National Tsing Hua University , Hsinchu 300, Taiwan.
J Org Chem. 2017 Feb 17;82(4):2045-2058. doi: 10.1021/acs.joc.6b02886. Epub 2017 Feb 7.
An improved synthesis of rings DEF of solanoeclepin A has been achieved from ent-Hajos Parrish ketone. A key tricyclo[5.3.2.0]decene intermediate having an additional vinyl group as a precursor of a hydroxyl functionality was synthesized, in which the key steps included (i) a [2,3]-Wittig rearrangement to provide trans-hydroindene with C11(R)-configuration, (ii) the introduction of a vinyl group as a masked OH at C6, (iii) an oxymercurative aldol to synthesize the tricyclo[5.3.2.0]decene moiety, (iv) an oxidative C-C bond cleavage to yield an aldehyde and an unsaturated methyl ketone, and (v) a radical cyclization for the cyclobutane ring formation to provide the tricyclo[5.2.1.0]decene compound.
已从（+）-霍霍巴醇酮实现了 Solanoeclepin A 的环 DEF 的改进合成。作为羟基官能团前体的额外乙烯基的三环[5.3.2.0]癸烯中间体被合成，其中关键步骤包括：（i）[2,3]-Wittig 重排以提供具有 C11（R）-构型的反-氢茚，（ii）作为 C6 处的掩蔽 OH 的乙烯基的引入，（iii）羟汞化-醛醇缩合合成三环[5.3.2.0]癸烯部分，（iv）氧化 C-C 键裂解以得到醛和不饱和甲基酮，以及（v）自由基环化形成环丁烷环以提供三环[5.2.1.0]癸烯化合物。
