Kobayashi Yuichi, Asano Moriteru, Yoshida Shinya, Takeuchi Akira
Department of Biomolecular Engineering, Tokyo Institute of Technology, Box B-52, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan.
Org Lett. 2005 Apr 14;7(8):1533-6. doi: 10.1021/ol050148t.
[reaction: see text] The core structure of decarestrictine D was constructed by stereoselective oxygenation of (2Z,4E)-alkadienyl alcohol, which could be synthesized by a nickel-catalyzed coupling reaction between the corresponding cis bromide and trans borate. Efficiency in macrocyclization of the seco acid with Yamaguchi reagent was found to be protective-group-dependent, and the best yield of 40% was obtained with the seco acid with tri-MOM protective groups.
[反应：见正文] 去甲苦参碱D的核心结构是通过对(2Z,4E)-链二烯醇进行立体选择性氧化构建的，该链二烯醇可通过相应的顺式溴化物与反式硼酸酯之间的镍催化偶联反应合成。发现使用山口试剂对裂环酸进行大环化的效率取决于保护基团，带有三甲基氧甲基（tri-MOM）保护基团的裂环酸获得了40%的最佳产率。
