Contrasting Reactivity of CS 2 with Cyclic vs. Acyclic Amidines
The interaction between carbon dioxide (CO 2 ) and amidines such as 1,8‐diazabicyclo[5.4.0]undecane (DBU) has been extensively studied, but the reaction of isovalent CS 2 with such bases has been largely ignored, apart from a single crystallography report. Acyclic acetamidines are cleaved by CS 2 at...
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Veröffentlicht in: | European journal of organic chemistry 2015-11, Vol.2015 (33), p.7334-7343 |
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Hauptverfasser: | , , , , , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
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Zusammenfassung: | The interaction between carbon dioxide (CO
2
) and amidines such as 1,8‐diazabicyclo[5.4.0]undecane (DBU) has been extensively studied, but the reaction of isovalent CS
2
with such bases has been largely ignored, apart from a single crystallography report. Acyclic acetamidines are cleaved by CS
2
at room temperature to give an isothiocyanate and a thioacetamide. Because the pathway to that cleavage involves a rotation that is difficult for cyclic amidines, the reaction of CS
2
with cyclic amidines produces an entirely different product: a cyclic carbamic carboxylic trithioanhydride structure. The path to that product involves sp
3
C‐H activation leading to the formation of a new C–C bond at a carbon α to the central carbon of the amidine group. Alkylation and ring‐opening of the cyclic carbamic carboxylic trithioanhydride has also been demonstrated under ambient conditions. |
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ISSN: | 1434-193X 1099-0690 |
DOI: | 10.1002/ejoc.201500973 |