Rhodium-Catalyzed anti-Markovnikov Addition of Secondary Amines to Arylacetylenes at Room Temperature

Abstract

An efficient method for synthesis of E-enamines by the anti-Markovnikov addition of secondary amines to terminal alkynes is described. The reaction of a variety of aryl- and heteroarylacetylenes proceeded at room temperature using a combination of a 8-quinolinolato rhodium complex and P(p-MeOC(6)H(4))(3) as a catalyst. The products were obtained as enamines by simple bulb-to-bulb distillation.

The Origin of Anti‐Markovnikov Regioselectivity in Alkene Hydroamination Reactions Catalyzed by [Rh(DPEphos)]+

“…[14] In recent years, the use of Ir-and Rhbased catalysts, and more recently Cu hydride catalysts, [15,16] has enabled significant advances in controlling regioselectivity. [17] Rhodium(I) complexes haven provent ob ep articularly efficient forp romoting selectivea nti-Markovnikov hydroamination of both terminal alkynes [18] and vinylarenes. [19,20] In 1999, Beller reportedt he first intermolecular anti-Markovnikov oxidative amination and hydroamination of styrenes catalyzed by the cationic [Rh(COD) 2 ]BF 4 /PPh 3 complex.…”

Efficient and Selective Synthesis of E‐Vinylamines via Tungsten(0)‐Catalyzed Hydroamination of Terminal Alkynes

“…To the best of our knowledge, this is the first example of the hydroamination of alkynes with such a very well‐known and simple tungsten complex as catalyst. It should be noted that the catalytic activity of Ia meets or exceeds the activity of other catalytic systems based on Rh and Ru 2d,e,f,h. It is also worth mentioning that the hydroamination reaction can be realized in the presence of W(CO) 6 Ib , as the precursor of the catalyst Ia .…”

Avanços recentes na hidroaminação de compostos insaturados

“…35 Durante o desenvolvimento dessa metodologia baseada em catálise de Ru (I), observou-se que alcinos internos não sofreram hidroaminação sob as condições mostradas no Esquema 11 e que a adição de aminas ocorre exclusivamente no carbono terminal, indicando que o mecanismo passa pela formação de uma espécie vinilideno-rutênio (70). 36 Na sequência, a piperidina (67) atacaria o carbono ligado diretamente no centro metálico e a protonação da ligação Ru-C levaria à enamina 69 e à espécie catalítica de rutênio.…”