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活性二铑卡宾配合物的首个晶体结构以及通过铑到金的金属转移制备金卡宾的通用方法。

The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium-to-Gold Transmetalation.

作者信息

Werlé Christophe, Goddard Richard, Fürstner Alois

机构信息

Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany).

出版信息

Angew Chem Int Ed Engl. 2015 Dec 14;54(51):15452-6. doi: 10.1002/anie.201506902. Epub 2015 Nov 4.

DOI:10.1002/anie.201506902
PMID:26534892
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4832834/
Abstract

The dirhodium carbene derived from bis(4-methoxyphenyl)diazomethane and [Rh(tpa)4 ]⋅CH2 Cl2 (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X-ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4-methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf2 ] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect.

摘要

由双（4-甲氧基苯基）重氮甲烷和[Rh（tpa）4]·CH2Cl2（tpa = 三苯基乙酸酯）衍生的二铑卡宾通过紫外光谱、红外光谱、核磁共振光谱、高分辨质谱以及X射线衍射进行了表征。分离得到的配合物表现出典型的铑卡宾反应活性，即在低温下它能使4-甲氧基苯乙烯环丙烷化。关于这种重要类型的反应中间体的实验结构信息极其稀少，因此总体上可作为铑催化机理讨论的参考点。此外，已表明二铑卡宾在用[LAuNTf2]（L = 膦）处理时会发生非常容易的卡宾转移。这种形式上的金属转移为难以通过其他方式制备的金卡宾配合物开辟了一条有价值的新途径；三个完全表征的代表物说明了这一方面。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/02dffd3a23e7/ANIE-54-15452-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/12ea5257bde2/ANIE-54-15452-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/09e3433efa17/ANIE-54-15452-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/a50f6dcc3cbd/ANIE-54-15452-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/0b8f95de42a8/ANIE-54-15452-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/a39c6582fdbf/ANIE-54-15452-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/02dffd3a23e7/ANIE-54-15452-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/12ea5257bde2/ANIE-54-15452-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/09e3433efa17/ANIE-54-15452-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/a50f6dcc3cbd/ANIE-54-15452-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/0b8f95de42a8/ANIE-54-15452-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/a39c6582fdbf/ANIE-54-15452-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/86e0/4832834/02dffd3a23e7/ANIE-54-15452-g007.jpg

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