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Theoretical study of the Wittig reaction of cyclic ketones with phosphorus ylide

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Abstract

The Wittig reaction of cyclopropanone, cyclobutanone and cyclopentanone with phosphorus ylide (Me3P = CH2) in gas phase was investigated computationally at B3LYP/6-31G** level of theory. In the Wittig reaction of cyclic ketones, two transition states (TS1 and TS2), corresponding to formation and decomposition of oxaphosphetane (OP) were located and investigated. Two loosely bound intermediates, a reactant complex (RC) and a product complex (PC) were also found. In the reaction of cyclopropanone, cyclobutanone and cyclopentanone, two oxaphosphetanes (OP1 and OP2) were predicted. OP1 initially formed was converted into OP2 by pseudorotation. In contrast to the reactions with cyclobutanone and cyclopentanone, an early TS1 was found in the reaction of cyclopropanone. The order of first activation energy barrier relative to reactant total energy was found to be cyclopropanone (−4.97 kcal mol−1) < cyclobutanone (0.30 kcal mol−1) < cyclopentanone (3.60 kcal mol−1).

The Wittig reaction of monocyclic ketones with phosphorus ylide Me3PCH2.

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Notes

  1. That the Wittig reaction of non-stabilized ylides proceeds through initial electron transfer from the ylide to the carbonyl group has been suggested by several authors., see [15, 16]

  2. This suggestion has not been viewed formally overall because of its inconsistency with other observations, See [4, 14]

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Acknowledgments

One of the authors (N.J.) is thankful to the council of scientific and industrial research (CSIR), Government of India for the award of a fellowship.

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  1. Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India

    Nisha Jarwal & Pompozhi Protasis Thankachan

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  1. Nisha Jarwal
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Correspondence to Pompozhi Protasis Thankachan.

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ESM 1

Total electronic energy, enthalpy and Gibbs free energy (in Hartree) and the Cartesian coordinates of all optimized structures with imaginary frequencies of transition states (TS) are given in the supporting information. (DOCX 524 kb)

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Jarwal, N., Thankachan, P.P. Theoretical study of the Wittig reaction of cyclic ketones with phosphorus ylide. J Mol Model 21, 87 (2015). https://doi.org/10.1007/s00894-015-2571-y

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