Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 28, 2020
Previous Article Next Article

On the development of a nucleophilic methylthiolation methodology

Author affiliations

Abstract

Methylthiolation reactions are usually explored to access organosulfur compounds using methanethiol, an extremely flammable and toxic compound. Herein, methylthiomethyl esters were successfully applied as novel methylthiolation reagents in a low cost, transition-metal-free methodology. These reagents allowed the methylthiolation of a wide scope of chalcones, acyl ester derivatives and Morita–Baylis–Hillman acetates with good group tolerance, affording the methylthiolated products in moderate to excellent yields. The reaction mechanism was investigated through several control experiments, as well as by theoretical calculations employing Density Functional Theory. The results strongly support that a sulfurane and a sulfonium ylide appear as key intermediates and that a Pummerer type rearrangement is also crucial for the formation of this novel reagent. Furthermore, the methylthiolation mechanism is likely to proceed through the nucleophilic attack of the reagent, followed by an entropically favoured step involving the acetate attack to the positively charged species, then releasing the product.

Graphical abstract: On the development of a nucleophilic methylthiolation methodology

Back to tab navigation

Supplementary files

Article information


Submitted
02 Jun 2020
Accepted
02 Jul 2020
First published
02 Jul 2020

Org. Biomol. Chem., 2020,18, 5420-5426
Article type
Paper

On the development of a nucleophilic methylthiolation methodology

B. B. P. D. P. Carvalho, A. A. P. Amaral, P. P. de Castro, F. C. M. Ferreira, B. A. C. Horta and G. W. Amarante, Org. Biomol. Chem., 2020, 18, 5420
DOI: 10.1039/D0OB01149E

Social activity

Search articles by author

Spotlight

Advertisements