On the development of a nucleophilic methylthiolation methodology.

Organic & Biomolecular Chemistry
Bernardo Basbaum Portinho de Puga CarvalhoGiovanni Wilson Amarante

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.

References

Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
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Mar 26, 2013·Organic Letters·Mahendra PatilWalter Thiel
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Nov 20, 2018·The Journal of Organic Chemistry·Isabellar F S MarraGiovanni Wilson Amarante
Sep 17, 2019·The Journal of Organic Chemistry·Pedro P De CastroGiovanni W Amarante

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Citations

Apr 21, 2021·Organic & Biomolecular Chemistry·Shuangyang ChenLan-Gui Xie

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Methods Mentioned

BETA
NMR
column chromatography

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