Eine allgemeine und selektive Eisen‐katalysierte Aminocarbonylierung von Alkinen: Synthese von Acryl‐ und Zimtsäureamiden

Abstract

Effizient und preisgünstig: Die erste allgemeine Methode zur Eisen‐katalysierten Monocarbonylierung von Alkinen wurde entwickelt. Ausgehend von kommerziell erhältlichen Aminen und Alkinen wurde eine Reihe von Zimtsäure‐ und Acrylamiden selektiv in Gegenwart katalytischer Mengen [Fe3(CO)12] und des Liganden L erhalten (siehe Schema). Die Methode ist hoch chemo‐ und regioselektiv und erfordert keinen teuren Katalysator.

Microwave‐Assisted Aminocarbonylation of Ynamides by Using Catalytic [Fe3(CO)12] at Low Pressures of Carbon Monoxide

“…Microwave irradiation not only dramatically reduces reaction times, but also allows a better conver- 1 [a] [Fe(CO) 5 ] nPrNH 2 (6 equiv) 20 2 [b] -nPrNH 2 (6 equiv) -3 [a] A C H T U N G T R E N N U N G [Fe 3 (CO) 12 ] nPrNH 2 (6 equiv) 50 4 [c] A C H T U N G T R E N N U N G [Fe 3 (CO) 12 ] nPrNH 2 (1 equiv)/DIPEA (4 equiv) 53 5 [c] A C H T U N G T R E N N U N G [Fe 3 (CO) 12 ] nPrNH 2 (1 equiv)/DBU (4 equiv) 52 6 [c] A C H T U N G T R E N N U N G [Fe 3 (CO) 12 ] nPrNH 2 (1 equiv)/TEA (4 equiv) 70 7 [c] A C H T U N G T R E N N U N G [Fe 3 (CO) 12 ] nPrNH 2 (1 equiv)/DMF (4 equiv) 30 8 [c] A C H T U N G T R E N N U N G [b] THF 90 20 min -83 12 [c] THF www.chemeurj.org sion to be observed by using a lower pressure of CO (1.3 vs. 10 bar). [39] This cannot be related to any specific effect of microwaves but our results are completely in agreement with well-documented studies on microwave-assisted reactions in the presence of gaseous reagents; hydroformylation, hydrogenation, and carbonylation reactions can all be run inside a microwave cavity by using lower pressures of gas, giving the possibility of running these transformations in a safer manner. [4,5,10,11] The scope of the catalyst system was demonstrated by the microwave-assisted carbonylation of various ynamides in the presence of different nucleophiles (Table 3).…”

“…A few weeks ago, Beller and co-workers disclosed his results on the general selective iron-catalyzed aminocarbonylation of simple substituted alkynes. [39] Therefore, we report herein the preliminary achievements simultaneously obtained by our group.…”

Substituent‐Dependent, Iron‐Mediated Tandem Cyclization of Diynes with Benzaldehyde Acetals to Form Highly Functionalized Indene Derivatives

“…[7] Although enediynes have been documented for the synthesis of indenes, [8] diynes have seldom been applied for this purpose. [10][11][12] Very recently, we discovered that FeCl 3 and FeCl 3 ·6H 2 O can efficiently promote the intramolecular cyclization of monoalkynyl aldehyde acetals to generate solvent-dependent Prins-type products [13a] and a,b-unsaturated cyclic ketones, [13b] respectively (Scheme 1). [10][11][12] Very recently, we discovered that FeCl 3 and FeCl 3 ·6H 2 O can efficiently promote the intramolecular cyclization of monoalkynyl aldehyde acetals to generate solvent-dependent Prins-type products [13a] and a,b-unsaturated cyclic ketones, [13b] respectively (Scheme 1).…”

“…[9] Recently, iron catalysis has emerged as a promising, environmentally benign alternative to traditional transition-metal catalysis due to the many advantages of utilizing iron-catalyst precursors, such as low cost, nontoxicity, good stability, and straightforward methods of handling. [10][11][12] Very recently, we discovered that FeCl 3 and FeCl 3 ·6H 2 O can efficiently promote the intramolecular cyclization of monoalkynyl aldehyde acetals to generate solvent-dependent Prins-type products [13a] and a,b-unsaturated cyclic ketones, [13b] respectively (Scheme 1). Herein, we report the FeCl 3 -and FeBr 3 -mediated tandem cyclization of simple diynes with benzaldehyde acetals for the synthesis of highly functionalized indenes.…”

Efficient Copper(II)‐Catalyzed Transamidation of Non‐Activated Primary Carboxamides and Ureas with Amines

“…Alternatively, well-established name reactions (i.e., Ritter, [5] Schmidt, [6] Beckmann, [7] Ugi, [8] Wolff, [9] etc.) and more recently established approaches [10][11][12][13][14][15] are applied for their synthesis.…”