萘基取代的手性双噁唑啉-铜(Ⅰ)络合物催化下环烯烃不对称烯丙基氧化反应的研究

摘要

Synthesis of naphthyl substituted malonyl-derived (Box) and pyridine-based bisoxazolines ( PyBox) as well as their applications in the asymmetric allylic oxidation of cyclohexene with t-butyl p-ni-troperbenzoate have been carried out, with significantly improved reactivity (75%) while maintaining very good enantioselectivity (85% ) using the ligand with 1-naphthyl group as the side chain on oxazoline ring. The correlations between the nature of the substituents on the bisoxazolines and the reactivity/selectivity have been established.%阐述了萘基取代丙二酰衍生的手性双噁唑啉(Box)和吡啶为中心的双噁唑啉(PyBox)手性配体的合成方法,及它们的铜(Ⅰ)络合物与对硝基过苯甲酸特丁酯在环已烯的不对称烯丙基氧化反应中的催化应用.并对双噁唑啉配体的侧链取代基与反应活性和选择性的内在联系进行了深入的探讨.结果表明,当1-萘基取代的双噁唑啉铜(Ⅰ)作为催化剂时,反应活性得到极大提高(分离产率75％),同时能保持极好的对映体选择性(85％).通过对原始数据的研究,建立了双噁唑啉配体的侧链取代基与反应活性和选择性的内在联系.