Convincing Catalytic Performance of Oxo-Tethered Ruthenium Complexes for Asymmetric Transfer Hydrogenation of Cyclic α‑Halogenated Ketones through Dynamic Kinetic Resolution

• Published in: Organic letters Vol. 23; no. 8; pp. 3070 - 3075
• Main Authors: Touge, Taichiro, Nara, Hideki, Kida, Michio, Matsumura, Kazuhiko, Kayaki, Yoshihito
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 16.04.2021; Amer Chemical Soc
• Subjects: carboxamides; catalysts; catalytic activity; Chemistry; Chemistry, Organic; dopamine receptors; halogens; hydrogenation; ligands; Physical Sciences; ruthenium; Science & Technology; ALCOHOLS; ENANTIOSELECTIVE SYNTHESIS; REDUCTION; HALOHYDRINS; RECEPTOR; INTERMEDIATE; DERIVATIVES; ACCESS
• ISSN: 1523-7060; 1523-7052; 1523-7052
• DOI: 10.1021/acs.orglett.1c00739

A highly efficient dynamic kinetic resolution of cyclic halohydrins was achieved by the asymmetric transfer hydrogenation of racemic α-haloketones. Bifunctional oxo-tethered Ru­(II) catalysts could promote the reduction without deterioration of halogens. By structural tuning of the catalyst, chiral alcohols having halogen, ester, carboxamide, and sulfone functions were obtained variably with excellent diastereo- and enantioselectivities (up to >99:1 d.r. and >99.9 ee), which provided a concise synthetic approach to a dopamine D3 receptor ligand, (+)-PHNO.