Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Angew Chem Int Ed Engl. 2017 Mar 6;56(11):3064-3068. doi: 10.1002/anie.201611829. Epub 2017 Feb 6.
Recently, the phenomenon of enantiodivergence was uncovered as a new phenomenon in the biosynthesis of natural products. In nature, chiral natural products are usually produced in optically active form, but both enantiomers sometimes arise in different genera and/or species or in a single species. Here we show through enantioselective total synthesis that the natural product isodehydrothyrsiferol shows partial enantiodivergency in that six of the nine or ten asymmetric centers are enantiomeric to those of other members of the marine squalene-derived triterpenoid thyrsiferol family. In addition, isodehydrothyrsiferol and dehydrothyrsiferol, which show partial enantiodivergency, were isolated from the same producer, the red alga Laurencia viridis. These results demonstrate that partial enantiodivergence can develop even between natural products originating from a single species.
最近，对天然产物生物合成的研究发现了对映体分野现象这一全新现象。在自然界中，手性天然产物通常以光学活性形式产生，但两种对映体有时会出现在不同属和/或种中，或出现在单个种中。通过对映选择性全合成，我们证明天然产物异脱氢齐墩果酸在九个或十个不对称中心中的六个与海洋角鲨烯衍生的三萜类化合物齐墩果酸家族的其他成员具有对映异构性。此外，在同一生产者，红色海藻Laurencia viridis 中分离出了具有部分对映体分野的异脱氢齐墩果酸和脱氢齐墩果酸。这些结果表明，即使是来自单个种的天然产物也可能产生部分对映体分野。
