Department of Organic Synthesis & Process Chemistry , Indian Institute of Chemical Technology , Hyderabad 500007 , India.
Academy of Scientific and Innovative Research (AcSIR) , Ghaziabad 201002 , India.
J Org Chem. 2019 Aug 2;84(15):9584-9602. doi: 10.1021/acs.joc.9b01248. Epub 2019 Jul 18.
Two stereoselective routes to the C7-C22 subunit of amphidinolide K are disclosed. Jacobsen's hydrolytic kinetic resolution and Sharpless' asymmetric dihydroxylation reactions have been employed for the construction of the tetrahydrofuran ring. The C10-C11, C16-C17, C9-O, and C18-O bonds have been created using α-chloro sulfide intermediates and [2,3] sigmatropic rearrangement. Marshall's propargylation protocol is utilized to create the C4 stereogenic center, and regioselective hydrozirconation/iodine quench afforded an alkenyl iodide which is employed in the NHK coupling with the C7-C22 subunit. Oxonia-Cope rearrangement resulted in the creation of the C18 carbinol stereogenic center and chain elongation.
公开了两种对 Amphidinolide K 的 C7-C22 亚基具有立体选择性的路线。Jacobsen 的水解动力学拆分和 Sharpless 的不对称双羟化反应已被用于构建四氢呋喃环。C10-C11、C16-C17、C9-O 和 C18-O 键已使用α-氯代亚砜中间体和[2,3]σ重排来构建。Marshall 的炔丙基化方案用于创建 C4 立体中心，区域选择性的锆氢化/碘猝灭得到烯基碘化物，该碘化物用于与 C7-C22 亚基的 NHK 偶联。Oxonia-Cope 重排导致 C18 手性碳原子和链延长的形成。
