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. 2020 Sep 1;59(36):15512-15516.
doi: 10.1002/anie.202002936. Epub 2020 Jun 15.

Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions

Laura Castoldi  1 , Ester Maria Di Tommaso  1 , Marcus Reitti  1 , Barbara Gräfen  1 , Berit Olofsson  1
Affiliations

Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions

Laura Castoldi et al. Angew Chem Int Ed Engl. .

Abstract

The iodine(III) reagents vinylbenziodoxolones (VBX) were employed to vinylate a series of aliphatic and aromatic thiols, providing E-alkenyl sulfides with complete chemo- and regioselectivity, as well as excellent stereoselectivity. The methodology displays high functional group tolerance and proceeds under mild and transition metal-free conditions without the need for excess substrate or reagents. Mercaptothiazoles could be vinylated under modified conditions, resulting in opposite stereoselectivity compared to previous reactions with vinyliodonium salts. Novel VBX reagents with substituted benziodoxolone cores were prepared, and improved reactivity was discovered with a dimethyl-substituted core.

Keywords: alkenyl sulfides; benziodoxolones; hypervalent compounds; synthetic methods; vinylbenziodoxolones.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Preparation of vinylbenziodoxol(on)es and vinylations with VBX.
Scheme 2
Scheme 2
Scope of thiol vinylation with VBX, products were obtained with E/Z>20:1 unless specified. [a] E/Z 16:1 [b] At 50 °C. [c] E/Z 5:1 [d] With 2 a (2.1 equiv) and base (2.0 equiv). [e] With 2 a (1.5 equiv) at 50 °C. [f] With 2.0 equiv base.
Scheme 3
Scheme 3
Scope with substituted VBX reagents.
Scheme 4
Scheme 4
S‐Vinylation of heterocycles with VBX.
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