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DOI: 10.1055/a-2022-2206
Investigating the Mechanism of the Catalytic Intramolecular Aza-Wittig Reaction Involved in the Synthesis of 2-Methylbenzothiazole from the Perspective of Bonding Evolution Theory
A.I.A. thanks the University of Namur (Belgium) for his UNamur-CERUNA Ph.D. Mobility Fellowship. V.L. thanks the FNRS-FRFC for his Research Associate position. The calculations were performed on the computers of the Consortium des Equipements de Calcul Intensif (CECI, http://www.ceci-hpc.be) and particularly those of the Technological Platform of High-Performance Computing, for which the authors gratefully acknowledge the financial support of the F.R.S.-FNRS (GEQ U.G006.15, RW/GEQ2016, U.G018.19, U.G011.22), of the Walloon Region (RW1610468, RW/GEQ2016, and RW2110213), and of the University of Namur.
This work is dedicated to Prof. Alain Krief at the occasion of his 80th birthday. Prof. Alain Krief has introduced two of us to Organic Chemistry and has trained them to many marvelous facets of Organic Synthesis.
Abstract
Bonding evolution theory has been used at the density functional theory level [ωB97X-D exchange-correlation functional, 6-311G(d,p) basis set, and solvent (toluene) effects with polarizable continuum model] to unravel the reaction mechanism of the intramolecular aza-Wittig reaction of 2-(acetylthio)phenyl isocyanate (1) catalyzed by 3-methyl-1-phenyl-2-phospholene 1-oxide (2) to form 2-methylbenzothiazole (3). The reaction involves four steps (transition states) corresponding to (1) the formation of a cycloadduct (O–C then P–N bonds), (2) a decarboxylation leading to the formation of an iminophosphorane, and (3) an intramolecular [2+2] cycloaddition (N–C then P–O bonds) followed by (4) a retro [2+2] cycloaddition (cleavage of the P–N then O–C bonds) to get the product and regenerate the catalyst. Step 1 is the rate-determining step with an activation Gibbs free enthalpy of 21 kcal mol–1 and it is favored with respect to a competitive pathway leading to the formation of another cycloadduct (P–C then O–N bonds). The whole reaction is exergonic with a Gibbs free energy decrease of 31 kcal mol–1, associated with the liberation of a CO2 molecule and the formation of the aromatic benzothiazole. Following the scale of Domingo, the successive steps of the reaction have a polar nature.
Key words
Wittig reaction - bonding evolution theory - DFT calculations - 2-methylbenzothiazole synthesis - aza-WittigSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2022-2206.
- Supporting Information
Publication History
Received: 15 November 2022
Accepted after revision: 30 January 2023
Accepted Manuscript online:
30 January 2023
Article published online:
08 March 2023
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