School of Environmental and Chemical Engineering, Shanghai Institute of Technology, Shanghai 201418, PR China.
Innovation Research Institute of Traditional Chinese Medicine (IRI), Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, PR China.
Org Lett. 2023 May 19;25(19):3497-3501. doi: 10.1021/acs.orglett.3c01082. Epub 2023 May 8.
This report describes a streamlined synthesis of immunosuppressive mycestericin E and G through a highly stereoselective nitroso-ene cyclization in 11-12 steps using readily available materials. The stereochemical outcome in the formation of a α-quaternary stereogenic center is rationalized by a trajectory based on the polar diradical intermediate and subsequent hydrogen transfer. Julia olefination offers a facile chain elongation method that presents a viable strategy for structural derivatization in future medicinal applications.
本报告描述了通过高度立体选择性的亚硝基亚烯环化反应，在 11-12 步中用易得的原料简化了免疫抑制霉菌素 E 和 G 的合成。通过基于极性自由基中间体和随后的氢转移的轨迹，合理地解释了在形成 α-季立体中心时的立体化学结果。Julia 烯丙基化提供了一种简便的链延伸方法，为未来药物应用中的结构衍生化提供了可行的策略。
