Gore Babasaheb Sopan, Kuo Chiao-Ying, Garkhedkar Amol Milind, Chang Yu-Lun, Wang Jeh-Jeng
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, No. 100, Shiquan First Road, Sanmin District, Kaohsiung City, 807, Taiwan.
Department of Medical Research, Kaohsiung Medical University Hospital, No. 100, Tzyou First Road, Sanmin District, Kaohsiung City, 807, Taiwan.
Org Lett. 2020 Aug 7;22(15):6160-6165. doi: 10.1021/acs.orglett.0c02240. Epub 2020 Jul 24.
A general protocol for the synthesis of multisubstituted 2,3-dihydrofuran-2-carbonitriles and 4,5-dihydrofuran-3-carbonitriles was demonstrated under a metal-free regime with the same oxidant, TBHP. By simply switching the reaction solvent and base, the reaction proceeds via two pathways. An unexpected -CN group migration rearrangement and hydroxylation have occurred in nonpolar and polar solvents, respectively, under the reported conditions. Furthermore, the source of the hydroxyl group and hydrogen in the reaction is indirectly confirmed with isotope labeling studies.
在无金属体系下，使用相同的氧化剂叔丁基过氧化氢（TBHP），展示了一种合成多取代2,3-二氢呋喃-2-甲腈和4,5-二氢呋喃-3-甲腈的通用方案。通过简单地切换反应溶剂和碱，反应通过两条途径进行。在所报道的条件下，分别在非极性和极性溶剂中发生了意外的-CN基团迁移重排和羟基化反应。此外，通过同位素标记研究间接证实了反应中羟基和氢的来源。
