152326-82-4Relevant articles and documents
Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions
Novacek, Johanna,Roiser, Lukas,Zielke, Katharina,Robiette, Rapha?l,Waser, Mario
supporting information, p. 11422 - 11428 (2016/08/03)
The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.
Dual catalyst system for asymmetric alternating copolymerization of carbon dioxide and cyclohexene oxide with chiral aluminum complexes: Lewis base as catalyst activator and lewis acid as monomer activator
Nishioka, Kiyoshi,Goto, Hidetoshi,Sugimoto, Hiroshi
, p. 8172 - 8192 (2013/01/15)
Optically active aluminum complexes such as Schiff base, binuclear β-ketoiminate, and bisprolinol complexes were found to promote asymmetric alternating copolymerizations of carbon dioxide and cyclohexene oxide. The aluminum Schiff base complexes-tetraethylammonium acetate afforded isotactic poly(cyclohexene carbonate)s with low enantioselectivities. Lewis bases having two coordinating sites were utilized to enhance activity and selectivity based on the binuclear structure of the aluminum β-ketoiminate clarified by X-ray crystallography. [2gAlMe]2-bulky bisimidazole produced the alternating copolymer with high enantioselectivity (62% ee). The polymerization is considered to preferentially proceed at more crowded, enantioselective site owing to coordination of bulky Lewis bases to aluminums in less enantioselective sites. 32AlMe-2-picoline also exhibited a high enantioselectivity (67% ee). Methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) was applied to perform faster and more enantioselective copolymerizations at low temperature (82% ee). The asymmetric copolymerizations were found to be significantly dependent on size of epoxide, temperature, and kind/amount of activators.
Enantioselective michael addition to α,β-Unsaturated aldehydes: Combinatorial catalyst preparation and screening, reaction optimization and mechanistic studies
Fleischer, Ivana,Pfaltz, Andreas
supporting information; experimental part, p. 95 - 99 (2010/03/26)
Shortcut to chiral catalysts: An efficient combinatorial strategy based on back reaction screening by ESI-MS allows rapid evaluation of organocatalysis for the asymmetric Michael addition to α,β-unsaturated aldehydes (see scheme). An unexpected nonlinear effect has been observed in this reaction, resulting from a double nucleophilic-electrophilic activation mechanism involving two catalyst molecules "Chemical Equation Presented"