Nanba Yutaro, Shinohara Riku, Morita Masao, Kobayashi Yuichi
Department of Biotechnology, Tokyo Institute of Technology, B-52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan.
Org Biomol Chem. 2017 Oct 18;15(40):8614-8626. doi: 10.1039/c7ob02291c.
The reaction of TMS-substituted epoxy alcohols (and derivatives) with dimsyl sodium (NaDMSO) to give 1-alkene-3,4-diols was used for the synthesis of enantiomerically enriched 17(R),18(S)-EpETE and two diastereoisomers of isoleukotoxin diol. In the synthesis of 17(R),18(S)-EpETE, the α-ethoxyethyl ether (EE) of the epoxy alcohol derived from (R)-1-TMS-1-penten-3-ol underwent reaction with NaDMSO to give the mono EE-protected 1-hexene-3,4-diol. The aldehyde obtained by hydroboration/oxidation was subjected to Wittig reaction to afford a mono EE-protected diol. The corresponding mono mesylate was prepared and subjected to epoxide ring formation to afford 17(R),18(S)-EpETE stereoselectively. Similarly, a reaction of the anti epoxy alcohol derived from (R)-1-TMS-1-octen-3-ol with NaDMSO gave the anti form of 1-nonene-3,4-diol, which was converted to 12(S),13(R)-isoleukotoxin diol through Wittig reaction. 12(R),13(R)-Isoleukotoxin diol was synthesized in a similar manner.
用TMS取代的环氧醇（及其衍生物）与二甲基亚砜钠（NaDMSO）反应生成1-烯烃-3,4-二醇，用于合成对映体富集的17(R),18(S)-环氧二十碳三烯酸（EpETE）和异白三烯二醇的两种非对映异构体。在17(R),18(S)-EpETE的合成中，源自(R)-1-TMS-1-戊烯-3-醇的环氧醇的α-乙氧基乙基醚（EE）与NaDMSO反应，得到单EE保护的1-己烯-3,4-二醇。硼氢化/氧化得到的醛进行维蒂希反应，得到单EE保护的二醇。制备相应的单甲磺酸酯并进行环氧化反应，立体选择性地得到17(R),18(S)-EpETE。类似地，源自(R)-1-TMS-1-辛烯-3-醇的反式环氧醇与NaDMSO反应，得到反式1-壬烯-3,4-二醇，通过维蒂希反应将其转化为12(S),13(R)-异白三烯二醇。12(R),13(R)-异白三烯二醇以类似的方式合成。
