A Palladium Bipyridyl Complex Grafted onto Nanosized MCM‐41 as a Heterogeneous Catalyst for Negishi Coupling

Abstract

The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM‐41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70 °C for electron‐deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110 °C were required if electron‐rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50 °C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.

An Expedient Route to 9‐Arylmethylanthracene Derivatives via Tandem Ni‐Catalyzed Alkene Dicarbofunctionalization and Acid‐Promoted Cyclization‐Aromatization

“…al. report the synthesis of anthracene derivatives using Negishi coupling of aryl halides with organozinc chlorides catalyzed by a palladium bipyridyl complex . Herein, we report an efficient one pot synthesis of 9‐arylmethylanthracene from vinylarenes, aryl iodides and arylzinc reagents.…”

“…report the synthesis of anthracene derivatives using Negishi coupling of aryl halides with organozinc chlorides catalyzed by a palladium bipyridyl complex. [10] Herein, we report an efficient one pot synthesis of 9-arylmethylanthracene from vinylarenes, aryl iodides and arylzinc reagents. In this process, we utilize a Ni-catalyzed alkene dicarbofunctionalization reaction [11] in tandem with an acid-promoted cyclizationaromatization process to construct the 9-arylmethylanthracene scaffold.…”

Synthesis, characterization, and reactivity of Au/MCM-41 catalysts prepared by homogeneous deposition–precipitation (HDP) method for vapor phase oxidation of benzyl alcohol

“…3(a). All the samples exhibit Langmuir type IV isotherms [23,24] which are characteristic feature of mesoporous materials. The isotherms of all Au/MCM-41 catalysts are identical to the isotherm of mesoporous MCM-41 ( Fig.…”

“…3(a)). The nitrogen adsorption isotherms of mesoporous MCM-41 and Au/MCM-41 catalysts exhibit H4-type hysteresis loop corresponding to pores with narrow necks and wider bodies [25] and features a sharp step in the P/P 0 range of 0.6-0.9, the sharpness of this step is indicative of the uniformity of the pore-size [24], However, the hysteresis loops of all Au/MCM-41 catalysts become smaller, and position of the step shifts towards lower relative pressure in the range of 0.45-0.89 (as observed from the Fig. 3(a)), indicating that a smaller pore-size is formed.…”

Cross‐Coupling Arylations: Precedents and Rapid HistoricalReview of the Field

“…For example, in 2013, Wu et al [181] reported on the Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41). For example, in 2013, Wu et al [181] reported on the Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41).…”