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非典型和不对称的 1,3-P,N 配体：环亚氨基膦烷的合成、配位和催化性能。

Atypical and Asymmetric 1,3-P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes.

机构信息

Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.

Department of Chemistry, University of Helsinki, A. I. Virtasen aukio 1, P.O. Box 55, FIN-00014, Helsinki, Finland.

出版信息

Chemistry. 2021 Oct 7;27(56):14007-14016. doi: 10.1002/chem.202101921. Epub 2021 Sep 8.

DOI:10.1002/chem.202101921
PMID:34403555
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8519111/
Abstract

Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These "cycloiminophosphanes" possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-κ - and P,N-κ -tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl ] demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ and κ species; treatment with AgOTf gives full conversion to the κ complex. The potential for catalysis was shown in the Ru -catalyzed, solvent-free hydration of benzonitrile and the Ru - and Ir -catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-κ -Rh and a P-κ -Ru complexes.

摘要

新型七元环亚胺基 1,3-P,N 配体是通过捕获环己酮原位生成的贝克曼腈离子中间体与苯并三唑反应得到的，然后在三氟甲磺酸促进下用仲膦取代。这些“环亚氨基膦”具有灵活的非异构化的四氢氮杂环，碱性较高；这使它们有别于之前报道的亚氨基磷烷。通过使用它们的 P-κ-和 P,N-κ-钨(0)羰基配合物来研究配体的给电子强度，通过确定反式-CO 配体的 IR 频率。[RhCp*Cl]的配合物表现出配体的半配位能力，形成了κ和κ物种的动态平衡；用 AgOTf 处理可完全转化为 κ 配合物。在无溶剂条件下，通过 Ru 催化苯甲腈的水合反应以及在异丙醇中通过 Ru 和 Ir 催化环己酮的转移氢化反应，展示了其催化潜力。最后，为了能够获得不对称催化剂，从 L-薄荷酮制备了手性环亚氨基膦，以及它们的 P,N-κ-Rh 和 P-κ-Ru 配合物。

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