镍催化的大环内酯基序区域发散方法。
Nickel-Catalyzed Regiodivergent Approach to Macrolide Motifs.
作者信息
Shareef Abdur-Rafay, Sherman David H, Montgomery John
机构信息
Department of Chemistry, 930 N. University Ave. University of Michigan, Ann Arbor, MI 48109-1055.
出版信息
Chem Sci. 2012 Jan 1;3(3):892-895. doi: 10.1039/C2SC00866A. Epub 2011 Dec 6.
Abstract
A strategy for regiochemical reversal of reductive macrocyclizations of aldehydes and terminal alkynes has been developed. Using an advanced synthetic intermediate directed towards the methymycin/neomethymycin class of macrolides, selective endocyclization provides the natural twelve-membered ring series, whereas ligand alteration enables selective exocyclization to provide access to the unnatural eleven-membered ring series. The twelve-membered ring adduct was converted to 10-deoxymethynolide, completing an efficient total synthesis of this natural product.
摘要
已开发出一种使醛与末端炔烃的还原大环化反应的区域化学反转的策略。使用一种针对甲基霉素/新甲基霉素类大环内酯的先进合成中间体，选择性内环化可得到天然的十二元环系列，而配体改变则能实现选择性外环化，从而获得非天然的十一元环系列。将十二元环加合物转化为10-脱氧甲基炔内酯，完成了该天然产物的高效全合成。
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