Department of Chemistry, The University of Kansas, Lawrence, Kansas 66045, USA.
Org Lett. 2009 Dec 17;11(24):5630-3. doi: 10.1021/ol902065p.
Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd(2)(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitriles in the presence of much more acidic alpha-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.
钯催化的腈的脱羧 α-烯丙基化反应很容易发生，使用 Pd(2)(dba)(3) 和 rac-BINAP。这种催化剂混合物也允许在更酸性的α-质子存在下高度区域选择性地进行腈的α-烯丙基化。因此，所报道的方法提供了通过碱介导的烯丙基化化学方法不易获得的化合物的途径。最后，机理研究表明，中间体腈稳定的阴离子的 C-和 N-烯丙基化之间存在竞争，并且 N-烯丙基化后迅速发生[3,3]-σ重排。
