Enantioselective Synthesis of Chiral Biaryl Chlorides/Iodides by a Chiral Phosphoric Acid Catalyzed Sequential Halogenation Strategy

• Published in: Advanced synthesis & catalysis Vol. 357; no. 1; pp. 35 - 40
• Main Authors: Mori, Keiji, Kobayashi, Manato, Itakura, Tsubasa, Akiyama, Takahiko
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 12.01.2015; WILEY‐VCH Verlag; Wiley
• Subjects: asymmetric synthesis; Asymmetry; biaryls; Chemistry; Chemistry, Applied; Chemistry, Organic; Chlorides; desymmetrization; Halogenation; halogenations; Iodides; kinetic resolution; Physical Sciences; Reaction kinetics; Science & Technology; Selectivity; Strategy; Synthesis; ACTIVATION; desymmetrization; REAGENTS; ASYMMETRIC BROMOLACTONIZATION; NATURAL-PRODUCTS; ORGANOCATALYTIC ALPHA-CHLORINATION; BROMOCYCLIZATION; HALOCYCLIZATION; asymmetric synthesis; biaryls; LIGANDS; halogenations; kinetic resolution; IODOLACTONIZATION
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201400611

We report herein a highly enantioselective synthesis of multisubstituted biaryl chlorides/iodides by sequential halogenation reactions (desymmetrization/kinetic resolution sequence). The selectivity of biaryl chlorides/iodides obtained in the first asymmetric reaction (desymmetrization) could be enhanced by the kinetic resolution‐type asymmetric bromination to afford the corresponding chiral biaryl chlorides/iodides in excellent selectivities (up to 99 % ee).