title: Molecular assembly of an achiral phosphine and a chiral primary amine: a highly efficient supramolecular catalyst for the enantioselective Michael reaction of aldehydes with maleimides.
abstract: A combined catalyst system of a cinchonidine-derived primary amine and triphenylphosphine (CD-NH2 /PPh3 ) exhibited high catalytic performance in the Michael reaction of aldehydes with maleimides, thereby affording the corresponding functionalized aldehydes in excellent yields (up to 99 %) and enantioselectivities (>99 % ee). More interestingly, the significance of the phosphine in enhancing the enantioselectivities in the chiral-primary-amine-catalyzed Michael reaction was revealed. Furthermore, we explored the origin of the reaction mechanism in the Michael addition promoted by the dual organocatalytic system. On the basis of experimental results and spectroscopic analysis, such as UV/Vis, fluorescence emission (FL), NMR, and circular dichroism (CD) spectroscopy, as well as ESI-MS, we found that the molecular assembly of phosphine and primary amine played a crucial role in this enantioselective reaction, in which a possible supramolecular complex was formed as an effective chiral catalyst through noncovalent molecular interactions of a cinchona alkaloid-derived primary amine with triphenylphosphine.
authors.affiliation: Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, PR China.
authors.forename: Wei
authors.initials: W
authors.lastname: Yang
authors.forename: Ke-Zhi
authors.initials: KZ
authors.lastname: Jiang
authors.forename: Xing
authors.initials: X
authors.lastname: Lu
authors.forename: Hua-Meng
authors.initials: HM
authors.lastname: Yang
authors.forename: Li
authors.initials: L
authors.lastname: Li
authors.forename: Yixin
authors.initials: Y
authors.lastname: Lu
authors.forename: Li-Wen
authors.initials: LW
authors.lastname: Xu
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D002930:Cinchona Alkaloids / Q000737:chemistry; D046911:Macromolecular Substances / Q000737:chemistry*; D008301:Maleimides / Q000737:chemistry*; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000588:Amines; D002930:Cinchona Alkaloids; D046911:Macromolecular Substances; D008301:Maleimides; D009943:Organophosphorus Compounds; C061896:triphenylphosphine