1236039-19-2Relevant articles and documents
Linking conformational flexibility and kinetics: Catalytic 1,4-type friedel-crafts reactions of phenols utilizing 1,3-diamine-tethered guanidine/bisthiourea organocatalysts
Sohtome, Yoshihiro,Shin, Bongki,Horitsugi, Natsuko,Noguchi, Keiichi,Nagasawa, Kazuo
supporting information; scheme or table, p. 2463 - 2470 (2012/07/13)
Herein, we present details of our conformationally flexible, 1,3-diamine-tethered guanidine/bisthiourea organocatalysts for chemo-, regio-, and enantioselective 1,4-type Friedel-Crafts reactions of phenols. These organocatalysts show a unique stereo-discrimination governed by the differential activation entropy (δδS+), rather than by the differential activation enthalpy (δδH+). Extensive kinetic analyses using Eyring plots for a series of guanidine/bisthiourea organocatalysts revealed the key structural motif in the catalysts associated with a large magnitude of differential activation entropy (δδS +). A plausible guanidine-thiourea cooperative mechanism for the enantioselective Friedel-Crafts reaction is proposed. Copyright