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Published on: October 4, 2019
A Concise Bioinspired Semisynthesis of Rumphellaones A-C and Their C-8 Epimers from β-Caryophyllene
Georgijs Stakanovs1, Anatoly Mishnev1, Dace Rasina1
1Latvian Institute of Organic Synthesis, Aizkraukles Street 21, LV-1006, Riga, Latvia.
Abstract:
The first semisynthetic route toward rumphellaones B (2) and C (3) and their C-8 epimers as well as the shortest synthesis of rumphellaone A (1) and its C-8 epimer from the most accessible sesquiterpene, β-caryophyllene (4), is presented. Synthetic routes involved caryophyllonic acid as a key intermediate, which was converted to rumphellaone A (and epimer) via acid-catalyzed lactonization and rumphellaone C (and epimer) using one-pot epoxidation-lactonization. Rumphellaone B (2) and its epimer were obtained from rumphellaone A (1) and its epimer, respectively, using Saegusa-Ito oxidation. The absolute configuration at C-8 was confirmed by single-crystal X-ray analysis of rumphellaone B (2) and an acylated derivative of rumphellaone C.
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