Organofluorine compounds are of high value. NHC-catalyzed fluorination and fluoroalkylation have served as powerful versatile vehicles for accessing the related organofluorines. This review focuses on recent developments in this area.

Comprehensive Summary Vicinal all‐carbon quaternary stereocenters are widely present in natural products and bioactive molecules. However, the construction of such motif one step from readily available starting materials remains a significant challenge. Herein, we report phosphine‐catalyzed divergent γ,γ‐ ε,γ‐umpolung domino addition bisoxindoles with allenoates. This method serves as practical tool for concise synthesis series bisoxindole derivatives bearing sterically hindered vicinal...

Annulation reactions are recognized for their efficiency in constructing complex cyclic compounds with multiple substitutions, aligning well green chemistry principles. Herein, we report a transition metal-free, chemodiverse cycloaddition reaction...

Abstract A palladium‐catalyzed regiodivergent C 1 insertion multicomponent reaction involving aryne, CO, and 2‐iodoaniline is established to construct the scaffolds of phenanthridinone acridone alkaloids. Regioselective control achieved under guidance selective ligands. The phenanthridinones are solely obtained ligand‐free condition. In comparison, application electron‐abundant bidentate ligand dppm afforded acridones with high efficiency. release rate aryne from precursor assists...

A P(NMe2)3-catalyzed [4 + 2] annulation of 2-amino-β-nitrostyrenes and β′-acetoxy allenoates followed by a Zn/AcOH-mediated reduction–hydroamination–isomerization has been developed.

A palladium-catalyzed cascade coupling between glycals and racemic α-nitroesters enables the stereoselective construction of C-glycosyl amino acids bearing two contiguous stereocenters, achieving dual stereocontrol (exclusive β-C1, up to 10:1 diastereomeric ratio at C7). This one-pot protocol room temperature accommodates diverse substrates (25 examples). Mechanistic studies demonstrate that decarboxylation-induced C4-oxyanion directs 1,4-syn selectivity, while steric modulation governs C7...

A uniformly strategic total synthesis of Aspidosperma alkaloids (+)-vincadifformine, (−)-quebrachamine, (+)-aspidospermidine, (−)-aspidospermine, (−)-pyrifolidine, and nine others from efficiently constructed tricyclic ketone 13 is reported. Highlights these divergent practical syntheses include (i) stereoselective intermolecular [4 + 2] cycloaddition to establish a C–E ring with one all-carbon quaternary stereocenter (C-5) two bridged contiguous cis-stereocenters (C-12 C-19), (ii)...

An Fe-catalyzed 2-deoxy glycosylation method was developed from 3,4-O-carbonate glycals directly at room temperature. This novel approach enabled facile access to alkyl and aryl glycosides in high yields with exclusive α-stereoselectivity, tolerating various alcohols, phenols, glycals. The synthetic utility advantage of this strategy have been demonstrated by the modification six natural products construction a tetrasaccharide.

A stereocontrolled synthesis of an aryl

A concise and stereocontrolled strategy for the syntheses of oxygenated Aspidosperma Vinca alkaloids, via a stereoselective intermolecular inverse-electron-demand [4 + 2] cycloaddition, challenging α,β-unsaturated ketone indolization rearrangement with excellent regio- stereoselectivity, an efficient Pd/C-catalyzed one-pot cascade reaction. The has been demonstrated by asymmetric antitumor drug (+)-vinblastine five other alkaloids.

A novel phosphine-mediated α-umpolung/Wittig olefination/cyclization cascade process between o -aminobenzaldehydes and Morita–Baylis–Hillman (MBH) carbonates has been ingeniously developed for the facile synthesis of a broad range 2-vinylindolines.

Highly enantioselective and chemodivergent domino reactions between γ-substituted allenoates activated alkenes have been developed.

A highly diastereo- and enantioselective phosphine-catalyzed sequential [3 + 2]/[3 2] annulation of allenoates with arylidenemalononitriles has been developed. This reaction allows for the facile construction multifunctionalized cis-fused bicyclic[3,3,0]octene scaffolds, encompassing three consecutive stereogenic centers one quaternary carbon center, in a one-step operation from readily available materials. The reported protocol is scalable, operates under mild conditions, creates core...

A stereodivergent synthesis of β- and α-O-glycosides using 3-O-quinaldoyl glucals was developed by palladium catalysis at 60 110 °C respectively. Various alcohols, monosaccharides, amino acid were glycosylated to form α- products in good yields with high stereoselectivity. Mechanistic studies indicated no classic Pd–N (quinoline) coordination, but π–π stacking interactions promoted the anomeric stereodiversity. The practicality demonstrated glycosylating natural products/drugs synthesizing a...

Abstract Selective functionalization via cleavage of the C–N bond amines has proven to be challenging partly because its relatively high dissociation energy, even though are abundant and readily available. To meet this challenge, many new transformations based on pre-activation before have been developed. Among them, conversion into quaternary ammonium salts certain advantages, such as easy preparation from primary, secondary, or tertiary amines, well stable storage usage. Although...

In this review, we elaborate and discuss the recent applications of straight-chain amino-α,β-unsaturated carbonyl compounds as versatile synthons in organocatalytic reactions for creation five- six-membered saturated nitrogen-containing heterocycles.

Herein, we developed an efficient nucleophile-controlled regiodivergent domino reaction between enetriones and γ-bromocrotonates. This method allowed for the rapid synthesis of a range 1,3-dienic esters tetrasubstituted pyrans under metal-free conditions. In presence pyridine, SN2 substitution/Michael addition/elimination sequence formed in satisfactory yields with high E-stereoselectivities. Alternatively, addition/cyclization/cyclopropanation/cyclopropane ring-opening process forged good...

Harnessing aryltrifluoroborates' stability and reactivity, we developed a Pd-catalyzed stereoselective C-glycosylation under ambient conditions, yielding diverse C-aryl glycosides with exclusive α-stereoselectivity compatibility hydroxyl, amide, amine groups. This method enables functionalization to produce unprotected C-pyranosides, 2,3-dideoxy 2,3-epoxy sugars, late-stage of natural products drugs.

A stereodivergent synthesis of bicyclic α-C-, β-O-, and α-O-glycosides is achieved with nonprecious Co(dpm)3, K2CO3, DBU, respectively. Cobalt-catalyzed decarboxylative allylation 2,3-unsaturated 4-keto glycosyl carbonates 1,3-diketones delivers α-C-glycosides in good yields exclusive chemo- regiocontrol excellent diastereoselectivity (>20:1 dr). K2CO3 enables β-O-glycosides via a cascaded intermolecular Michael addition/SN2-like cyclization, whereas DBU promotes further C5 epimerization to...

Abstract A one‐pot synthesis of 2,3,4‐unprotected β‐ N ‐glycopyranosides from glycals and amines with exclusive β‐stereoselectivity under room temperature conditions is reported. This method was achieved via palladium‐catalyzed Tsuji‐Trost amination followed by dihydroxylation directly, tolerating anilines, heterocyclic aromatic amines, , O ‐dimethylhydroxylamine, especially the reaction primary has not been reported before. Furthermore, protocol applied to modify clinical drugs (prazosin,...