on the formation of an electrondonor–acceptorcomplexbetween the substrates and enzyme cofactor and simplifies the reaction system by obviating the addition of a cofactor regeneration mixture. More importantly, the GluER variant exhibits high reactivity and enantioselectivity and a broad substrate scope. Mechanistic studies support the proposed oxidation-initiated mechanism and reveal that a tyrosine-mediated
控制氢原子转移(HAT)反应的对映选择性一直是一个长期存在的合成挑战。虽然光酶催化的最新进展已经证明了非天然光酶的巨大潜力,但所有转化都是由底物的单电子还原引发的,只有一个明显的例外。在此,我们报告了使用葡糖杆菌烯还原酶的新型突变体(GluER-W100F-W342F)进行氧化引发的烯烃光酶对映选择性氢磺酰化。与已知的光酶系统相比,我们的方法不依赖于底物和酶辅因子之间电子供体-受体复合物的形成,并且通过避免添加辅因子再生混合物来简化反应系统。更重要的是,GluER 变体表现出高反应活性和对映选择性以及广泛的底物范围。机理研究支持了所提出的氧化引发机制,并揭示了酪氨酸介导的 HAT 过程的参与。
Highly Enantioselective Organocatalytic Carbonyl-Ene Reaction with Strongly Acidic, Chiral Brønsted Acids as Efficient Catalysts
作者:Magnus Rueping、Thomas Theissmann、Alexander Kuenkel、René M. Koenigs
DOI:10.1002/anie.200802139
日期:2008.8.25
The Reaction between Maleic Anhydride and Vinyl Hydrindenes