Bonsignore Riccardo, Thomas Sophie R, Klooster Wim T, Coles Simon J, Jenkins Robert L, Bourissou Didier, Barone Giampaolo, Casini Angela
School of Chemistry, Cardiff University, Main Building, Park Place, CF10 3AT, Cardiff, UK.
School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK.
Chemistry. 2020 Apr 1;26(19):4226-4231. doi: 10.1002/chem.201905392. Epub 2020 Mar 6.
With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the Au -mediated C -P bond formation occurring upon reaction of C^N cyclometalated Au complexes with phosphines. The [Au(C^N)Cl ] complex 1 featuring the bidentate 2-benzoylpyridine (C N) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C-P reductive elimination. A mechanism is proposed for the title reaction based on in situ P{ H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C-P coupling has been generalized to other C^N cyclometalated Au complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated Au compounds and establishes initial structure-activity relationships to develop Au -mediated C-P cross-coupling reactions.
为了开发用于交叉偶联反应的新型有机金属物种，我们在此报告在C^N环金属化金配合物与膦反应时发生的金介导的C-P键形成。发现具有双齿2-苯甲酰基吡啶（C^N）骨架的[Au（C^N）Cl]配合物1在温和条件下（包括在水中）与PTA（1,3,5-三氮杂-7-磷杂金刚烷）反应，通过C-P还原消除得到相应的鏻盐5。基于原位P{H} NMR和HR-ESI-MS分析并结合DFT计算，提出了标题反应的机理。C-P偶联已推广到其他C^N环金属化金配合物和其他叔膦。总体而言，这项工作为环金属化金化合物的反应性提供了新的见解，并建立了初步的构效关系以开发金介导的C-P交叉偶联反应。
