Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University , Nanjing 211816, China.
Org Lett. 2017 Oct 20;19(20):5593-5596. doi: 10.1021/acs.orglett.7b02731. Epub 2017 Oct 5.
In this work, an organopromoted metal-free pharmaceutical-oriented selectivity-switchable benzylic oxidation was developed, affording mono-, di-, and trioxygenation products, respectively, using oxygen as the oxidant under mild conditions. This process facilitates dioxygenation of 2,6-benzylic positions of heterocycles, which could be inhibited by heterocycle chelation to the metal cocatalysts. Enantiopure chiral ketones could also be prepared. The noninvolvement of transition metals and toxins avoids metal or hazardous residues, consequently ensuring a final-stage gram-scale synthesis of Lenperone.
在这项工作中，开发了一种有机促进的无金属医药导向选择性开关苄位氧化，分别使用氧气作为氧化剂，在温和条件下得到单、二和三氧化产物。该过程促进了杂环的 2,6-苄位的双氧化，杂环螯合金属共催化剂可以抑制其双氧化。也可以制备对映纯手性酮。不涉及过渡金属和毒素避免了金属或有毒残留物，从而保证了 Lenperone 的最终阶段克级合成。
