53153-95-0Relevant academic research and scientific papers
Preparation of 2-arylquinolines from β-arylpropionitriles with aryllithiums and NIS through iminyl radical-mediated cyclization
Naruto, Hiroki,Togo, Hideo
, p. 5760 - 5770 (2019/06/18)
Treatment of β-arylpropionitriles with aryllithiums, followed by the reaction with water and then with NIS under irradiation with a tungsten lamp gave 2-arylquinolines in good to moderate yields. The present reaction proceeds through the formation of N-iodoimines from imines with NIS, the generation of imino-nitrogen-centered radicals, and their cyclization onto the aromatic rings of the imines to form 2-aryl-3,4-dihydroquinolines. Finally, the oxidation of 2-aryl-3,4-dihydroquinolines with NIS proceeds smoothly to generate 2-arylquinolines.
Vanadium-catalyzed solvent-free synthesis of quaternary α-trifluoromethyl nitriles by electrophilic trifluoromethylation
Früh, Natalja,Togni, Antonio
supporting information, p. 10813 - 10816 (2015/05/13)
The direct electrophilic trifluoromethylation of silyl ketene imines (SKIs) with hypervalent iodine reagents leads to the formation of quaternary α-trifluoromethyl nitriles in good yields. This new reaction has been carried out with a variety of substitut
Metalated nitriles: Internal 1,2-asymmetric induction
Fleming, Fraser F.,Liu, Wang,Ghosh, Somraj,Steward, Omar W.
, p. 2803 - 2810 (2008/09/19)
(Chemical Equation Presented) Alkylations of conformationally constrained acyclic nitriles containing vicinal dimethyl groups and an adjacent phenyl group or trisubstituted alkene are exceptionally diastereoselective. Probing the alkylation stereoselectivity with a series of C- and N-metalated nitriles implicates a reactive conformation in which an sp2-hybridized substituent projects over the metalated nitrile to avoid allylic strain. Steric screening thereby directs the electrophilic attack to the face of the metalated nitrile opposite the projecting substituent. Excellent stereoselectively is maintained in a diverse range of alkylations that efficiently install quaternary centers, even with isopropyliodide in which a contiguous array of tertiary-quaternary-tertiary stereocenters is created! Screening the conformational requirements with a series of acyclic nitriles and esters reveals the key structural requirements for high selectivity while providing a robust, predictive model that accounts for comparable ester alkylations affording the opposite diastereomer! The intensive survey of metalated nitrile alkylations identifies the key structural features required for high 1,2-asymmetric induction, addresses the long-standing challenge of asymmetric alkylations with acylic metalated nitriles, and provides a versatile method for installing hindered quaternary centers with excellent stereocontrol.
