Microwave-assisted palladium-catalyzed C–C coupling versus nucleophilic aromatic substitution of hydrogen (SNᴴ) in 5-bromopyrimidine by action of bithiophene and its analogues

Verbitskiy, Egor V.; Cheprakova, Ekaterina M.; Zhilina, Ekaterina F.; Kodess, Mikhail I.; Ezhikova, Marina A.; Pervova, Marina G.; Slepukhin, Pavel A.; Subbotina, Julia O.; Schepochkin, Aleksandr V.; Rusinov, Gennady L.; Chupakhin, Oleg N.; Charushin, Valery N.

Microwave-assisted palladium-catalyzed C–C coupling versus nucleophilic aromatic substitution of hydrogen (SNᴴ) in 5-bromopyrimidine by action of bithiophene and its analogues

2013

5-Bromopyrimidine reacts with 2,2′-bithiophene, [2,2′:5′,2″]terthiophene and 2-phenylthiophene in the presence of a palladium catalyst to give 5-(het)aryl substituted pyrimidines due to the palladium-catalyzed aryl–aryl C–C coupling. However 5-bromo-4-(het)aryl-pyrimidines have been prepared from the same starting materials through the SN ᴴ-reaction catalyzed by a Lewis acid. Conditions for both types of reactions were optimized. All components of the reaction mixtures, including by-products, have been elucidated by gas–liquid chromatography/mass-spectrometry. Evidence for the structure of 4- and 5-bithiophenyl-substituted pyrimidines has first been obtained by means of X-ray crystallography analysis. Molecular orbital calculations (TDDFT), as well as the redox and optical measurements for all new compounds have also been performed.

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