A Pd–Sn heterobimetallic catalyst for carbonylative Suzuki, Sonogashira and aminocarbonylation reactions using chloroform as a CO surrogate

Abstract

Herein, we report a heterobimetallic Pd-Sn catalyst for the carbonylative Suzuki coupling, aminocarbonylation reaction, and carbonylative Sonogashira coupling of aryl halides with boronic acid, amine, and aromatic alkyne leading to...

Aminocarbonylation Reaction Using a Pd–Sn Heterobimetallic Catalyst: Three-Component Coupling for Direct Access of the Amide Functionality

“…According to the proposal, the mechanism may involve a Pd(II)/(0) pathway. 16 As shown in Scheme 6, the Pd−Sn complex (A) is presumed to act as a precatalyst and generate the active Pd(0) catalyst (B) in situ. The subsequent steps would involve (i) oxidative addition of aryl iodide across Pd(0) to form the arylpalladium(II) intermediate (C) followed by (ii) CO insertion into the aryl palladium intermediate, resulting in the acylpalladium intermediate (D).…”

“…Although further work is warranted, a plausible mechanism is illustrated in Scheme . According to the proposal, the mechanism may involve a Pd­(II)/(0) pathway . As shown in Scheme , the Pd–Sn complex (A) is presumed to act as a precatalyst and generate the active Pd(0) catalyst (B) in situ.…”

“…The subsequent steps would involve (i) oxidative addition of aryl iodide across Pd(0) to form the arylpalladium­(II) intermediate (C) followed by (ii) CO insertion into the aryl palladium intermediate, resulting in the acylpalladium intermediate (D). Based on the literature and our insight, the acylpalladium complex could be the key intermediate. A transmetalation step with the tin adduct followed by reductive elimination will result in the aminocarbonylation product and regenerate the active Pd(0) catalyst.…”

“…13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ: 170.3,160.8,129.1,127.2,113.7,66.8, Methanone (3e). 16 Purification by chromatography (petroleum ether/EtOAc = 3:2) afforded 3e as a yellow solid (100 mg, 85%): 1 H NMR (400 MHz, CDCl 3 ) δ 8.39− 8.14 (m, 2H), 7.63−7.46 (m, 2H), 3.93−3.26 (m, 8H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ: 167.6,141.7,139.8,133.5,131.7,130.7,130.2,129.9,129.7,128.2,127.6,64.5, phenyl) Methanone (3f).…”

SnCl2-catalyzed multicomponent coupling: synthesis of 1,3-oxazolidine derivatives using paraformaldehyde as a C1 feedstock

“…36–42 Apart from this, the orbital structure of tin compounds facilitates their complex formation with various transition metals, leading to highly active catalysts. 43–49…”