Synthesis of Fused Metallaaromatics via Intramolecular C–H Activation of Thiophenes
Synthesis of Fused Metallaaromatics via Intramolecular C–H Activation of Thiophenes
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DOI：
10.1021/acs.organomet.6b00083
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发表时间：
2016-04
期刊：
影响因子：
2.8
通讯作者：
Qingde Zhuo;Xiaoxi Zhou;Huijun Kang;Zhiyong Chen;Yuhui Yang;Feifei Han;Hong Zhang;H. Xia
中科院分区：
文献类型：
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作者：
Qingde Zhuo;Xiaoxi Zhou;Huijun Kang;Zhiyong Chen;Yuhui Yang;Feifei Han;Hong Zhang;H. Xia
提出了一种利用分子内C-H活化噻吩合成新型熔融钌/锇环的简便方法。用RuCl2(PPh3)3或OsCl2(PPh3)3处理HC≡CCH(OH)R （R = 2-噻吩基）得到羟基配位的金属乙烯基化合物1和4。1/4与酸反应生成金属烯基碳配合物3/5，通过噻基的C(sp2) -H活化，进一步转化为相应的熔融金属芳构物2/7。7是具有熔融五元环（噻吩环）的金属酶的第一个例子。这些熔合的金属原子在溶液和空气中的固态中都是热稳定的。x射线晶体学分析、核磁共振光谱和DFT计算都表明这些熔融金属芳构体（2和7）具有芳香特征。
A convenient method to synthesize novel fused ruthena-/osmacycles via intramolecular C–H activation of thiophenes has been developed. Treatment of HC≡CCH(OH)R (R = 2-thienyl) with RuCl2(PPh3)3 or OsCl2(PPh3)3 afforded hydroxyl-coordinated metal vinyl compounds 1 and 4. Reaction of 1/4 with acid produced metal alkenylcarbene complexes 3/5, which can further convert to the corresponding fused metallaaromatics 2/7 via the C(sp2)–H activation of the thienyl groups. 7 is the first example of a metallabenzyne with a fused five-membered ring (thiophene ring). These fused metallaaromatics are thermally stable both in solution and in the solid state in air. The X-ray crystallographic analysis, NMR spectra, and DFT calculations all suggest that these fused metallaaromatics (2 and 7) show aromatic character.