RESUMEN
A new type of spirocyclic bisoxindole-based C2-symmetric diols (SBIDOLs) was designed and synthesized. A series of racemic SBIDOL derivatives (6a-6g) were readily synthesized from commercially available 2-halo-5-methoxyanilines 1 (X = Cl or Br) through N-mono alkylation, acylation, oxidation, double intramolecular Friedel-Crafts reaction, and demethylation reactions. The optical resolution of racemic 6b was achieved via fractional crystallization of their bis-l-menthoxycarboxylates. Further modifications of SBIDOLs were investigated, leading to 5,5'-diaryl SBIDOL derivatives (11a and 11b) through Pd-catalyzed Suzuki coupling and DM-SBIDOL 12 by Pd/C-catalyzed hydrogenative dechlorination reactions.
RESUMEN
Herein, we report a highly efficient organocatalytic asymmetric synthesis of axially chiral biaryl phosphonates with p-quinone phosphonates and 2-naphthols via CPA-catalyzed asymmetric arylations. A series of chiral biaryl monophosphonates were obtained in excellent yields and enantioselectivities (up to 99% yield and 95% ee). This reaction could be operated at a gram scale with a low catalyst loading (0.5 mol %). Remarkably, our approach provides a green and ready access to chiral biaryl monophosphorus ligands. Compound 4ca was successfully converted to novel chiral biaryl monophosphorus ligands 7a, 7b, and 8 with high enantioselectivities in three steps.
RESUMEN
An enantioselective (3+2) cycloaddition of enals and cyclic N-sulfonyl trifluoromethyl ketimines via N-heterocyclic carbene-catalyzed homoenolate addition is described. This reaction can efficiently construct fused N-heterocycle γ-lactams bearing two adjacent chiral centers with >20 : 1 dr and 94-99% ee, with one chiral center as a trifluoromethylated α-tetrasubstituted carbon stereocenter.