Active Site Design in a Chemzyme: Development of a Highly Asymmetric and Remarkably Temperature-Independent Catalyst for the Imino Aldol Reaction
                                
                                    
                                        作者:Song Xue、Su Yu、Yonghong Deng、William D. Wulff                                    
                                    
                                        DOI:10.1002/1521-3773(20010618)40:12<2271::aid-anie2271>3.0.co;2-n
                                    
                                    
                                        日期:2001.6.18
                                    
                                    Unusually robust: A remarkably temperature-independent catalyst has been developed for the imino aldol reaction of imines derived from ortho-aminophenols. This catalyst is prepared from two equivalents of the VAPOL ligand and a zirconium tetraalkoxide. From a consideration of likely intermediates in the catalytic cycle it was deduced that a methyl substituent ortho to the phenol (R1 ) should enhance induction. This resulted in asymmetric inductions in excess of 98 % ee at room temperature as well as at 100°C. TMS=trimethylsilyl.