Palladium‐Catalyzed N‐Arylation of Iminodibenzyls and Iminostilbenes with Aryl‐ and Heteroaryl Halides

Abstract

Compounds containing the iminodibenzyl and iminostilbene ring systems are prevalent in medicinal targets and functional materials. Herein, we report palladium-catalyzed conditions for the N-arylation of these ring systems. This protocol could be applied to a variety of (hetero)aryl chloride and bromide substrates, including ones, which are sterically hindered or those containing a variety of functional groups. Use of the fourth-generation palladacycle precatalyst gave good to excellent yields by using low palladium-catalyst loadings (0.1 to 1 mol %).

A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

“…Thus, the reaction of 2 e with 1 i gave 3ie exclusively without the formation of 3′ ie . This unusual functional group selectivity is in sharp contrast to the transition metal catalysis, and also other reactions . As already stated, the indium salt catalyzes the S N Ar‐based biheteroaryl synthesis .…”

Preparation and Photoluminescent Properties of Three 5‐Amino Benzothiadiazoles (5‐amBTDs)

“…Three 5‐aminobenzothiadiazoles (5‐amBTDs) were prepared in moderate yields through Buchwald‐Hartwig coupling [13] between 5‐benzothiadiazole and three secondary amines as shown in Scheme 1. These compounds were fully characterized by 1 H and 13 C NMR spectroscopy (Figures S1–S6) and HRMS (Figures S7–S9) as well as by single crystal analysis (Table S1).…”

Iptycene-Containing Azaacenes with Tunable Luminescence

“…Unfortunately, initial attempts using a variety of ligands (XPhos, t-BuBrettPhos, Ru-Phos, or t-BuXPhos) only produced unreacted and reduced forms of 7. However, the N-arylation with iminodibenzyl, which is known to be a better nucleophile than carbazole, 31 proceeded smoothly to give 14 in 56% yield using the Buchwald precatalyst Pd-RuPhos-G4 (Scheme 2).…”

“…Unfortunately, initial attempts using a variety of ligands (XPhos, tBuBrettPhos, RuPhos or tBuXPhos) only produced unreacted and reduced forms of 7. However, the Narylation with iminodibenzyl, which is known to be a better nucleophile than carbazole, [31] proceeded smoothly to give 14 in 56% yield using the Buchwald precatalyst Pd-RuPhos-G4 (Scheme 2). These promising coupling results with aryl bromides also encouraged us to synthesize a (triisopropylsilyl)acetylene product (15) via a Sonogashira reaction catalyzed by Pd(PPh3)4 and CuI in 57% yield (Scheme 3).…”