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Regiodivergent and Enantioselective Synthesis of Cyclic Sulfones via Ligand-Controlled Nickel-Catalyzed Hydroalkylation.
Fan, Chao; Dhawa, Uttam; Qian, Deyun; Sakic, Davor; Morel, Jennifer; Hu, Xile.
Afiliación
  • Fan C; Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, ISIC-LSCI, BCH 3305, 1015, Lausanne, Switzerland.
  • Dhawa U; Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, ISIC-LSCI, BCH 3305, 1015, Lausanne, Switzerland.
  • Qian D; Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, ISIC-LSCI, BCH 3305, 1015, Lausanne, Switzerland.
  • Sakic D; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovacica 1, 10000, Zagreb, Croatia.
  • Morel J; Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, ISIC-LSCI, BCH 3305, 1015, Lausanne, Switzerland.
  • Hu X; Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, ISIC-LSCI, BCH 3305, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl ; 63(29): e202406767, 2024 Jul 15.
Article en En | MEDLINE | ID: mdl-38682392
ABSTRACT
Cyclic sulfones have demonstrated important applications in drug discovery. However, the catalytic and enantioselective synthesis of chiral cyclic sulfones remains challenging. Herein, we develop nickel-catalyzed regiodivergent and enantioselective hydroalkylation of sulfolenes to streamline the synthesis of chiral alkyl cyclic sulfones. The method has broad scope and high functional group tolerance. The regioselectivity can be controlled by ligands only. A neutral PYROX ligand favors C3-alkylation whereas an anionic BOX ligand favors C2-alkylation. This control is kinetic in origin as the C2-bound Ni intermediates are always thermodynamically more stable. Reactivity study of a wide range of relevant Ni intermediates reveal a NiI/NiIII catalytic cycle with a NiII-H species as the resting state. The regio- and enantio-determining step is the insertion of this NiII-H species into 2-sulfolene. This work provides an efficient catalytic method for the synthesis of an important class of organic compounds and enhances the mechanistic understanding of Ni-catalyzed stereoselective hydroalkylation.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: Suiza Pais de publicación: Alemania
Texto completo
Añadir a Mi BVS
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XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: Suiza Pais de publicación: Alemania