Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IIllinois 61801, United States.
Department of Small Molecule Process Chemistry, Genentech, Inc., 1 DNA Way, South San Francisco, California 94080, United States.
J Am Chem Soc. 2022 Dec 21;144(50):22950-22964. doi: 10.1021/jacs.2c08820. Epub 2022 Dec 7.
The atropselective iodination of 2-amino-6-arylpyridines catalyzed by chiral disulfonimides (DSIs) is described. Key to the development of this transformation was the use of a chemoinformatically guided workflow for the curation of a structurally diverse training set of DSI catalysts. Utilization of this catalyst training set in the atropselective iodination across a variety 2-aminopyridine substrates allowed for the recommendation of statistically higher-performing DSIs for this reaction. Data Fusion techniques were implemented to successfully predict the performance of catalysts when classical linear regression analysis failed to provide suitable models. This effort identified a privileged class of 3,3'-alkynyl-DSI catalysts which were effective in catalyzing the iodination of a variety of 2-amino-6-arylpyridines with high stereoselectivity and generality. Subsequent preparative-scale demonstrations highlighted the utility of this reaction by providing iodinated pyridines >90:10 er and in good chemical yield.
手性双磺酰胺(DSI)催化的 2-氨基-6-芳基吡啶的高立体选择性碘化作用描述。该转化的关键是使用化学信息学指导的工作流程对结构多样的 DSI 催化剂训练集进行管理。在各种 2-氨基吡啶底物的高立体选择性碘化反应中使用此催化剂训练集,为该反应推荐了统计上表现更好的 DSI。当经典线性回归分析无法提供合适的模型时,数据融合技术被用于成功预测催化剂的性能。这项工作确定了一类具有特权的 3,3'-炔基-DSI 催化剂,它们可有效地催化各种 2-氨基-6-芳基吡啶的碘化反应,具有高立体选择性和通用性。随后的制备规模示范通过提供大于 90:10 er 的碘化吡啶和良好的化学收率突出了该反应的实用性。