Rhodium-Catalyzed Alkenylation of C–H Bonds in Aromatic Amides with Alkynes

Abstract

The rhodium-catalyzed alkenylation of C-H bonds of aromatic amides with alkynes is reported. A variety of functional groups, including OMe, OAc, Br, Cl, and even NO, are applicable to this reaction to give the corresponding hydroarylation products. The presence of an 8-aminoquinoline group as the directing group is crucial for the success of the reaction.

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[190] Av ariety of substrates were found to be applicable to the reaction, with the expected products formed in high yields.I nt his reaction, the presence of ad irecting group is crucial for the success of this alkenylation reaction. [190] Av ariety of substrates were found to be applicable to the reaction, with the expected products formed in high yields.I nt his reaction, the presence of ad irecting group is crucial for the success of this alkenylation reaction.…”

“…Bidentate Amide Directing Groups CÀHb ond activation assisted by ab identate directing group is awell-established procedure for the functionalization of amides because of its strong coordination ability towards am etal center.O ne of the most versatile and reliable bidentate directing groups developed to date is the 8-aminoquinoline amide moiety,w hich was introduced by Daugulis and co-workers in 2005 for use in Pd-catalyzed CÀHarylation reactions. [187][188][189][190][191][192][193] In 2014, the Rh I -catalyzed alkylation of 8-aminoquinoline amides was first reported in the reaction of a,b-unsaturated esters (Scheme 53 a). [173][174][175][176][177][178][179][180][181][182][183][184][185][186] Theu tility of an 8aminoquinoline moiety for the Rh-catalyzed functionalization of amides discussed here was mainly reported by Chatani and co-workers in terms of various alkylation and alkenylation reactions.…”

“…[173][174][175][176][177][178][179][180][181][182][183][184][185][186] Theu tility of an 8aminoquinoline moiety for the Rh-catalyzed functionalization of amides discussed here was mainly reported by Chatani and co-workers in terms of various alkylation and alkenylation reactions. [187][188][189][190][191][192][193] In 2014, the Rh I -catalyzed alkylation of 8-aminoquinoline amides was first reported in the reaction of a,b-unsaturated esters (Scheme 53 a). [187] Av ariety of a,bunsaturated esters can be used in this reaction, with the desired products being produced in good to excellent yields.…”

Rhodiumkatalysierte sp2‐ und sp3‐C‐H‐Funktionalisierungen mit entfernbaren dirigierenden Gruppen

“…Der 8‐Aminochinolin‐Baustein kann leicht installiert und wieder entfernt werden, sodass sich viele Arbeitsgruppen auf diese dirigierende Gruppe konzentriert haben . Die hier diskutierte Anwendung des 8‐Aminochinolin‐Bausteins für die Rh‐katalysierte Funktionalisierung von Amiden geht hauptsächlich auf die von Chatani veröffentlichten Alkylierungs‐ und Alkenylierungsreaktionen zurück. Die Rh I ‐katalysierte Alkylierung von 8‐Aminochinolinamiden wurde erstmals 2014 bei der Reaktion von α,β‐ungesättigten Estern diskutiert (Schema a) .…”

The Use of a Rhodium Catalyst/8-Aminoquinoline Directing Group in the C-H Alkylation of Aromatic Amides with Alkenes: Possible Generation of a Carbene Intermediate from an Alkene

“…The reaction of the aromatic amide 1 with diphenylacetylene gave a mixture of E-and Z-isomers of the alkenylation product 12 in 88% yield along with the cyclized isoquinolinone derivative 13 in 8% yield (Scheme 25). 54 Rodríguez, Arrayás, Carretero, and coworkers reported on the Rh-catalyzed reaction of C-H bonds in picolinamide 14 with alkynes (Scheme 26). 55 The reaction site was controlled by the catalyst used.…”