N‐heterocyclic carbene (NHC) organocatalysis in the presence of transition metals is a challenge due to the high affinity of NHCs for metals. In their Communication (DOI: 10.1002/anie.201912584), J. Mao, P. J. Walsh, and co‐workers present a system for the conjugate addition of aryl iodides to enals through cooperative catalysis between an NHC and a Pd catalyst. The catalytic cycles intersect at Pd, where the two newly formed Pd−C bonds undergo reductive elimination to give a C−C bond.

NHC‐Organokatalyse (NHC=N‐heterocyclisches Carben) in Gegenwart von Übergangsmetallen ist schwierig, wegen der hohen Affinität von NHCs für Metalle. J. Mao, P. J. Walsh et al. präsentieren in ihrer Zuschrift (DOI: 10.1002/ange.201912584) ein System für die konjugierte Addition von Aryliodiden an Enale durch kooperative Katalyse zwischen einem NHC‐ und einem Pd‐Katalysator. Die Katalysezyklen überschneiden sich bei Pd, wo die beiden neu gebildeten Pd‐C‐Bindungen eine reduktive Eliminierung unter Bildung einer C‐C‐Bindung eingehen.

Amines are fundamental motifs in bioactive natural products and pharmaceuticals. Using simple toluene derivatives, a one-pot aminobenzylation of aldehydes is introduced that provides rapid access to amines. Simply combining benzaldehydes, toluenes, NaN(SiMe₃)₂, and additive Cs(O₂CCF₃) (0.35 equiv.) generates a diverse array of 1,2-diarylethylamine derivatives (36 examples, 56–98% yield). Furthermore, suitably functionalized 1,2-diarylethylamines were transformed into 2-aryl-substituted indoline derivatives via Buchwald–Hartwig amination. It is proposed that the successful deprotonation of toluene by MN(SiMe₃)₂ is facilitated by cation–π interactions between the arene and the group(I) cation that acidify the benzylic C–Hs.

Nonsteroidal anti-inflammatory drug derivatives (NSAIDs) are an important class of medications. Here we show a visible-light-promoted photoredox/nickel catalyzed approach to construct enantioenriched NSAIDs via a three-component alkyl arylation of acrylates. This reductive cross-electrophile coupling avoids preformed organometallic reagents and replaces stoichiometric metal reductants by an organic reductant (Hantzsch ester). A broad range of functional groups are well-tolerated under mild conditions with high enantioselectivities (up to 93% ee) and good yields (up to 90%). A study of the reaction mechanism, as well as literature precedence, enabled a working reaction mechanism to be presented. Key steps include a reduction of the alkyl bromide to the radical, Giese addition of the alkyl radical to the acrylate and capture of the α-carbonyl radical by the enantioenriched nickel catalyst. Reductive elimination from the proposed Ni(III) intermediate generates the product and forms Ni(I).