4.7 Article

Iridium-Catalyzed [2+2+2] Cycloaddition of α,ω-Diynes with Isocyanates

期刊

JOURNAL OF ORGANIC CHEMISTRY
卷 77, 期 2, 页码 908-920

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jo202083z

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资金

  1. Japan Society for the Promotion of Science [21550107]
  2. Ministry of Education, Culture, Sports, Science and Technology of Japan
  3. Grants-in-Aid for Scientific Research [21550107] Funding Source: KAKEN

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[Ir(cod)Cl](2)/BINAP was found to be an efficient catalyst for the [2+2+2] cycloaddition of alpha,omega-diynes with isocyanates to give 2-pyridones. A wide range of isocyanates can be used for this reaction. Both aliphatic and aromatic isocyanates smoothly reacted with alpha,omega-diynes to give 2-pyridones in high yields. Aliphatic isocyanates were more reactive than aromatic isocyanates. For aromatic isocyanates, the electronic properties of the substituents affected the reactivity: electron-donating substituents enhanced the reaction. The reaction of unsymmetrical alpha,omega-diynes possessing two different internal alkyne moieties with isocyanates was regiospecific and gave a single product. This regioselectivity could be explained by the reaction of iridacyclopentadiene with a nitrogen-carbon double bond. The regioselectivity of the reaction of malonate-derived diyne was controlled by a steric effect, while that of the reaction of ester-tethered diyne was controlled by an electronic effect. [Ir(cod)Cl](2)/chiral diphosphine catalyst could be used for the enantioselective synthesis of C-N axially chiral 2-pyridone. The reaction of diyne la with o-methoxyphenyl isocyanate (7a) gave C-N axially chiral 2-pyridone (R)-8aa in 78% yield with 94% ee.

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