Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
Org Lett. 2022 Jan 21;24(2):559-563. doi: 10.1021/acs.orglett.1c03998. Epub 2021 Dec 30.
Progress toward a stereoselective synthesis of tetrodotoxin (TTX) is presented. Oxidative dearomatization of a tetrasubstituted guaiacol arene yielded a masked -benzoquinone that intercepted an acyl nitroso species generated by the copper-catalyzed aerobic oxidation of an acyl hydroxylamine. The subsequent alkene dihydroxylation and reduction of a bis-neopentylic ketone proceeded with perfect diastereoselectivity to reveal advanced intermediates toward the synthesis of TTX.
呈现了朝向四氢巴马丁（TTX）的立体选择性合成的进展。四取代愈创木酚芳烃的氧化去芳构化产生了一个被掩蔽的 -苯醌，该苯醌拦截了酰基亚硝酮物种，该物种由酰基羟胺的铜催化有氧氧化生成。随后双新戊基酮的烯烃双羟化和还原以完美的非对映选择性进行，揭示了合成 TTX 的先进中间体。
