Silver-Catalyzed Asymmetric Desymmetrization of Cyclohexadienones via Van Leusen Pyrrole Synthesis.

A catalytic asymmetric desymmetrization of cyclohexadienones was accomplished via Van Leusen pyrrole synthesis in the presence of a chiral silver catalyst. The ready access to chiral-fused pyrrole derivatives is attributed to the identification of a suitable isocyanomethyl sulfone surrogate, NasMIC. The current Ag(I)-chiral phosphino-carboamide ligand system can be extended to the kinetic resolution of racemic cyclohexadienones, capitalizing on the differentiated reactivity of chiral quaternary complexes from AgSbF, chiral ligand (*), cyclohexadienone, and NasMIC.

Synthesis of novel naphthalene-heterocycle hybrids with potent antitumor, anti-inflammatory and antituberculosis activities.

Multitarget-directed drugs (hybrid drugs) constitute an efficient avenue for the treatment of multifactorial diseases. In this work, novel naphthalene hybrids with different heterocyclic scaffolds such as nicotinonitrile, pyran, pyranopyrazole, pyrazole, pyrazolopyridine, and azepine were efficiently synthesized tandem reactions of 3-formyl-4-benzo[]chromen-4-one 1 with different nucleophilic reagents. Analysis of these hybrids using PASS online software indicated different predicted biological activities such as anticancer, antimicrobial, antiviral, antiprotozoal, anti-inflammatory, By focusing on antitumor, anti-inflammatory, and antituberculosis activities, many compounds revealed remarkable activities.

Unorthodox synthesis, biological activity and DFT studies of novel and multifunctionalized naphthoxocine derivatives.

A new promising protocol has been developed for the synthesis of scarce oxocine derivatives 3a-e and 6 through addition of amine-based nucleophiles such as hydroxylamine hydrochloride, primary amine and hydrazide to chromonylidene benzothiazol-2-ylacetonitrile 2 in refluxing dioxane under metal free reaction conditions in moderate to good yields. Other nitrogen nucleophiles such as piperidine, hydrazine and thiosemicarbazide failed to afford the corresponding oxocinols, and instead pyridine derivatives 7, 8 and 10 were obtained exclusively. Predictive study for the biological activities using PASS (prediction of activity spectra for biologically active substances) online software showed optimistic activities for oxocinols 3a-e in the treatment of cancer, influenza A and microbial infections.

Synthesis, biological evaluation and molecular docking of novel 1-hydroxy-naphthyl substituted heterocycles.

The versatile precursor 2-acetyl-4-allyl-1-hydroxy naphthalene was synthesized efficiently via Claisen rearrangement 2-acetyl-1-allyloxynaphthalene. The Claisen-Schmidt condensation of latter precursor afforded the corresponding chalcones which were exploited to synthesize a series of potential heterocycles such as pyrazoline, isoxazoline, benzocoumarin and benzoflavone. The synthesized products showed potent antioxidant and antimicrobial activities.

Determination of the absolute configuration of compounds bearing chiral quaternary carbon centers using the crystalline sponge method.

Determination of the absolute configuration of chiral tetra-substituted carbon centers is one of the most taxing steps in the enantioselective construction of this structural motif in asymmetric synthesis. Here, we demonstrate that the crystalline sponge method provides an effective way to crystallographically determine the absolute configuration of organic compounds bearing chiral quaternary carbons (including tetra-substituted ones) that are synthesized by recently developed enantioselective catalytic reactions.

Enantio- and Diastereoselective Betti/aza-Michael Sequence: Single Operated Preparation of Chiral 1,3-Disubstituted Isoindolines.

The first enantio- and diastereoselective Betti/intramolecular aza-Michael sequence carried out using a C-symmetric chiral trisimidazoline organocatalyst is reported. The reaction of phenols and N-tosylimines bearing a Michael acceptor moiety afforded densely functionalized 1,3-disubstituted isoindolines bearing two stereogenic centers as single diastereomers in high yields (≤93%) and excellent enantioselectivities (≤99.9%).

Enantioselective synthesis of tetrahydrocyclopenta[b]indole bearing a chiral quaternary carbon center via Pd(ii)-SPRIX-catalyzed C-H activation.

The highly enantioselective cyclization of 3-alkenylindole via C-H activation has been established using Pd(OCOCF) in conjunction with the chiral spiro bis(isoxazoline) ligand (SPRIX). The presence of an N-allyl substituent on the substrate has a strong impact on both reactivity and selectivity, leading to tricyclic indole products (up to 96% ee) with a chiral quaternary carbon center.

Enantioselective organocatalytic oxidation of ketimine.

C3-Symmetric chiral trisimidazolines with m-chloroperbenzoic acid promoted the organocatalytic oxidation of N-sulfonyl ketimine. The present imidazoline catalysis produced oxaziridines bearing a tetrasubstituted carbon stereogenic center in high yields with up to 87% ee.