Copper(I)-Catalyzed Amination of Propargyl Esters. Selective Synthesis of Propargylamines, 1-Alken-3-ylamines, and (Z)-Allylamines

Lewis Acid-Catalyzed Propargylic Etherification and Sulfanylation from Alcohols in MeNO2-H2O

“…5,6) An alcohol used as a precursor for carbocations is usually activated by transforming it to the corresponding acetate, [7][8][9][10][11][12][13][14][15][16][17] carbonate, 18,19) halide, 20) phosphonate. 21,22) Prior activation of an alcohol is also necessary if it has to be used as a nucleophile because of its low nucleophilicity. This is usually achieved by converting the hydroxyl group to a metal alkoxide.…”

Chiral Tridentate P,N,N Ligands for Highly Enantioselective Copper‐Catalyzed Propargylic Amination with both Primary and Secondary Amines as Nucleophiles

“…Thus, all of chloro-substituted substrates 5a-c gave similar results (entries [1][2][3]. The electronic property of the substituent in the para-position of the phenyl ring had little effect in the reactivity (84-90% yield) and enantioselectivity (91-97% ee) (entries [4][5][6][7][8].…”

“…[3] A seminal report by Murahashi and co-workers sets the stage for an enantioselective Cu-catalyzed propargylic amination. [4] While still in the racemic series at that stage, it was shown that Cu sources promote the amination of propargylic esters smoothly under mild reaction conditions. In 2008, van Maarseveen and Nishibayashi independently reported the asymmetric version of the copper-catalyzed propargylic amination of propargylic acetates.…”

“…The results indicated that the substitution pattern and electronic property had little effect on the reactivity and enantioselectivity. All of N-methyl aromatic amines 6a-h reacted with 1-phenyl-2-propynyl acetate 5d in excellent enantioselectivities and yields (entries [1][2][3][4][5][6][7][8]. The propargylic amination of 1-phenyl-2-propynyl acetate 5d with secondary dialkylamine 6i was also investigated under the same reaction conditions as those with aromatic amines except that a longer reaction time (24 h) was required, affording the corresponding propargylic amine 8r in high yield (87%) and with excellent enantioselectivity (95% ee) (entry 9).…”

A novel and convenient copper-catalyzed three-component coupling of aldehydes, alkynes, and hydroxylamines leading to propargylamines

“…Propargylamines are important structural elements of drug molecules and versatile synthetic intermediates, which have attracted increasingly synthetic pursuit of chemists due to their wide applications in the synthesis of a variety of nitrogenous compounds. 2,3 Traditionally, propargylamines are prepared by amination of propargylic halides, 4 propargylic phosphates, 5 and propargylic triflates, 6 or through nucleophilic attack of lithium acetylides, Grignard reagents on imines or their derivatives. 7 However, these methods suffer from issues of moisture sensitivity and the requirement of strictly controlled reaction conditions.…”