A General Stereochemical Model for Grignard Additions to α ‐Alkoxy Nitrones: Density Functional Theory Evidence for an Intrinsic α ‐Chelation‐Controlled Pat

Nucleophilic additions of Grignard reagents to nitrones constitute a powerful and versatile methodology for stereoselective synthesis. The ability to control and even invert diastereoselectivity through LA coordination offers unique opportunities for divergent synthetic strategies. However, the complex electronic, conformational, and coordination properties of nitrones have long hindered the development of reliable mechanistic models. By comparing competing transition structures for nucleophilic attack under different coordination scenarios, it becomes possible to rationalize both the preservation and inversion of diastereoselectivity observed experimentally and to lay the groundwork for rational design and prediction in future applications.