Titanium-Catalyzed Intermolecular Hydroaminoalkylation of Terminal Alkynes.

(E)- N -(2-Cyclohexyl-1-phenyl-3-(trimethylsilyl)allyl)aniline (19) General procedure A was used to react I N i -benzylaniline (183 mg, 1.0 mmol) with (cyclohexylethynyl)trimethylsilane (180 mg, 1.0 mmol) in the presence of catalyst B II-Bu b (111 mg, 0.1 mmol) for 24 h at 140 °C. Keywords: alkynes; allylamines; C-H activation; hydroaminoalkyl-ation; titanium; catalysis EN alkynes allylamines C-H activation hydroaminoalkyl-ation titanium catalysis 3759 3776 18 11/01/23 20231116 NES 231116 Graph The catalytic hydroaminoalkylation of alkenes [1][8] (Scheme 1), which takes place by a 100% atom-economical addition of the -C-H bond of a primary, [8] secondary, [8][8][8][8] or tertiary [8][8] amine across the alkene double bond, has received considerable attention over the past 15 years. N -(3,3-Dimethyl-2-methylenebutyl)aniline (1) 4d General procedure A was used to react I N i -methylaniline (107 mg, 1.0 mmol) with I tert i -butylacetylene (99 mg, 1.2 mmol) in the presence of catalyst B II-DIPP b (194 mg, 0.1 mmol) for 24 h at 140 °C. 3-Chloro- N -(3,3-dimethyl-2-methylenebutyl)aniline (5) General procedure A was used to react 3-chloro- I N i -methylaniline (142 mg, 1.0 mmol) with I tert i -butylacetylene (99 mg, 1.2 mmol) in the presence of catalyst B II-DIPP b (194 mg, 0.1 mmol) for 24 h at 140 °C. N -(3,3-Dimethyl-2-methylenebutyl)-4-(trifluoromethoxy)aniline (7) General procedure A was used to react I N i -methyl-4-(trifluoromethoxy)aniline (191 mg, 1.0 mmol) with I tert i -butylacetylene (99 mg, 1.2 mmol) in the presence of catalyst B II-DIPP b (194 mg, 0.1 mmol) for 24 h at 140 °C. [Extracted from the article]