Gaykar Rahul N, George Malini, Guin Avishek, Bhattacharjee Subrata, Biju Akkattu T
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, India.
Org Lett. 2021 May 7;23(9):3447-3452. doi: 10.1021/acs.orglett.1c00911. Epub 2021 Apr 8.
An oxa-[2,3] sigmatropic rearrangement involving arynes is reported featuring the umpolung of ketones, where the C═O bond polarity is reversed. The in situ-generated sulfur ylides from β-keto thioethers and arynes undergo efficient rearrangement allowing the facile and robust synthesis of functionalized enol ethers in high yields and excellent functional group compatibility. Preliminary mechanistic studies rule out the possibility of Pummerer-type rearrangement operating in this case.
据报道，一种涉及芳炔的氧杂-[2,3] 迁移重排反应具有酮的极性反转特性，其中C═O键的极性发生了逆转。由β-酮硫醚和芳炔原位生成的硫叶立德能高效地进行重排反应，从而能够高产率且具有出色官能团兼容性地简便、稳健地合成官能化烯醇醚。初步机理研究排除了在此情况下发生普默勒尔型重排反应的可能性。
