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A direct enantioselective acylation of α-amino C(sp 3 )−H bonds with carboxylic acids has been achieved via the merger of transition metal and photoredox catalysis. This straightforward protocol enables cross-coupling of a wide range of carboxylic acids, one class of feedstock chemicals, with readily available N-alkyl benzamides to produce highly valuable α-amino ketones in high enantioselectivities under mild conditions. The synthetic utility of this method is further demonstrated by gram scale synthesis and application to late-stage functionalization. This method provides an unprecedented solution to address the challenging stereocontrol in metallaphotoredox catalysis and C(sp 3 )−H functionalization. Mechanistic studies suggest the α-C(sp 3 )−H bond of the benzamide coupling partner is cleavage by photocatalytically generated bromine radicals to form α-amino alkyl radicals, which subsequently engages in nickel-catalyzed asymmetric acylation.

Trace amounts of ionic liquids have been mixed in sulfuric acid to enhance the catalytic performance for the alkylation of isobutane with butene. The experimental results from batch reactors indicated that the reaction efficiency was significantly improved. The effective catalytic lifetime of concentrated H 2 SO 4 mixed with [Bmim][SbF 6 ] was twice compared with pure H 2 SO 4 . Under the optimal conditions, the alkylate research octane (RON) reached 98, and the selectivity of C8 was 90%. The ionic liquids with SbF 6 anion worked similar to buffer agents, which were in favor of keeping the acid strength of catalytic system, slowing the growth of acid soluble oil, and reducing acid consumption. In conclusion, the new catalytic system of acid and trace amounts of ionic liquids is very promising to substitute the old catalytic system of concentrated H 2 SO 4 alone for the alkylation.