Michel Nicholas W M, Jeanneret Alexandria D M, Kim Hyehwang, Rousseaux Sophie A L
Davenport Research Laboratories, Department of Chemistry , University of Toronto , 80 St George Street , Toronto , Ontario , M5S 3H6 , Canada.
J Org Chem. 2018 Oct 5;83(19):11860-11872. doi: 10.1021/acs.joc.8b01763. Epub 2018 Sep 19.
A nickel-catalyzed cyanation reaction of benzylic and allylic pivalate esters is reported using an air-stable Ni(II) precatalyst and substoichiometric quantities of Zn(CN). Alkene additives were found to inhibit catalysis, suggesting that avoiding β-hydride elimination side reactions is essential for productive catalysis. An enantioenriched allylic ester undergoes enantiospecific cross-coupling to produce an enantioenriched allylic nitrile. This method was applied to an efficient synthesis of (±)-naproxen from commercially available starting materials.
报道了一种使用空气稳定的Ni(II)预催化剂和亚化学计量的Zn(CN)进行苄基和烯丙基新戊酸酯的镍催化氰化反应。发现烯烃添加剂会抑制催化作用，这表明避免β-氢消除副反应对于有效催化至关重要。一种对映体富集的烯丙基酯进行对映体特异性交叉偶联以生成对映体富集的烯丙基腈。该方法应用于从市售起始原料高效合成(±)-萘普生。
