Reactivity of 1, 3-dichloro-1, 3-bis(dimethylamino)-propenium salts with primary amines. (13th July 2021)

• Record Type: Journal Article
• Authors: Land, Michael A.; Robertson, Katherine N.; Ylijoki, Kai E. O.; Clyburne, Jason A. C.
• Is Part Of: New journal of chemistry. Volume 45:Number 30(2021)
• Page Start: 13558
• Page End: 13570
• Publication Date: 2021-07-13
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d1nj02298a
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : 1, 3-Dichloro-1, 3-bis(dimethylamino)propenium salts react with primary amines to give different products depending on properties of the amine used, including the size of the R groups, whether it is aromatic, and if there is a hydrogen on the α-carbon. Abstract : 1, 3-Dichloro-1, 3-bis(dimethylamino)propenium salts react with primary amines to give different products depending on the structure of the amine. Reactions in which the primary amine is bonded to a tertiary carbon ( tert -butylamine and 1-adamantylamine) result in 1, 1-bis(dimethylamino)-3, 3-bis(alkylamino)propenium salts which form via a 1, 3-dimethylamino shift. In contrast, the reactions in which the primary amine is bonded to a secondary carbon (cyclohexylamine, cyclopentylamine, and sec -butylamine) result in 1-(ylidene)amino-1, 3-bis(dimethylamino)propenium salts which form via an intramolecular hydride shift. All of the synthesized compounds have been fully characterized using spectroscopic methods, including single crystal X-ray diffraction. Finally, the mechanisms of the intramolecular rearrangements have been investigated computationally at the ωB97X-D/6-311G(d, p) level of theory, suggesting that the reactions proceed through putative keteniminium species.