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Contrasting Reactivity of CS 2 with Cyclic vs. Acyclic Amidines
Author(s) -
Ang M. Trisha C.,
Phan Lam,
Alshamrani Aliyah K.,
Harjani Jitendra R.,
Wang Ruiyao,
Schatte Gabriele,
Mosey Nicholas J.,
Jessop Philip G.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500973
Subject(s) - chemistry , amidine , reactivity (psychology) , alkylation , carbamic acid , bond cleavage , medicinal chemistry , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
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.