Synthesis Of Chiral Metalloporphyrins And Their Catalytic Asymmetric Hydroxylation Of Phenylacetonitrile

Seeking highly effective chiral catalysts to catalyze asymmetric oxidation of hydrocarbons under normal pressure and room temperature is one of the global problems. Chiral metalloporphyrins can catalyze asymmetric oxidation of prochiral hydrocarbons under the mild condition because of their unique structure. Much attention was paid to design and synthesis of novel chiral metalloporphyrins to simulate the cytochrome P-450 enzyme's asymmetric catalytic oxidation. As we known from the documented literatures that the chiral structures affected the metalloporphyrin's catalytic activity, selectivity and stability. To get the highly efficient and stable chiral catalysts, it should be mentioned that the key step is to design and synthesis of the ideal chiral groups and metalloporphyrins with good topological optimization structure. In pursuit of a highly reactive chiral porphyrin catalyst to catalyze asymmetric hydroxylation of phenylacetonitrile, series of chiral porphyrins were synthesized and were applied to the catalysis and the researching contents were summarized below:1. Synthetic methodologies toward menthol modified C2 symmetric chiral metalloporphyrins and camphor modified chiral metalloporphyrins were investigated. And developed a synthetic methods to synthesize a series of menthol modified C2 symmetric chiral metalloporphyrins and camphor-containing chiral metalloporphyrins from menthol and camphor respectively. The newly synthesized target molecule and the corresponding intermediates were characterized by UV-Vis, MS (or HRMS), IR, 1HNMR, elemental analysis and the optical rotation.2. Application of above synthesized chiral porphyrins was studied for catalytic asymmetric oxidation of phenylacetonitrile. The menthol modified C2 symmetric chiral metalloporphyrins catalyzed asymmetric hydroxylation reaction of phenylacetonitrile with iodosobenzene was carried out at room temperature and the normal pressure. The same condtions were loaded for camphor modified chiral metalloporphyrins catalyzed asymmetric hydroxylation reaction of phenylacetonitrile with iodosobenzene. The results showed that these chiral porphyrins had an unique catalytic effect and somewhat asymmetry-induced effect for the asymmetric hydroxylation reaction of phenylacetonitrile. A new HPLC analysis method for the products of asymmetric hydroxylation reaction of phenylacetonitrile was obtained after investigation in detail which made the analysis result quite accurate.