Direct C–H Allylation of Unactivated Alkanes by Cooperative W/Cu Photocatalysis

Here we report a photocatalytic methodology that enables the direct allylation of strong aliphatic C–H bonds with simple allylic chlorides. The method relies on a cooperative interaction of two metal catalysts in which the decatungstate anion acts as a hydrogen-atom abstractor generating a nucleophilic carbon-centered radical that engages in an SH2′ reaction with an activated allylic π-olefin–copper complex. Because of this dual catalysis, the protocol allows for the functionalization of a range of chemical feedstocks and natural products under mild conditions in short reaction timesFinancial support from the European Research Council (ERC-CoG 863914-BECAME), Agencia Estatal de Investigación (PID2020-118237RB-I00), Xunta de Galicia (ED431C 2018/04; Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03), and the European Regional Development Fund (ERDF) is gratefully acknowledgedS

C–C bond formation via photocatalytic direct functionalization of simple alkanes

The direct functionalization of alkanes represents a very important challenge in the goal to develop more atom-efficient and clean C–C bond forming reactions. These processes, however, are hampered by the low reactivity of the aliphatic C–H bonds. Photocatalytic processes based on hydrogen atom transfer C–H bond activation strategies have become a useful tool to activate and functionalize these inert compounds. In this article, we summarize the main achievements in this field applied to the development of C–C bond forming reactions, and we discuss the key mechanistic features that enable these transformationFinancial support from the European Research Council (ERC-CoG 863914-BECAME), AEI (PID2020-118237RB-I00), Xunta de Galicia (ED431C 2022/27; Centro singular de investigación de Galicia accreditation 2019–2022, ED431G 2019/03) and the European Regional Development Fund (ERDF) is gratefully acknowledged. A. M. A.-C. thanks Xunta de Galicia for a predoctoral fellowshipS

Highly enantioselective iridium-catalyzed hydrogenation of 2-aryl allyl phthalimides

The iridium-catalyzed asymmetric hydrogenation of 2-aryl allyl phthalimides to afford enantioenriched β-aryl-β-methyl amines is presented. Recently developed Ir-MaxPHOX catalysts are used for this enantioselective transformation. The mild reaction conditions and the feasible removal of the phthalimido group makes this catalytic method easily scalable and of great interest to afford chiral amines. The importance of this new methodology is exemplified by the formal synthesis of (R)-Lorcaserin, OTS514 and enantiomerically enriched 3-methyl indolines