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.

A novel [4 + 3] annulation of indoline-based aza-dienes and crotonate-derived sulfur ylides is described. This method could be further expanded by using more efficient synthetic strategies, including three-component [3 + 1 + 3] cascade and the direct sulfide-catalyzed [4 + 3] cyclization. These protocols enable the rapid construction of azepino­[2,3-b]­indole cores, and a broad spectrum of the desired products with diverse substituents was facilely accessed in generally high yield.

Asymmetric construction of α-carbolinones with easily available starting materials has recently attracted considerable attention from the synthesis community, and the development of effective catalysis for this target is in great demand. Here, a bifunctional Brønsted base catalyzed asymmetric [3 + 3] cyclization of indolin-2-imines and α,β-unsaturated N-acylated succinimides was developed by using the strategy of noncovalent bonding catalysis. With this organocatalytic protocol, a variety of tetrahydro-α-carbolinones bearing different substituents were synthesized with up to 99% yield and up to 96:4 er.

A series of iminoindoline-derived alkenes was found to be a new class of excellent aza-diene electrophiles in NHC-catalyzed asymmetric [4 + 2] cyclizations. This transformation is mainly characterized by excellent compatibility, which allows aza-diene substrates to incorporate various substituents and functionalities, including (hetero)aryl, (linear or branched)alkyl, alkenyl, alkynyl, and ester groups. Forty examples of the desired tetrahydro-α-carbolinones were facilely synthesized using this method, with up to 99% yield and >99% ee. Letter pubs.acs.org/OrgLett

Spiroheterocycles are regarded as a privileged framework because of their wide distribution in various natural products and synthetic molecules and promising bioactivities. This review focuses on the recent advances in the synthesis of spiroheterocycles by using the strategy of N-heterocyclic carbene (NHC) organocatalysis, and is organized based on the stereoselectivity and the reactive intermediates. According to the stereochemistry, this review was divided into two main parts, covering racemic and enantioselective versions. In each part, we firstly describe the synthetic transformations using nucleophilic Breslow intermediates, and then discuss the reactions that employ electrophilic acylazolium or radical cation intermediates. With those distinct catalytic activation modes of NHC organocatlysis, we expect this synthetic protocol will possibly produce new molecules with structural novelty and complexity, which may warrant further research in the field of drug discovery.