Mukherjee Sumit, Lee Daesung
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607, USA.
Org Lett. 2009 Jul 2;11(13):2916-9. doi: 10.1021/ol900923c.
A tandem ring-closing metathesis of a silaketal-based dienyne substrate proceeded efficiently to provide a bicyclic siloxane, which upon removal of the silicon tether afforded an (E,Z)-1,3-dienediol. Further manipulation of this key functional motif rendered synthesis of the entire C1-C19 linear skeleton of (-)-cochleamycin A, a late-stage intermediate employed in the previous total synthesis of (+)-cochleamycin A by Roush and co-workers.
基于硅缩酮的二烯炔底物的串联闭环复分解反应高效进行，生成了一种双环硅氧烷，去除硅连接基后得到一种（E，Z）-1,3-二烯二醇。对这一关键功能基序的进一步操作实现了（-）-耳蜗霉素A完整C1-C19线性骨架的合成，（-）-耳蜗霉素A是Roush及其同事之前全合成（+）-耳蜗霉素A时所采用的后期中间体。
