Chemler S R, Danishefsky S J
Department of Bioorganic Chemistry, Sloan-Kettering Institute for Cancer Research, New York, New York 10021, USA.
Org Lett. 2000 Aug 24;2(17):2695-8. doi: 10.1021/ol0062547.
[reaction: see text]Transannular macrocyclizations via intramolecular B-alkyl Suzuki reactions are described. Regioselective terminal olefin hydroboration with 9-BBN followed by Pd(0)-catalyzed Suzuki reaction in the presence of a base such as TlOEt at high dilution generates macrocycles with a high degree of control over olefin geometry with isomerically pure E or Z vinyl iodide substrates. These reactions are complementary to ring closing metathesis (RCM) macrocyclizations and may prove superior in cases where control of olefin geometry is required.
[反应：见正文]描述了通过分子内硼烷基铃木反应进行的跨环大环化反应。用9-硼双环[3.3.1]壬烷对区域选择性末端烯烃进行硼氢化，然后在高稀释条件下，在诸如乙基铊之类的碱存在下，通过钯（0）催化的铃木反应，可生成对烯烃几何结构具有高度控制能力的大环化合物，底物为异构纯的E或Z型乙烯基碘。这些反应与闭环易位（RCM）大环化反应互补，并且在需要控制烯烃几何结构的情况下可能证明更具优势。
