Z 选择性分子内 Horner-Wadsworth-Emmons 反应在大环内酯合成中的应用。
Z-selective intramolecular Horner-Wadsworth-Emmons reaction for the synthesis of macrocyclic lactones.
机构信息
Department of Chemistry, Fuculty of Engineering, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan.
出版信息
Org Lett. 2010 Apr 2;12(7):1460-3. doi: 10.1021/ol100071d.
When the substrates (ArO)(2)P(O)CH(2)CO(2)---CHO (Ar = Ph, o-t-BuPh) were added to a THF solution containing 3 equiv of NaH at 0 degrees C or NaI-DBU at rt over 1-10 h, the intramolecular Horner-Wadsworth-Emmons reaction proceeded efficiently to give the 12-18-membered-ring lactones in 69-93% yields with 89-100% Z selectivity. On the other hand, (EtO)(2)P(O)CH(2)CO(2)---CHO gave the 13-18-membered-ring lactones in 52-82% yields with 89-99% E selectivity using LiCl-DBU in MeCN or THF.
当底物(ArO)(2)P(O)CH(2)CO(2)---CHO(Ar = Ph, o-t-BuPh)在 0 摄氏度下加入到含有 3 当量 NaH 的 THF 溶液中，或者在室温下加入到含有 NaI-DBU 的 THF 溶液中时，分子内 Horner-Wadsworth-Emmons 反应能够高效进行，以 69-93%的收率得到 12-18 元环内酯，并且具有 89-100%的 Z 选择性。另一方面，使用 LiCl-DBU 在 MeCN 或 THF 中，(EtO)(2)P(O)CH(2)CO(2)---CHO 可以得到 13-18 元环内酯，收率为 52-82%，并且具有 89-99%的 E 选择性。
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