuous flow conditions allowed for considerable process intensification to be achieved relative to previous batch methods.

The abundance, structural diversity, and versatility of ketones give prominence to this carbonyl functional group in synthetic chemistry. The assembly of ketones via the carbonylative hydroacylation of alkenes represents a powerful modular strategy for the synthesis of unsymmetric ketone products. Here, we report the photocatalytic carbonylative hydroacylation of styrenes with unactivated alkyl halides. This protocol unifies the visible-light multiphoton catalytic cycle of [Ir­(ppy)2(dtb-bpy)]+ with flow chemistry to engage energy-demanding alkyl bromides and iodides at moderate pressures of carbon monoxide. The mild and practical methodology was employed to prepare a diverse array of 44 unsymmetric dialkyl ketones from primary, secondary, and tertiary unactivated alkyl halides. We demonstrate the application of flow chemistry technology to achieve spatially resolved chemoselectivity and broad functional group tolerance for the mild generation of functionalized C­(sp3)-rich ketone products.

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