Giacomo Renno, Dongping Chen, Qing-Xia Zhang, Rosa M Gomila, Antonio Frontera, Naomi Sakai, Thomas R Ward, Stefan Matile
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引用次数: 0
摘要
本研究的目的是创建人工酶,利用生物催化中基本不存在的 s 孔相互作用--pnictogen 键。 为此,我们在 stibine 催化剂上添加了生物素衍生物,并将其与链霉亲和素突变体相结合,以确定一种高效的转移氢化催化剂,用于还原含氟喹啉底物。 从野生型链霉亲和素到最佳突变体催化活性的提高与 Sb(V)中心 s 孔的深度以及饱和动力学行为的出现相吻合。 迈克尔斯-门顿分析表明,过渡态的识别能力在低微摩尔范围内,比毫摩尔底物识别能力强三个数量级以上。 最佳突变体偏好的羧酸盐通过氢键离子配对和阴离子-π与新出现的吡啶产物的相互作用,促进了过渡态识别。 水性体系中出现的具有挑战性的立体选择性进一步强调了吡啶鎓键与高阶体系催化的兼容性。
The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a s-hole interaction that is essentially absent in biocatalysis. For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate. Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the s hole on the Sb(V) center, and the emergence of saturation kinetic behavior. Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition. Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product. The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.