Highly Enantioselective Synthesis of 2,3-Dihydroquinazolinones through Intramolecular Amidation of Imines

Enantioselective synthesis of 2,3-dihydroquinazolinones (DHQZs) was accomplished using readily available Sc(III)-<i>inda</i>-pybox as the catalyst. This is the first report on the metal catalyzed asymmetric intramolecular amidation of imines to synthesize DHQZs

Stereodivergent Synthesis of 3‑Aminooxindole Derivatives Containing Vicinal Tetrasubstituted Stereocenters via the Mannich Reaction

A highly enantioselective stereodivergent synthesis of 3-aminooxindole derivatives was accomplished via asymmetric Mannich reaction between 2-substituted benzofuran-3-one and isatin-derived ketimines. Both <i>anti</i> and <i>syn</i>-selective chiral 3,3-disubstituted amino oxindoles bearing two adjacent tetrasubstituted stereogenic centers with high yield and excellent enantioselectivities were obtained using readily available cinchona-alkaloid derived organocatalysts. The control experiment revealed that oxygen atom present in the benzofuran ring played an important role in switching diastereodivergence. The obtained Mannich product was further transformed into a biologically important 2,3-dihydrobenzofuran derivative having three contiguous stereocenters with no loss of enantioselectivity

Enantioselective Synthesis of Dihydrospiro[indoline-3,4′-pyrano[2,3‑<i>c</i>]pyrazole] Derivatives via Michael/Hemiketalization Reaction

A new bifunctional squaramide organocatalyst derived from l-proline mediated the first enantioselective synthesis of dihydrospiro­[indoline-3,4′-pyrano­[2,3-<i>c</i>]­pyrazole] derivatives in excellent enantioselectivity by reacting pyrazolones with isatylidine β,γ-unsaturated α-ketoester. This new catalyst outperformed widely used thioureas and squaramides in inducing enantioselectivity

Stereodivergent Synthesis of 3‑Aminooxindole Derivatives Containing Vicinal Tetrasubstituted Stereocenters via the Mannich Reaction

A highly enantioselective stereodivergent synthesis of 3-aminooxindole derivatives was accomplished via asymmetric Mannich reaction between 2-substituted benzofuran-3-one and isatin-derived ketimines. Both <i>anti</i> and <i>syn</i>-selective chiral 3,3-disubstituted amino oxindoles bearing two adjacent tetrasubstituted stereogenic centers with high yield and excellent enantioselectivities were obtained using readily available cinchona-alkaloid derived organocatalysts. The control experiment revealed that oxygen atom present in the benzofuran ring played an important role in switching diastereodivergence. The obtained Mannich product was further transformed into a biologically important 2,3-dihydrobenzofuran derivative having three contiguous stereocenters with no loss of enantioselectivity

Stereodivergent Synthesis of 3‑Aminooxindole Derivatives Containing Vicinal Tetrasubstituted Stereocenters via the Mannich Reaction

A highly enantioselective stereodivergent synthesis of 3-aminooxindole derivatives was accomplished via asymmetric Mannich reaction between 2-substituted benzofuran-3-one and isatin-derived ketimines. Both <i>anti</i> and <i>syn</i>-selective chiral 3,3-disubstituted amino oxindoles bearing two adjacent tetrasubstituted stereogenic centers with high yield and excellent enantioselectivities were obtained using readily available cinchona-alkaloid derived organocatalysts. The control experiment revealed that oxygen atom present in the benzofuran ring played an important role in switching diastereodivergence. The obtained Mannich product was further transformed into a biologically important 2,3-dihydrobenzofuran derivative having three contiguous stereocenters with no loss of enantioselectivity

Highly Enantioselective Synthesis of 2,3-Dihydroquinazolinones through Intramolecular Amidation of Imines

Enantioselective synthesis of 2,3-dihydroquinazolinones (DHQZs) was accomplished using readily available Sc(III)-<i>inda</i>-pybox as the catalyst. This is the first report on the metal catalyzed asymmetric intramolecular amidation of imines to synthesize DHQZs

Diastereoselective Construction of Tetrahydro-Dispiro[indolinone-3,2′-pyran-5′,4″-pyrazolone] Scaffolds via an Oxa-Michael Cascade [4 + 2] Annulation Reaction

A straightforward metal-free oxa-Michael cascade [4 + 2] annulation reaction was established between isatin-derived Morita–Baylis–Hillman (Is-MBH) alcohols with alkylidene pyrazolones to access structural diverse tetrahydro-dispiro[indolinone-3,2′-pyran-5′,4″-pyrazolone] scaffolds bearing two tertiary and two quaternary stereocenters. The Is-MBH alcohol was utilized as an oxa-Michael donor for the first time as a new approach in highly atom-economical transformations. This method offered a wide range of bioinspired novel tetrahydro-dispirooxindole-pyran-pyrazolone derivatives in excellent yields (up to 96%) and diastereoselectivities (up to >20:1) in a shorter reaction time (15 min)

Diastereo- and Enantioselective Synthesis of 2,2-Disubstituted Benzofuran-3-one Bearing Adjacent Quaternary and Tertiary Stereocenters

The first highly diastereo- and enantioselective synthesis of armeniaspirol analogues was achieved using L-proline derived bifunctional squaramide which outperformed commonly used organocatalysts. Excellent yield (up to 99%) with diastereoselectivity (up to 99:1) and enantioselectivity (up to 99%) were obtained for a wide range of substrates

Palladium Catalyzed Asymmetric Allylation of 3‑OBoc-Oxindoles: An Efficient Synthesis of 3‑Allyl-3-hydroxyoxindoles

3-Allyl-3-hydroxyoxindoles were synthesized in very good enantio- (up to 97% ee) and diastereoselectivities (dr up to 7.6:1) with contiguous quaternary and tertiary stereogenic centers by employing tartrate derived bi­(oxazoline) in Pd-catalyzed allylation of 3-OBoc-oxindole. Synthetic utility of 3-allyl-3-hydroxyoxindole was demonstrated by synthesizing a highly substituted spiro­(oxindole-3,2′-tetra­hydro­furan) derivative in good yield and stereoselectivity