ChemInform Abstract: 2-Aza-1,3-dienes with Electron-Releasing Substituents at the 1,3 Positions. Reagents for the Construction of Pyridine and Pyrimidine Derivatives

Autor:	G. Morel, S. Sinbandhit, Jean Paul Pradere, Loïc Toupet, E. Marchand
Rok vydání:	2010
Předmět:	Dimethyl acetylenedicarboxylate chemistry.chemical_compound Allylic rearrangement Deprotonation chemistry Pyrimidine Stereochemistry Phenyl isothiocyanate Pyridine General Medicine Acrylonitrile Medicinal chemistry Adduct
Zdroj:	ChemInform. 27
ISSN:	0931-7597
Popis:	New 2-aza-1,3-dienes bearing 1 and 3-donor substituents are prepared from N-thioacylacetamidines through deprotonation of N-ylidene acetamidinium iodides. The 2-aza-3-(dimethylamino)-1-(methylthio)-1-phenylbutadiene (3) is trapped in situ by the residual precursor salt acting as a heterodienophile to give the pyrimidine 5. Substituted 2-aza-1-(dimethylamino)-3-(methylthio) analogues react readily with a variety of electron-deficient dienophiles to yield pyridine or pyrimidine derivatives. The stereochemistry of the hetero Diels-Alder reaction in the cases of dimethyl fumarate and acrylonitrile has been assigned by X-ray diffraction analyses of the resulting tetrahydropyridines and corresponds to an exo selectivity. The number and nature of cycloadducts in the cases of dimethyl acetylenedicarboxylate and phenyl isothiocyanate depend on C-4 substitution. The results obtained from the C-4 unsubstituted azabutadiene 8 are explained by an allylic rearrangement involving the 1,3-migration of dimethylamino group in the primary [4+2] adduct.
Databáze:	OpenAIRE
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