An NHC‐organocatalyzed remote C(sp3)−H acylation of amides is developed based on a 1,5‐hydrogen atom transfer strategy. As reported in the Research Article by Jun‐Long Li et al. (e202116629), over 120 functionalized δ‐amino ketones and isoquinolinones were synthesized in up to 99 % yield under mild conditions. Mechanistic investigations, including control reactions, KIE experiments, and computational studies, shed light on the organocatalytic radical reaction mechanism.

The multicomponent acylfluoroalkylation of olefins through N‐heterocyclic carbene (NHC) organocatalysis is presented by J.‐L. Li, B. Han, Q.‐Z. Li and co‐workers in their Research Article page 1863. A broad spectrum of olefins, including styrenes, cyclic alkenes, indoles, vinyl ethers, vinyl esters, and unactivated alkenes, are compatible with this system. The generality of this method is further highlighted by the late‐stage modification of pharmaceutical skeletons.

The efficient and enantioselective construction of cyclic compounds with a halogenated tetrasubstituted carbon through various catalytic strategies remains challenging. Thus, research on modern asymmetric catalysis is important. In this review, recent achievements that streamlined the synthesis of halogenated cyclic molecules through organocatalysis or transition-metal catalysis were introduced. 2.7. Chiral Boron Catalysis 2.8. Chiral Brønsted Acid Catalysis 2.9. Chiral Iodoarene Catalysis 2.10.

We report here a stereoselective [3+2] cyclization of 5‐alkenyl thiazolones and ketimines that allows the assembly of three diastereoisomers through the combination of stereodivergent organocatalysis and the following diastereoselective transformation of products. A broad spectrum of pyrrolidinyl spirooxindoles featuring stereochemical diversity has been synthesized through organocatalytic formal 1,3‐dipolar cycloadditions with up to 98% yield, >20:1 dr and 99:1 er.magnified image

Fluorinated ketones are widely prevalent in numerous biologically interesting molecules, and the development of novel transformations to access these structures is an important task in organic synthesis. Herein, we report the multicomponent radical acylfluoroalkylation of a variety of olefins in the presence of various commercially available aromatic aldehydes and fluoroalkyl reagents through N‐heterocyclic carbene organocatalysis. With this protocol, over 120 examples of functionalized ketones with diverse fluorine substituents have been synthesized in up to 99 % yield with complete regioselectivity. The generality of this catalytic strategy was further highlighted by its successful application in the late‐stage functionalization of pharmaceutical skeletons. Excellent diastereoselectivity could be achieved in the reactions forging multiple stereocenters. In addition, preliminary results have been achieved on the catalytic asymmetric variant of the olefin difunctionalization process.