Palladium-catalyzed cross-dehydrogenative coupling of maleimides with simple arenes: a fast track to highly substituted maleimides

Abstract

A combination of PivOH/TFA, accelerates an unprecedented palladium-catalyzed CDC diarylation of unfunctionalized maleimides with simple arenes.

Chemodivergence in Fluorine Source-Controlled Cascade Reaction of Aryne Precursors to Synthesize Pyrrolo[3,4-b]indoles and 3-Arylated Maleimides

“…13 C{ 1 H} NMR (100 MHz, DMSO-d 6 ): δ 176.9, 176.1, 148.9, 131.9, 125.6, 122.5, 121.9, 120.6, 66.5, 48.1, 46.9, 33.1, 18.4, 12.6, 12.6. HRMS (ESI-TOF + ) m/ z: calcd for C 15…”

Recent Developments in Palladium-Catalysed Non-Directed C–H Bond Activation in Arenes

“…In 2016, Shamsianpour and Jafarpour described the diarylation of an olefinic bond for the synthesis of highly substituted maleimides, which represent a group of organic photochromic compounds (Scheme 21). 40 The method required AgOAc as the oxidant and followed a Pd(II)/Pd(0) catalytic cycle. The catalytic system gave good yields of diarylated products with both electron-rich and electron-poor arenes.…”

“…Dehydrogenative cross-coupling of arenes and maleimides reported by Shamsianpour and Jafarpour 40 Alsters and Fernández-Ibáñez recently developed an aerobic CDC coupling of o-xylene (Scheme 22) for the synthesis of an industrially useful monomer, 4,4′-biphthalic anhydride, under industrially relevant conditions. 41,42 The catalytic system omitted the Cu co-catalyst that was used in previous procedures, 43 and more importantly, proceeded under neat conditions.…”

Developing a straightforward route toward the synthesis of arylaminomaleimides by palladium-catalyzed arylation of one-pot synthesized aminomaleimides

“…34 However, our group previously reported the challenging diarylation of maleimides by the Heck coupling and also the cross-dehydrogenative reaction. 10,31 In addition, monoarylation of maleimides by the Heck reaction using potassium acetate as a weak base has been reported. 35 It is worth mentioning that according to the literature, electron-donating group-bearing olefins, such as enamines, have been reported to show selectivity mostly for arylation through the Heck cross-coupling reaction with aryl halides at the α-position of the amine substituent instead of the β-position.…”

“…30 One of the noticeable strategies for addressing this goal is the direct C–H functionalization of organic moieties as an atomic economical method. 31 Accordingly, the Heck cross-coupling reaction catalyzed by palladium is a well-known coupling reaction for direct functionalization of olefin's C–H with vinyl and aryl halides. 32,33 Despite the electron deficiency of maleimides, they suffer from hydrolysis and ring-opening of the maleimide core under basic conditions.…”