Beatty Joel W, Stephenson Corey R J
Department of Chemistry, University of Michigan , Ann Arbor, Michigan 48109, United States.
J Am Chem Soc. 2014 Jul 23;136(29):10270-3. doi: 10.1021/ja506170g. Epub 2014 Jul 9.
Natural product modification with photoredox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis.
利用光氧化还原催化对天然产物进行修饰，能够在化学空间的复杂区域中以温和、化学选择性的方式获得一系列相关结构，为新型结构基序以及有用数量的稀有同系物提供了可能性。虽然胺添加剂已被广泛用作光催化的化学计量电子供体，但通过单电子氧化对胺底物进行可控修饰对于生物碱的合成和修饰而言是理想的。在此，我们报道了利用可见光光氧化还原催化将胺（+）-长春花碱转化为天然产物（-）-假石蒜碱、（-）-假长春花碱和（+）-冠狗牙花定碱。
