Department of Chemistry, University of Utah , 315 South 1400 East, Salt Lake City, Utah 84112, United States.
Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
J Am Chem Soc. 2017 Sep 20;139(37):12943-12946. doi: 10.1021/jacs.7b08791. Epub 2017 Sep 8.
Computed descriptors for acyclic diaminocarbene ligands are developed in the context of a gold catalyzed enantioselective tandem [3,3]-sigmatropic rearrangement-[2+2]-cyclization. Surrogate structures enable the rapid identification of parameters that reveal mechanistic characteristics. The observed selectivity trends are validated in a robust multivariate analysis facilitating the development of a highly enantioselective process.
在金催化的对映选择性串联[3,3]-σ重排-[2+2]-环化反应的背景下,开发了非循环二氨基卡宾配体的计算描述符。替代结构能够快速识别揭示机理特征的参数。通过稳健的多元分析验证了观察到的选择性趋势,从而促进了高对映选择性过程的开发。