Max-Planck-Institut für Kohlenforschung , Kaiser-Wilhelm-Platz 1, 45470 Mülheim, Germany.
J Am Chem Soc. 2013 Oct 9;135(40):14968-71. doi: 10.1021/ja408856p. Epub 2013 Sep 30.
A one-pot protocol for the asymmetric α-allylation reaction is reported relying on a key efficient asymmetric Claisen rearrangement, triggered by electrophilic activation of chiral pseudoephedrine amides. Subsequent reduction or hydrolysis of the resulting iminium ions provides highly enantioenriched α-allylic aldehydes or carboxylic acids in a traceless manner. Compared to traditional alternatives which make use of strongly basic conditions, the work presented herein displays unprecedented functional group tolerance.
本文报道了一种通过手性伪麻黄碱酰胺的亲电活化引发关键高效的不对称 Claisen重排实现不对称 α-烯丙基化反应的一锅法策略。随后对生成的亚胺离子进行还原或水解，以无痕迹的方式得到高度对映富集的α-烯丙基醛或羧酸。与传统的强碱性条件方法相比，本文所展示的方法具有前所未有的官能团耐受性。
