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芳基 C(sp)-X 键偶联反应（X = C、N、O、Cl）及在 Pt(IV) 中心对伯胺的 N-单芳基化和 N,N-双芳基化的简易控制

Aryl C(sp)-X Coupling (X = C, N, O, Cl) and Facile Control of N-Mono- and N,N-Diarylation of Primary Alkylamines at a Pt(IV) Center.

机构信息

School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States.

出版信息

J Am Chem Soc. 2020 Dec 9;142(49):20725-20734. doi: 10.1021/jacs.0c09452. Epub 2020 Nov 23.

DOI:10.1021/jacs.0c09452
PMID:33226792
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7884019/
Abstract

We present the first example of an unprecedented and fast aryl C(sp)-X reductive elimination from a series of isolated Pt(IV) aryl complexes (Ar = -FCH) LPtF(py)(Ar)X (X = CN, Cl, 4-OCHNO) and LPtF(Ar)(HX) (X = NHAlk; Alk = -Bu, PhCH, cyclo-CH, -Bu, cyclopropylmethyl) bearing a bulky bidentate 2-[bis(adamant-1-yl)phosphino]phenoxide ligand (L). The C(sp)-X reductive elimination reactions of all isolated Pt(IV) complexes follow first-order kinetics and were modeled using density functional theory (DFT) calculations. When a difluoro complex LPtF(Ar)(py) is treated with TMS-X (TMS = trimethylsilyl; X= NMe, SPh, OPh, CCPh) it also gives the corresponding products of the Ar-X coupling but without observable LPtF(py)(Ar)X intermediates. Remarkably, the LPtF(Ar)(HX) complexes with alkylamine ligands (HX = NHAlk) form selectively either mono- (ArNHAlk) or diarylated (ArNAlk) products in the presence or absence of an added EtN, respectively. This method allows for a one-pot preparation of diarylalkylamine bearing different aryl groups. These findings were also applied in unprecedented mono- and di-N-arylation of amino acid derivatives (lysine and tryptophan) under very mild conditions.

摘要

我们提出了首例前所未有的、快速的芳基 C(sp)-X 还原消除反应的实例，该反应来自一系列分离的 Pt(IV)芳基配合物（Ar = -FCH） LPtF(py)(Ar)X（X = CN、Cl、4-OCHNO）和 LPtF(Ar)(HX)（X = NHAlk； Alk = -Bu、PhCH、cyclo-CH、-Bu、环丙基甲基），它们带有一个庞大的双齿 2-[双（金刚烷-1-基）膦基]苯酚配体（L）。所有分离的 Pt(IV)配合物的 C(sp)-X 还原消除反应均遵循一级动力学，并使用密度泛函理论（DFT）计算进行了模拟。当二氟配合物 LPtF(Ar)(py)与 TMS-X（TMS = 三甲基硅烷基；X= NMe、SPh、OPh、CCPh）反应时，它也会得到相应的 Ar-X 偶联产物，但没有观察到 LPtF(py)(Ar)X 中间体。值得注意的是，带有烷基胺配体的 LPtF(Ar)(HX)（HX = NHAlk）配合物在添加或不添加 EtN 的情况下，分别选择性地形成单（ArNHAlk）或二芳基化（ArNAlk）产物。该方法允许在一锅法中制备带有不同芳基的二芳基烷基胺。这些发现还应用于在非常温和的条件下对氨基酸衍生物（赖氨酸和色氨酸）进行前所未有的单和双 N-芳基化。

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