Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
J Org Chem. 2020 May 15;85(10):6815-6821. doi: 10.1021/acs.joc.0c00770. Epub 2020 May 6.
We describe the total synthesis of epoxyquinoid natural products (+)-pestalofone A and (+)-iso-A82775C. The synthesis of (+)-16-oxo-iso-A82775C, the putative biosynthetic precursor of pestalofone C, is also presented. The allene moiety present in (+)-iso-A82775C and (+)-16-oxo-iso-A82775C was constructed from the ketodiene-yne group via a biosynthetically relevant sequence involving a conjugate reduction and a base-catalyzed tautomerization. Attempted Diels-Alder reaction-based dimerizations of (+)-16-oxo-iso-A82775C and (+)-iso-A82775C toward pestalofones B and C are also described.
我们描述了环氧倍半萜天然产物 (+)-pestalofone A 和 (+)-iso-A82775C 的全合成。同时还展示了 (+)-16-氧代-iso-A82775C 的合成，它是 pestalofone C 的假定生物合成前体。(+)-iso-A82775C 和 (+)-16-氧代-iso-A82775C 中存在的丙二烯部分是通过涉及共轭还原和碱催化互变异构的生物相关序列从酮二烯-炔基团构建的。还描述了 (+)-16-氧代-iso-A82775C 和 (+)-iso-A82775C 对 pestalofones B 和 C 的基于 Diels-Alder 反应的二聚尝试。
