Palladium-Catalyzed Cascade Carbonylation Reaction: Synthesis of Fused Isoindolinones.

A palladium-catalyzed cascade carbonylation reaction of 2-bromo--(2-iodophenyl)benzamides with benzylidenecyclopropanes for the synthesis of fused isoindolinone derivatives has been developed. A broad range of 6/5/6/6 tetracyclic isoindolinone products were efficiently prepared in moderate to good yields with diverse substitution. Two carbonyl groups were incorporated into the substrates in a single step with the formation of four carbon-carbon bonds and two carbon-heteroatom bonds.

Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters.

2,3-Allenamides are an important class of unsaturated group-substituted carbonyl compounds. A palladium-catalyzed aminocarbonylation of propargyl acetates with amines for the synthesized tri-/tetrasubstituted 2,3-allenamides has been developed. A broad range of tri-/tetrasubstituted 2,3-allenamides have been prepared from propargyl acetates in good to excellent yields.

Cooperative Cu/Pd-Catalyzed 1,5-Boroacylation of Cyclopropyl-Substituted Alkylidenecyclopropanes.

A Cu/Pd-cocatalyzed 1,5-boroacylation of cyclopropyl-substituted ACPs with Bpin and acid chlorides has been developed. Using cyclopropyl-substituted ACPs as the starting material, a broad range of 1,5-boroacylated products with multiple functional groups was prepared in good yields with excellent regio- and stereoselectively. Both aromatic and aliphatic acid chlorides were tolerated in this reaction.

Acid-Promoted Cyclization of α-Azidobenzyl Ketones through C═N Bond Formation: Synthesis of 6-Substituted Quinoline Derivatives.

An acid-promoted cyclization of α-azidobenzyl ketones has been developed for the synthesis of 6-substituted quinoline derivatives. A variety of synthetically useful 6-OTf or -OMs quinoline derivatives were obtained in moderate to good yields. The reaction proceeds via C═N bond formation without organophosphine, providing convenient access to structurally interesting and synthetically important 6-substituted quinoline derivatives in moderate to good yields.

Ruthenium-Catalyzed Carbonylation of α-Aminoaryl-Tethered Alkylidenecyclopropanes: Synthesis of Eight-Membered Benzolactams.

The synthesis of medium-sized lactams is a great challenge because of the unfavorable transannular interactions and entropic barriers in the transition state. We have developed a ruthenium-catalyzed carbonylation of α-aminoaryl-tethered alkylidenecyclopropanes (ACPs) that allows for the efficient preparation of valuable eight-membered benzolactams under ligand-free conditions. The amino group served a dual role of both directing group and nucleophile to facilitate the metallacycle formation and the carbonylation.

Photoinduced reductive Reformatsky reaction of α-haloesters and aldehydes or ketones by cooperative dual-metal catalysis.

A photoinduced reductive Reformatsky reaction by cooperative dual-metal catalysis is described. This methodology enables the implementation of this venerable reaction in environmentally friendly conditions, obviating the need for a stoichiometric amount of metals. A broad range of synthetically useful β-hydroxy esters can be efficiently prepared in moderate to high yields using this protocol.

Total Synthesis of (+)-Peniciketal B.

An efficient synthesis of (+)-peniciketal B has been accomplished in 15 steps from the commercially available materials atraric acid, acryloyl chloride, and (+)-homoallylic alcohol. A convergent synthetic approach that is quite concise for constructing either "hemisphere" of (+)-peniciketal B with a common intermediate is employed that relies on a cascade intermolecular FeCl-mediated "inner sphere" Michael-type reaction/double cyclization of an α,β-unsaturated ketone and substituted phenol to build the benzo-fused 2,8-dioxabicyclo[3.3.

Palladium Catalyzed Annulation of -Iodo-Anilines with Propargyl Alcohols: Synthesis of Substituted Quinolines.

A palladium catalyzed annulation of -iodo-anilines with propargyl alcohols for the synthesis of substituted quinolines has been developed. The reaction tolerates diverse functional groups under mild conditions, providing direct access to 2,4-disubstituted quinolines from easily available starting materials. A broad range of 2,4-disubstituted quinolines were efficiently prepared in good to excellent yields.

Palladium-catalyzed intramolecular asymmetric hydrocyclopropanylation of alkynes: synthesis of cyclopropane-fused γ-lactams.

A palladium-catalyzed intramolecular asymmetric hydrocyclopropanylation of alkynes C(sp)-H activation has been developed for the synthesis of cyclopropane-fused γ-lactams. The presented strategy proceeds in a selective and 100% atom-economical manner. A range of cyclopropane-fused γ-lactams were prepared from readily available substrates in good yields and enantioselectivities with a chiral phosphoramidite ligand.

Anti-α-Glucosidase, SAR Analysis, and Mechanism Investigation of Indolo[1,2-b]isoquinoline Derivatives.

To find potential α-glucosidase inhibitors, indolo[1,2-b]isoquinoline derivatives (-) were screened for their α-glucosidase inhibitory effects. All derivatives presented potential α-glucosidase inhibitory effects with IC values of 3.44 ± 0.

Enantioselective synthesis of α,α-diarylketones by sequential visible light photoactivation and phosphoric acid catalysis.

Chiral ketones and their derivatives are useful synthetic intermediates for the synthesis of biologically active natural products and medicinally relevant molecules. Nevertheless, general and broadly applicable methods for enantioenriched acyclic α,α-disubstituted ketones, especially α,α-diarylketones, remain largely underdeveloped, owing to the easy racemization. Here, we report a visible light photoactivation and phosphoric acid-catalyzed alkyne-carbonyl metathesis/transfer hydrogenation one-pot reaction using arylalkyne, benzoquinone, and Hantzsch ester for the expeditious synthesis of α,α-diarylketones with excellent yields and enantioselectivities.

Molybdenum-Mediated Reductive Hydroamination of Vinylcyclopropanes with Nitroarenes: Synthesis of Homoallylamines.

A molybdenum-mediated reductive hydroamination of vinylcyclopropanes with nitroarenes has been developed. A broad range of substituted homoallylamines were prepared in good to excellent yields from readily available starting materials. No noble metal catalysts were used in this reaction, and Mo(CO) acted as both catalyst and reductant.

Palladium- and Brønsted acid-catalyzed enantio-, site- and /-selective addition of alkylidenecyclopropanes with imines.

Transition-metal catalyzed functionalization of ACPs has been widely investigated in cycloaddition and 1,3-difunctionalization reactions. However, the transition metal catalyzed nucleophilic reactions of ACPs have rarely been reported. In this article, an enantio-, site- and /-selective addition of ACPs with imines for the synthesis of dienyl substituted amines has been developed palladium- and Brønsted acid co-catalysis.

Bismuth(III)-Catalyzed 1,8-Addition/Cyclization/Rearrangement of Propargylic -Quinone Methides with 2-Vinylphenol: Synthesis of Indeno[2,1-]chromenes.

The unique reactivity of generated propargylic quinone methides as a new type of five-carbon synthon has been discovered by a novel bismuth(III)-catalyzed tandem annulation reaction. This 1,8-addition/cyclization/rearrangement cyclization cascade reaction is characterized by unusual structural reconstruction of 2-vinylphenol, involving cleavage of the C1'═C2' bond and formation of four new bonds. This method provides a convenient and mild approach to generate synthetically important functionalized indeno[2,1-]chromenes.

Base-promoted [4 + 2] annulation of pyrrole-2-carbaldehyde derivatives with β,γ-unsaturated α-ketoesters: syntheses of 5,6-dihydroindolizines.

A base-promoted [4 + 2] annulation of pyrrole-2-carbaldehyde derivatives with β,γ-unsaturated α-ketoesters for the syntheses of multisubstituted 5,6-dihydroindolizines was developed. Using DBN as a base, the reaction proceeds smoothly under mild conditions to provide the target products in moderate to high yields, and many useful functional groups can be tolerated.

Studies toward synthesis of the core skeleton of spiroaspertrione A.

Bioassay-guided isolation of spiroaspertrione A from cultures of . TJ23 in 2017 demonstrated potent resensitization of oxacillin against methicillin-resistant by lowering the oxacillin minimal inhibitory concentration up to 32-fold. To construct this unique spiro[bicyclo[3.

Brønsted acid catalyzed remote C6 functionalization of 2,3-disubstituted indoles with β,γ-unsaturated α-ketoester.

A metal-free catalytic approach for the remote C6-functionalization of 2,3-disubstituted indoles has been developed. In the presence of catalytic amounts of Brønsted acid, the -unsaturated -ketoesters react with 2,3-disubstituted indoles at the C6 position selectively. Under mild reaction conditions, a range of C6-functionalized indoles were prepared with good yields and excellent regioselectivity.

Palladium-Catalyzed Nucleophilic Reaction of Alkylidenecyclopropanes with β,γ-Unsaturated α-Ketoesters: Ligand-Controlled Divergent Synthesis.

A palladium-catalyzed ligand-controlled selective 1,4-addition and cycloaddition reaction of β,γ-unsaturated α-ketoesters with alkylidenecyclopropanes (ACPs) has been developed. Using ACPs and β,γ-unsaturated α-ketoesters as starting materials, γ-dienyl-α-ketoesters and dihydro-2-pyrans could be prepared selectively by modulating the ligand. A range of multisubstituted α-ketoesters and dihydro-2-pyrans were obtained in moderate to excellent yields with excellent regioselectivities.

Palladium Catalyzed Dicarbonylation of α-Iodo-Substituted Alkylidenecyclopropanes: Synthesis of Carbamoyl Substituted Indenones.

A palladium catalyzed dicarbonylation of α-iodo-substituted ACPs for the synthesis of carbamoyl substituted indenones has been developed. Two carbonyl groups were incorporated into the product with the cleavage of the proximal C-C bond of the ACPs. A broad range of carbamoyl substituted indenones were efficiently prepared in good to excellent yields.

Palladium-Catalyzed Intramolecular Heck/Aminocarbonylation of Alkene-Tethered Iodobenzenes with Nitro Compounds: Synthesis of Carbamoyl-Substituted Benzoheterocycles.

A palladium-catalyzed intramolecular Heck/aminocarbonylation of alkene-tethered iodobenzenes with nitro compounds has been developed for the synthesis of carbamoyl-substituted benzoheterocycles. Using Mo(CO) as a solid CO source, no external reductant or additives were needed in this procedure. Both nitroarenes and nitroalkanes were well tolerated.

Copper-catalyzed 1,2-Borylacylation of 1,3-Enynes: synthesis of β-Alkynyl ketones.

A copper catalyzed 1,2-borylacylation of 1,3-enynes with Bpin and acid chlorides has been developed. Using readily available 1,3-enynes, Bpin and acid chlorides as substrates, a range of highly functionalized α,α-disubstituted β-alkynyl ketones were readily prepared under mild conditions in moderate to good yields. The borylacylated products can be easily derivatized to give several valuable structures.