利用硫脲-氯超分子配合物中的非共价π型相互作用:重氮杂环的不对称脱芳化

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Marta Velázquez, Pilar Elías-Rodríguez, Tomás Tejero, Rosario Fernández*, Pedro Merino*, José M. Lassaletta* and David Monge*, 
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引用次数: 0

摘要

研究了阴离子结合催化重氮杂环的对映选择性脱芳。该过程包括将亲核试剂磷亲核加成到原位生成的n -苯甲酰氯,使用叔亮氨酸衍生的硫脲作为氢键给体催化剂,从而获得吸引人的环肼膦酸盐及其衍生物。机理研究表明,这些盐的低溶解度可能有利于形成超分子硫脲-氯化物-铝2:1:1配合物,该配合物被认为是催化相关的物质,可以解释所观察到的非线性效应。实验和计算数据支持通过这种高度有序的离子对的4h活化模型,其中两个硫脲分子以反平行的方向排列在氯离子周围,产生c2对称槽。因此,通过关键的非共价π型相互作用,保证了n -苯甲酰铵的立体插入,从而最大限度地提高了对映体诱导事件。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Harnessing Noncovalent π-Type Interactions in Thiourea–Chloride Supramolecular Complexes: Toward the Asymmetric Dearomatization of Diazaheterocycles

Enantioselective dearomatization of diazaheterocycles through anion-binding catalysis has been developed. The process involves the nucleophilic addition of phosphorus nucleophiles to in situ generated N-benzoyliminium chlorides, using a tert-leucine-derived thiourea as an H-bond donor catalyst, thereby providing access to appealing cyclic hydrazino phosphonates and their derivatives. Mechanistic investigations suggest that the low solubility of these salts might favor the formation of a supramolecular thiourea–chloride–iminium 2:1:1 complex, which is proposed as the catalytically relevant species accounting for the observed nonlinear effect. Experimental and computational data support a 4H-activation model via this highly ordered ion pair, in which two thiourea molecules are arranged in an antiparallel orientation around the chloride, generating a C2-symmetric groove. Hence, stereodefined insertion of the N-benzoyliminium is ensured by key noncovalent π-type interactions, thereby maximizing the enantioinduction event.

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来源期刊
ACS Catalysis
ACS Catalysis CHEMISTRY, PHYSICAL-
CiteScore
20.80
自引率
6.20%
发文量
1253
审稿时长
1.5 months
期刊介绍: ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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