Parameterization of Acyclic Diaminocarbene Ligands Applied to a Gold(I)-Catalyzed Enantioselective Tandem Rearrangement/Cyclization

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.

本研究针对金催化对映选择性串联[3,3]-σ重排-[2+2]环化反应体系，开发了无环二氨基卡宾配体的计算描述符。通过替代结构模型可快速识别能够揭示反应机理特征的参数。经稳健的多变量分析验证了所观测到的选择性规律，为高对映选择性反应体系的开发提供了有力支撑。