Baldassarre Sophia M, Sato Heidi S, Louise Adam P, Summer Layna L, Wilson Benjamin P, Hemric Brett N
Department of Chemistry and Biochemistry, University of Tampa, Tampa, Florida 33606, United States.
J Org Chem. 2024 Nov 15;89(22):16865-16872. doi: 10.1021/acs.joc.4c02244. Epub 2024 Nov 3.
A mild, metal-free 1,2-dioxygenation of 1,3-dienes using TEMPO and carboxylic acids is reported. This method includes examples for a variety of 1,3-dienes as well as aliphatic and aromatic carboxylic acids. This reaction also demonstrates complete site- and regioselectivity in the oxygen addition. Furthermore, extensive derivatization of the differential oxygen groups in the product has been demonstrated, including reduction of the remaining alkene to access alkyl, vicinally dioxygenated scaffolds. Finally, this reaction is shown both experimentally and computationally to occur through carboxylic acid-driven disproportionation of TEMPO.
据报道，使用TEMPO和羧酸可实现温和的、无金属的1,3 - 二烯的1,2 - 双氧化反应。该方法涵盖了多种1,3 - 二烯以及脂肪族和芳香族羧酸的实例。该反应在氧加成过程中还表现出完全的位点和区域选择性。此外，已证明产物中差异氧基团可进行广泛的衍生化，包括将剩余的烯烃还原以获得烷基、邻位双氧化支架。最后，通过实验和计算表明，该反应是通过羧酸驱动的TEMPO歧化反应发生的。
