Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich , Butenandtstrasse 5-13, 81377, Munich, Germany.
J Am Chem Soc. 2016 May 25;138(20):6420-3. doi: 10.1021/jacs.6b03720. Epub 2016 May 13.
We have developed the first synthesis of the unique oxetane containing diterpene (+)-dictyoxetane. Our retrosynthetic planning was guided by the putative biosynthesis of the unprecedented 2,7-dioxatricyclo[4.2.1.0(3,8)]nonane ring system. A bioinspired 4-exo-tet, 5-exo-trig cyclization sequence enabled the construction of the synthetically challenging dioxatricyclic framework. The overall synthesis proceeds in 15 linear steps from a known and readily available trans-hydrindane fragment. In addition, we were able to realize the first dyotropic rearrangement of an epoxide-oxetane substrate.
我们已经开发出了独特的含环氧乙烷二萜 (+)-dictyoxetane 的首次合成。我们的逆合成规划受到了前所未有的 2,7-二氧杂三环[4.2.1.0(3,8)]壬烷环系统的假定生物合成的指导。受生物启发的 4-外式-五内式环化序列使构建具有挑战性的二氧杂三环骨架成为可能。该全合成从已知且易于获得的反式-氢化茚片段经过 15 步线性反应得到。此外，我们还实现了首例环氧化物-环氧乙烷底物的双稠合重排。
