Lin Yun, Zhu Lei, Lan Yu, Rao Yu
MOE Key Laboratory of Protein Sciences, Department of Pharmacology and Pharmaceutical Sciences, School of Medicine and School of Life Sciences, Tsinghua University, Beijing, 100084 (P. R. China).
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 (P. R. China).
Chemistry. 2015 Oct 12;21(42):14937-42. doi: 10.1002/chem.201502140. Epub 2015 Aug 27.
We report the first example of Rh(II) -catalyzed chemoselective double C(sp(3) )-H oxygenation, which can directly transform various toluene derivatives into highly valuable aromatic aldehydes with great chemoselectivity and practicality. The critical combination of catalyst Rh(OAc)2 , oxidant Selectfluor, and solvents of TFA/TFAA promises the successful delivery of the oxidation with satisfactory yields. A possible mechanism involving a unique carbene-Rh complex is proposed, and has been supported by both experiments and theoretical calculations.
我们报道了首例铑（II）催化的化学选择性双C(sp(3) )-H氧化反应，该反应能够以高化学选择性和实用性将各种甲苯衍生物直接转化为高价值的芳香醛。催化剂Rh(OAc)2、氧化剂Selectfluor和TFA/TFAA溶剂的关键组合确保了氧化反应能够成功进行并获得令人满意的产率。我们提出了一种可能的机理，涉及一种独特的卡宾-铑配合物，并且该机理得到了实验和理论计算的支持。
