Stevens Benjamin D, Bungard Christopher J, Nelson Scott G
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
J Org Chem. 2006 Aug 18;71(17):6397-402. doi: 10.1021/jo0605851.
Boron-substituted di(allyl) ethers provide an efficient conduit for expanding the structural diversity available from olefin isomerization-Claisen rearrangement (ICR) reactions. Easily prepared allyl propargyl ethers undergo chemoselective Zr(IV)-catalyzed hydroboration to afford the boron-substituted ICR substrates. The boron-substituted allyl residue undergoes chemoselective Ir(I)-catalyzed olefin isomerization and in situ Claisen rearrangement to afford stereodefined beta-boryl aldehyde products. Functionalization of the C-B linkage by oxidation or Suzuki cross-coupling provides a route to Claisen adducts previously inaccessible from the ICR methodology.
硼取代的二（烯丙基）醚为扩展烯烃异构化-克莱森重排（ICR）反应可得的结构多样性提供了一条有效途径。易于制备的烯丙基炔丙基醚经化学选择性Zr(IV)催化硼氢化反应，得到硼取代的ICR底物。硼取代的烯丙基残基经化学选择性Ir(I)催化烯烃异构化及原位克莱森重排反应，得到立体定向的β-硼基醛产物。通过氧化或铃木交叉偶联对C-B键进行官能团化，为通过ICR方法以前无法获得的克莱森加合物提供了一条合成路线。
