Bioinspired Synthesis of Nortriterpenoid Propindilactone G

Abstract

A concise bioinspired synthesis of Schisandra nortriterpenoid propindilactone G has been accomplished from a readily accessible steroidal lactone. Key transformations include a Breslow remote functionalization, a Suárez remote radical functionalization, a ring expansion enabled by a Wagner–Meerwein rearrangement, a stereoinversion of a tertiary alcohol, and a biomimetic transesterification/oxa-Michael addition cascade. This work also provides experimental evidence of the putative propindilactone G biosynthesis pathway.

Recent Advance in the Synthesis of Natural Products of Schisandra Triterpenoid

“…2015 年, 杨震小组 [33] 就采用不对称 Diels-Alder 反应、 Pauson-Khand 反应等构建主要骨架, 再通过氧化偶联反 应引入侧链实现了 propindilactone G 的全合成, 并对原 始结构进行了修正. 而桂敬汉小组 [37]…”

“…自 2011 年杨震小组报道了首例五味子三萜化合物 (±)-schindilactone A 的全合成以来 [29][30][31][32] , 该小组先后完 成了 propindilactone G [33] 的不对称全合成, 以及 19dehydroxyl arisandilactone A [34] 、lancifodilactone G acetate [35] 和 pre-schisanartanin C [36] 的全合成. 近期, 桂敬汉 小组 [37][38] 也完成了 propindilactone G 的全合成. 李昂小 组 [39][40] 于 2014 年和 2016 年先后完成了 rubriflordilactone A 和 rubriflordilactone B 的不对称全合成.…”

Development of Biomimetic Synthesis of Propindilactone G†

“…Recently, we reported a strategy for the synthesis of propindilactone G from a known steroid lactone, [ 11 ] which was largely inspired by a biogenetic proposal. In this article, we will detail the synthesis more comprehensively.…”

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

“…It was discovered by Sun and co‐workers from plants of the Schisandraceae . Propindilactone G along with other members of this family are being used as the medications in China for more than thousands of years to cure insomnia, hepatitis, and asthenia …”

“…Recently, Gui and coworker have accomplished an efficient synthesis of propindilactone G with a readily available steroidal lactone (Scheme ) . Key steps of this synthesis consist of Breslow as well as Suárez remote functionalization, followed by ring expansion via Wagner ‐ Meerwein rearrangement, stereo‐inversion of alcohol, and oxa‐Michael/ transesterification cascade addition.…”