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The Effect of Solvent-Substrate Noncovalent Interactions on the Diastereoselectivity in the Intramolecular Carbonyl-Ene and the Staudinger [2 + 2] Cycloaddition Reactions.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-09-07 , DOI: 10.1021/acs.jpca.0c05738 Shailja Jain 1, 2 , Kumar Vanka 1, 2
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-09-07 , DOI: 10.1021/acs.jpca.0c05738 Shailja Jain 1, 2 , Kumar Vanka 1, 2
Affiliation
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Noncovalent interactions (NCIs) have been identified as important contributing factors for determining selectivity in organic transformations. However, cases where NCIs between solvents and substrates are responsible for a major extent for determining selectivity are rare. The current computational study with density functional theory identifies two important transformations where this is the case: the intramolecular carbonyl-ene reaction and the Staudinger [2 + 2] cycloaddition reaction. In both cases, the role of explicit solvent molecules interacting noncovalently with the substrate has been taken into account. Calculations indicate that the diastereomeric ratio would be 95.0:5.0 for the formation of tricyclic tetrahydrofuran diastereomers via the intramolecular carbonyl-ene reaction and 94.0:6.0 for the formation of the triflone diastereomers via the Staudinger [2 + 2] cycloaddition reaction, which corroborates with the experiment. Interestingly, in both the cases, the calculations indicate that noninclusion of explicit solvent molecules would lead to only a small difference between the competing transition states, which leads to the conclusion that solvent–substrate NCIs are the major cause for diastereoselectivity in both the cases considered.
中文翻译：
溶剂-底物非共价相互作用对分子内羰基-烯和Staudinger [2 + 2]环加成反应中非对映选择性的影响。
非共价相互作用（NCI）已被确定为决定有机转化选择性的重要贡献因素。但是，溶剂和底物之间的NCI在很大程度上决定选择性的情况很少见。当前使用密度泛函理论的计算研究确定了两种重要的转化：分子内的羰基-烯反应和Staudinger [2 + 2]环加成反应。在这两种情况下，都已经考虑了显式溶剂分子与底物非共价相互作用的作用。计算表明，通过分子内羰基-烯反应形成三环四氢呋喃非对映异构体的非对映异构体比例为95.0：5.0，为94.0：6。0通过Staudinger [2 + 2]环加成反应形成三链体非对映异构体，这与实验相符。有趣的是，在两种情况下，计算均表明，不包括显式溶剂分子只会导致竞争的过渡态之间只有很小的差异，这得出结论，在两种情况下，溶剂-底物NCI都是导致非对映选择性的主要原因。
更新日期：2020-10-02
中文翻译：
溶剂-底物非共价相互作用对分子内羰基-烯和Staudinger [2 + 2]环加成反应中非对映选择性的影响。
非共价相互作用（NCI）已被确定为决定有机转化选择性的重要贡献因素。但是，溶剂和底物之间的NCI在很大程度上决定选择性的情况很少见。当前使用密度泛函理论的计算研究确定了两种重要的转化：分子内的羰基-烯反应和Staudinger [2 + 2]环加成反应。在这两种情况下，都已经考虑了显式溶剂分子与底物非共价相互作用的作用。计算表明，通过分子内羰基-烯反应形成三环四氢呋喃非对映异构体的非对映异构体比例为95.0：5.0，为94.0：6。0通过Staudinger [2 + 2]环加成反应形成三链体非对映异构体，这与实验相符。有趣的是，在两种情况下，计算均表明，不包括显式溶剂分子只会导致竞争的过渡态之间只有很小的差异，这得出结论，在两种情况下，溶剂-底物NCI都是导致非对映选择性的主要原因。
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