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Theoretical Study of a Derivative of Chlorophosphine with Aliphatic and Aromatic Grignard Reagents: SN2@P or the Novel SN2@Cl Followed by SN2@C?

preprint
submitted on 16.11.2020, 16:05 and posted on 17.11.2020, 11:07 by Nandini Savoo, Lydia Rhyman, Ponnadurai Ramasami

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 SN2@P pathway while the reaction with the aromatic nucleophile proceeds through a novel SN2@Cl mechanism, followed by a frontside SN2@C mechanism. To the best of our knowledge, this is the first time that a SN2@Cl mechanism is reported. We also found that on reducing the bulkiness of substituents around the phosphorus atom, the backside SN2@P 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.

History

Email Address of Submitting Author

nandini.savoo@gmail.com

Institution

University of Mauritius

Country

Mauritius

ORCID For Submitting Author

0000-0002-8034-0368

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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