Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
Chemistry. 2022 Nov 11;28(63):e202202464. doi: 10.1002/chem.202202464. Epub 2022 Sep 6.
In this work an approach for the synthesis of furanocembranoid natural products containing the C-7,8-diol moiety is disclosed. This culminated in the first total synthesis of the natural product molestin E, together with ent-sinulacembranolide A and ent-sinumaximol A as well as a thorough exploration of their chemistry. Late-stage ring-closure of the C-7,8-diols to the corresponding epoxides was also demonstrated. Key features of this synthetic strategy include a stereoselective Baylis-Hillman reaction, ring-closing metathesis and Shiina macrolactonisation. Chiral-pool materials were deployed to ensure the desired absolute stereochemistry which was confirmed by late-stage single crystal X-ray diffraction.
本工作揭示了一种合成含有 C-7,8-二醇部分的呋喃半船型天然产物的方法。这最终导致了天然产物 molestin E 的首次全合成，以及 ent-sinulacembranolide A 和 ent-sinumaximol A 的全合成，以及对它们化学性质的深入研究。还证明了 C-7,8-二醇的后期环合形成相应的环氧化物。该合成策略的关键特点包括立体选择性的 Baylis-Hillman 反应、闭环复分解反应和 Shiina 大环内酯化反应。手性池材料的使用确保了所需的绝对立体化学，这通过后期的单晶 X 射线衍射得到了证实。
