Theoretical and Computational Chemistry

Theoretical Study of a Derivative of Chlorophosphine with Aliphatic and Aromatic Grignard Reagents: [email protected] or the Novel [email protected] Followed by [email protected]?

Authors

Abstract

The proposed SN2 reactions of a hindered organophosphorus reactant with aliphatic and aromatic nucleophiles [Ye et al., Org. Lett. 19, 5384–5387 (2017)] were studied theoretically in order to explain the observed stereochemistry of the products. Our computations indicate that the reaction with the aliphatic nucleophile occurs through a backside SN[email protected] pathway while the reaction with the aromatic nucleophile proceeds through a novel SN[email protected] mechanism, followed by a frontside SN[email protected] mechanism. To the best of our knowledge, this is the first time that a SN[email protected] mechanism is reported. We also found that on reducing the bulkiness of substituents around the phosphorus atom, the backside SN[email protected] mechanism is preferred. The conclusions made from investigating the steric effect should help experimentalists to decide for the organophosphorus reactant to achieve the products of desired stereochemistry.

Content

Thumbnail image of Manuscript.pdf

Supplementary material

Thumbnail image of Supplementary Information.pdf
Supplementary Information