An experimental and computational study (including DFT calculations and distortion/interaction analysis) was conducted to assess the effect of the nitrone structure in the outcome of dipolar 1,3-cycloadditions with levoglucosenone, a biomass derived chiral enone. While B3LYP/6-31G* (the most popular method for modeling these reactions according to our literature search) provides qualitatively good results, large outliers were found for some systems. An exhaustive exploration of other levels allowed us to determine the most appropriate ones to predict simultaneously reactivity and selectivity. The systematically predicted high exo selectivity by the majority of the levels led us to reconsider our initial assignment for the reaction with the nitrone derived from piperidine, which resulted in the discovery of an interesting case of conformational dynamics.

中文翻译：

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在 DFT 中，我们相信：对硝酮和左旋葡萄糖烯酮之间 1,3-偶极环加成的详尽探索揭示了构象动力学的一个奇怪案例


进行了实验和计算研究（包括 DFT 计算和畸变/相互作用分析），以评估硝酮结构对左旋葡萄糖烯酮（一种生物质衍生的手性烯酮）偶极 1,3-环加成结果的影响。虽然 B3LYP/6-31G*（根据我们的文献检索对这些反应进行建模的最流行方法）提供了良好的定性结果，但在某些系统中发现了较大的异常值。对其他水平的详尽探索使我们能够确定最合适的水平来同时预测反应性和选择性。系统预测的大多数水平的高外切选择性使我们重新考虑与哌啶衍生的硝酮反应的最初分配，这导致了构象动力学的一个有趣的案例的发现。