Design of Chiral Bifunctional Dialkyl Sulfide Catalysts for Regio‐, Diastereo‐, and Enantioselective Bromolactonization

• Published in: Chemistry : a European journal Vol. 24; no. 63; pp. 16747 - 16752
• Main Authors: Nishiyori, Ryuichi, Tsuchihashi, Ayano, Mochizuki, Ayaka, Kaneko, Kazuma, Yamanaka, Masahiro, Shirakawa, Seiji
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 13.11.2018; Wiley Subscription Services, Inc
• Subjects: asymmetric synthesis; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Dialkyl sulfides; Enantiomers; lactonizations; organocatalysis; Physical Sciences; Science & Technology; Sulfide; Sulfides; transition states; Urea; Ureas; ORGANIC-SYNTHESIS; SULFUR YLIDES; HYDRANGEAE DULCIS FOLIUM; PHASE-TRANSFER CATALYST; OLEFINIC 1,3-DIOLS; lactonizations; organocatalysis; ALKENES; asymmetric synthesis; transition states; ASYMMETRIC EPOXIDATION; SULFONIUM YLIDES; YLIDE-MEDIATED EPOXIDATION; sulfides; REGIOSELECTIVE BROMOCYCLIZATION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201803703

Although a wide variety of chiral organocatalysts have been developed for asymmetric transformations, effective chiral dialkyl sulfide organocatalysts remain relatively rare and under‐developed, despite the potential utility of dialkyl sulfide catalysts. Herein, we report the development of chiral bifunctional dialkyl sulfide catalysts possessing a urea moiety for regio‐, diastereo‐, and enantioselective bromolactonization. The importance of the bifunctional design of chiral sulfide catalysts was clearly demonstrated in the present work. The roles of both the sulfide and urea moieties of the catalyst were clarified based on the results of experimental and theoretical investigation. Chiral bifunctional dialkyl sulfide catalysts bearing a urea moiety were designed for enantioselective bromolactonization. The roles of both sulfide and urea moieties on the catalyst are discussed and clarified based on the results of both experimental and theoretical investigation.