Department of Chemistry, The University of Adelaide, Adelaide, SA 5005 (Australia).
Org Lett. 2022 Apr 1;24(12):2276-2281. doi: 10.1021/acs.orglett.2c00325. Epub 2022 Mar 16.
Synthetic approaches to bicyclo[4.2.0]octadiene natural products frequently employ the synthesis of linear tetraenes to initiate a biosynthetic 8π/6π-electrocyclization cascade. This work forges a functionalized bicyclo[4.2.0]octadiene in two steps from cyclooctatetraene. The versatility of this method is demonstrated through natural product synthesis, including the first total synthesis of kingianic acid A and formal syntheses of kingianins A, D, and F and cryptobeilic acid D ethyl ester. The unexpected formation of an ,,,-tetraene byproduct is rationalized through density functional theory modeling.
双环[4.2.0]辛二烯天然产物的合成方法通常采用线性四烯的合成来引发生物合成的 8π/6π-电环化级联反应。这项工作从环辛四烯出发，分两步得到官能化的双环[4.2.0]辛二烯。该方法的通用性通过天然产物合成得到了证明，包括 kingianic 酸 A 的首次全合成以及 kingianins A、D 和 F 和 cryptobeilic 酸 D 乙酯的形式合成。通过密度泛函理论模拟对意外形成的,,,-四烯副产物进行了合理化解释。
