Dimethylamin als Substrat in Hydroaminoalkylierungsreaktionen

Abstract

Übergangsmetallkatalysierte Hydroaminoalkylierungen von Alkenen haben im vergangenen Jahrzehnt große Fortschritte gemacht und entwickeln sich zu einer greifbaren Alternative zur industriellen Synthese von Aminen durch Hydroformylierung von Alkenen und nachfolgende reduktive Aminierung.E in großes Hindernis war in der Vergangenheit, dass Methylamin und Dimethylamin als industriell wichtigste Amine in diesen Reaktionen nicht zufriedenstellend umgesetzt werden konnten. Wirz eigen hier erstmals die erfolgreiche Umsetzung von Dimethylamin in katalytischen Hydroaminoalkylierungen von Alkenen mit guten Ausbeuten, sowie die Anwendbarkeit füre ine Reihe verschiedener Alkene und die Toleranz gegenüber verschiedenen funktionellen Gruppen. Zusätzlich präsentieren wir die katalytischeD ihydroaminoalkylierungsreaktion mit Dimethylamin, über die nie zuvor berichtet wurde.

Cyclic Ureate Tantalum Catalyst for Preferential Hydroaminoalkylation with Aliphatic Amines: Mechanistic Insights into Substrate Controlled Reactivity

“…Hydroaminoalkylation can be catalyzed by both early (Sc, Ti, , Zr, Nb, Ta, ,,, ) and late transition metals, (Ru, Co, Rh, Ir, Pd,). Two regioisomers can be formed in the hydroaminoalkylation of terminal alkenes: the linear or branched products .…”

Hydroaminoalkylation of Allenes

“…In a 25 mL ampoule with magnetic stir bar, N-(hepta-5,6-dien-1-yl)-4-methylaniline (1, 101 mg, 0.5 mmol) and the catalyst (IV, 27 mg, 0.05 mmol, 10 mol%) were dissolved in p-cymene (15 mL). The ampoule was sealed [8] and heated to 160 °C for 24 h. The product was isolated by chromatography (250 g SiO2, l = 1 m, ID = 20 mm, PE/Et2O = 30/1, Rf = 0.24) and was obtained as slightly yellow oil (35 mg, 0.17 mmol, 35 %). The chromatography also afforded a small amount of the intermediate 4-methyl-N-(2-methylenecyclohexyl)aniline (4, 4 mg, 0.02 mmol, 4 %) as a yellow liquid.…”

“…In a 25 mL ampoule with magnetic stir bar, N-(octa-6,7-dien-1-yl)-4-methylaniline (6, 108 mg, 0.5 mmol) and the catalyst (IV, 27 mg, 0.05 mmol, 10 mol%) were dissolved in p-cymene (15 mL). The ampoule was sealed [8] and heated to 160 °C for 16 h. Thin layer chromatography (SiO2, n-hexane/Et2O = 10/1, Rf = 0.56) and subsequent capillary distillation afforded the product (12 mg, 0.06 mmol, 10 %, mixture of 8/7 = 87/13 according to GC) as a slightly yellow oil. To obtain a pure sample of 8, 40 mg of such a mixture were separated by chromatography (45 g 97 %-SiO2-3 %-AgNO3, l = 1 m, ID = 10 mm, PE/Et2O = 1/1, Rf = 0.8) and subsequent capillary distillation.…”

“…In a 25 mL Schlenk tube with magnetic stir bar, N-(hexa-4,5-dien-1-yl)-4-methylaniline (9, 94 mg, 0.5 mmol) and the catalyst (IV, 27 mg, 0.05 mmol, 10 mol%) were dissolved in p-cymene (15 mL). The tube was sealed [8] and heated to 160 °C for 2 h. The solvent was removed under vacuum at room temperature. Pentan-1-ol (1 mL) was added and the mixture was shaken.…”

“…In a Glovebox under N2-atmosphere, a 25 mL ampoule with magnetic star bar was charged with the catalyst (IV, 82 mg, 0.15 mmol, 10 mol%), N-methylaniline (161 mg, 1.5 mmol) and 1,2-propadiene solution in toluene (0.40 M, 18.8 mL, 7.5 mmol). The ampoule was sealed [8] and heated to 160 °C for 6 h. The product was isolated by chromatography (150g SiO2, PE/EtOAc = 30/1, Rf = 0.15) and was obtained as a colorless oil (47 mg, 0.25 mmol, 17 %). 1 H NMR (C6D6, 500 MHz): δ = 1.44 (s, 3 H), 1.77-1.82 (m, 1 H), 2.11-2.16 (m, 1 H), 2.37-2.52 (m, 3 H), 2.64 (d, J = 16.1 Hz, 1 H), 3.67 (br.…”