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The ability to selectively functionalize ubiquitous C-H bonds streamlines the construction of complex molecular architectures from easily available precursors. Here we report enzyme catalysts derived from a cytochrome P450 that use a nitrene transfer mechanism for the enantioselective amination of primary, secondary and tertiary C(sp3)-H bonds. These fully genetically encoded enzymes are produced and function in bacteria, where they can be optimized by directed evolution for a broad spectrum of enantioselective C(sp3)-H amination reactions. These catalysts can aminate a variety of benzylic, allylic and aliphatic C-H bonds in excellent enantioselectivity with access to either antipode of product. Enantioselective amination of primary C(sp3)-H bonds in substrates that bear geminal dimethyl substituents furnished chiral amines that feature a quaternary stereocentre. Moreover, these enzymes enabled the enantioconvergent transformation of racemic substrates that possess a tertiary C(sp3)-H bond to afford products that bear a tetrasubstituted stereocentre, a process that has eluded small-molecule catalysts. Further engineering allowed for the enantioselective construction of methyl-ethyl stereocentres, which is notoriously challenging in asymmetric catalysis.

A method was developed for ketone synthesis via a photoredox‐assisted reductive acyl cross‐coupling (PARAC) using a nickel/photoredox dual‐catalyzed cross‐electrophile coupling of two different carboxylic acid esters. A variety of aryl, 1°, 2°, 3°‐alkyl 2‐pyridyl esters can act as acyl electrophiles while N‐(acyloxy)phthalimides (NHPI esters) act as 1°, 2°, 3°‐radical precursors. Our PARAC strategy provides an alternative and reliable way to synthesize various sterically congested 3°‐3°, 3°‐2°, and aryl‐3° ketones under mild and highly unified conditions, which have been otherwise difficult to access. The combined experimental and computational studies identified a Ni0/NiI/NiIII pathway for ketone formation. [ABSTRACT FROM AUTHOR]

In this work, we develop an oxidation-induced C–H functionalization strategy, which not only leads to a new avenue to build C–N bonds, but also leads to different site-selectivity compared with “classic directing-groups”. The high selectivity of our new catalytic system originates from the heterogeneous electron-density distribution of the radical cation species which are induced by single electron transfer between the aromatics and oxidant-Cu(ii) species. [ABSTRACT FROM AUTHOR]

In this study, we broke through the directing function of the amide group. The coordination interaction between metal and directing-group enhanced the reactivity of the substrate. Using this strategy, we realized the selective amination of 8-aminoquinolines at the C5 position via employing azoles as the source of amine. Various kinds of 8-aminoquinolines and different substituted azoles were compatible to afford the corresponding C–N coupling products. [ABSTRACT FROM AUTHOR]

The title reaction is optimized and the mechanism in the presence of the Ni catalyst is investigated and discussed in detail. [ABSTRACT FROM AUTHOR]