作者:Mario Janjetovic、Annika M. Träff、Göran Hilmersson
DOI:10.1002/chem.201406097
日期:2015.2.23
chemoselectively manipulating the strong aliphatic CF bond with direct transformation into a CN bond under mild conditions is reported. The activation and subsequent substitution of primary alkyl fluorides is mediated by La[N(SiMe3)2]3, and results in high to excellent yields of tertiary amines. The methodology displays high selectivity towards the C(sp3)F bond, and a variety of secondary amines are applicable
报道了在温和条件下化学选择性处理强脂族CF键并直接转化为CN键的方法。La [N(SiMe 3)2 ] 3介导伯烷基氟化物的活化和随后的取代,从而导致叔胺的产率高至优异。该方法显示出对C(sp 3)F键的高度选择性,并且各种仲胺都可以用作亲核试剂。机理研究表明,相对于[La [N(SiMe 3)2 ] 3 ],[R 1 R2 NH]和[烷基氟化物],并提出了六元环状过渡态。另外,1 H NMR光谱显示La [N(SiMe 3)2 ] 3是参与取代的活性物质,并且胺的质子分解产生La [NR 1 R 2 ] 3降低了反应性。