- Studies on Pyrimidine Derivatives. XXXVIII. Cross-Coupling Reaction of N-Heteroaryl Iodides with Ethoxycarbonylmethylzinc Bromide in the Presence of Palladium Catalyst
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In the presence of tetrakis(triphenylphosphine)palladium, 2-iodo-4,6-dimethylpyrimidine and 4-iodo-2,6-dimethylpyrimidine reacted with ethoxycarbonylmethylzinc bromide (Reformatsky reagent) to give ethyl 4,6-dimethyl-2-pyrimidineacetate and ethyl 2,6-dimethyl-4-pyrimidineacetate, respectively.In contrast, the reaction of 5-iodo-2,4-dimethylpyrimidine with the same reagent resulted in recovery of the starting iodide.Similar results were observed in the reactions of various N-heteroaryl iodides.Keywords - Reformatsky reagent; cross-coupling reaction; N-heteroaryl halide; N-heteroarylacetic acid; palladium catalyst; ethyl bromoacetate
- Yamanaka, Hiroshi,An-naka, Masayuki,Kondo, Yoshinori,Sakamoto, Takao
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p. 4309 - 4313
(2007/10/02)
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- Studies on Tertiary Amine Oxides. LXXXI. Formation of 1-Isoquinolinio-methylides by the reaction of Isoquinoline 2-Oxide with Cyanoacetic Acid and Benzoylacetonitrile in the Presence of Acetic Anhydride
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Isoquinoline 2-oxide (1) reacts with cyanoacetic acid in the presence of Ac2O to afford various types of 1-substituted isoquinolines (2, 4, 6, and 7) and N-ylides (3 and 5a) depending upon the reaction conditions and processing procedures (Table I).The reaction in Ac2O gives initially α-acetoxycarbonyl-1-isoquinolineacetonitrile (2) and 2-isoquinolinio-acetoxycarbonylcyanomethylide (3), and that in Ac2O-dimethylformamide yields only 3.Products 2 and 3 are readily convertible into α-acetyl-1-isoquinolineacetonitrile (4) and 2-isoquinolinio-acetylcyanomethylide (5a), respectively, by processing involving heating.The reaction in ethanol gives ethyl α-cyano-1-isoquinolineacetate (6) and di(1-isoquinolyl)acetonitrile (7).The reaction of 1 with benzoylacetonitrile affords both the corresponding 1-substituted isoquinoline (10) and N-ylide (11).Reactions with ethyl benzoylacetate and, methyl and ethyl acetoacetates produce 1-substituted isoquinolines (12 and 14a, b) and 4-acetoxyisoquinoline (13), no ylide being formed.Keywords - isoquinoline 2-oxide; nucleophilic reaction; decarboxylative acyl migration; α-acetoxycarbonyl-1-isoquinolineacetonitrile; α-acetyl-1-isoquinolineacetonitrile; ethyl α-cyano-1-isoquinolineacetate; α-benzoyl-1-isoquinolineacetonitrile; 2-isoquinolinio-acetoxycarbonylcyanomethylide; 2-isoquinolinio-acetylcyanomethylide; 2-isoquinolinio-benzoylcyanomethylide.
- Funakoshi, Kazuhisa,Inada, Haruaki,Hamana, Masatomo
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p. 4731 - 4739
(2007/10/02)
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