16076-58-7Relevant academic research and scientific papers
Expanding Blaise-Type Reactions towards Indium-Mediated Transformations of α-Bromo-β-keto Esters with Nitriles
Li, Luomo,Babaoglu, Emre,Harms, Klaus,Hilt, Gerhard
supporting information, p. 4543 - 4547 (2017/08/30)
The aim of this work is the identification of mild reaction conditions for the Blaise-type transformation of brominated β-keto esters with nitriles to generate enamino-substituted keto esters. The best results were obtained when a combination of indium metal (0.7 equiv.) with indium trichloride (1.6 equiv.) were applied at 60 °C for 20 to 72 hours, and these conditions could be applied to a broad range of nitriles and a significant number of different β-keto esters. The transformation of aliphatic nitriles proved to be difficult and gave only moderate yields. However, aromatic nitriles gave good yields in many cases. The applicability range of β-keto esters is acceptable while some electron-deficient aryl-substituents on the keto ester were challenging substrates. Nevertheless, we were able to expand the scope of the Blaise-type reaction towards brominated β-keto esters significantly.
Facile access to cyclooctanoid ring systems via microwave-assisted tandem 6-exo dig cyclization-rearrangement sequence
Feldman, Aaron W.,Ovaska, Sami I.,Ovaska, Timo V.
, p. 4147 - 4155 (2014/06/09)
Appropriately substituted 5-alkyn-1-ol systems bearing a nitrile moiety at the triple bond serve as versatile precursors to a variety of cyclooctenone derivatives via a 'one-pot' base-catalyzed oxyanionic 6-exo dig cyclization/Claisen rearrangement sequence under microwave irradiation. It was found that the initially formed cyclic intermediate consists of a mixture of endo and exocyclic isomers, which appear to be in equilibrium under the reaction conditions. However, the only observed products from these reactions are α-cyano-substituted cyclooctenones, derived from the exocyclic dihydrofuran intermediates.
