Department of Process Research and Development, Merck Sharp & Dohme Corp., Rahway, NJ 07065, USA.
Angew Chem Int Ed Engl. 2017 Nov 27;56(48):15274-15278. doi: 10.1002/anie.201707537. Epub 2017 Oct 26.
Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H O or O as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow.
在分子的远程位置上含氧的脂肪胺是一类重要的合成砌块，目前尚无直接的方法可以得到。本文报道了一种高效、可规模化的方法，该方法依赖于酸性条件下的过钨酸盐光催化，以 H2O 或 O2 作为末端氧化剂。使用这些反应条件，可以将一系列简单、无偏见的脂肪胺起始原料氧化为有价值的酮类产物。最后，使用原位 LED 辐照样品的 NMR 光谱学来监测反应动力学，从而能够直接将反应转化为流动反应。
