Dong Gao, Li Bohui, O'Doherty George
Department of Chemistry, West Virginia University, Morgantown, WV 26506, US.
Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, US.
Org Chem Front. 2020 Nov 21;7(22):3608-3615. doi: 10.1039/d0qo01121e. Epub 2020 Oct 12.
Two formal syntheses and one total synthesis of fostriecin () have been achieved, as well as, the synthesis of its related congener dihydro-dephospho-fostriecin. All the routes use the Sharpless dihydroxylation to set the absolute stereochemistry at -8/9 positions and a Leighton allylation to set the -5 position of the natural product. In the formal syntheses a Noyori transfer hydrogenation of an ynone was used to set the -11 position while the total synthesis employed a combination of asymmetric dihydroxylation and Pd-π-allyl reduction to set the -11 position. Finally in the total synthesis, a trans-hydroboration of the -12/13 alkyne was used in combination with a Suzuki cross coupling to establish the ,,-triene of fostriecin ().
已完成了福司曲星（）的两次形式合成和一次全合成，以及其相关同系物二氢 - 脱磷 - 福司曲星的合成。所有路线均使用夏普莱斯双羟基化反应来确定 -8/9 位的绝对立体化学，并使用莱顿烯丙基化反应来确定天然产物的 -5 位。在形式合成中，使用炔酮的野依转移氢化反应来确定 -11 位，而全合成则采用不对称双羟基化反应和钯 - π - 烯丙基还原反应的组合来确定 -11 位。最后在全合成中，-12/13 炔烃的反式硼氢化反应与铃木交叉偶联反应相结合，构建了福司曲星（）的 ,,,- 三烯。
