Pd-Metalated Conjugated Nanoporous Polycarbazoles for Additive-Free Cyanation of Aryl Halides: Boosting Catalytic Efficiency through Spatial Modulation.

Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. The catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.

[1]  S. Dai,et al.  Pyrolysis of conjugated nanoporous polycarbazoles to mesoporous N-doped carbon nanotubes as efficient electrocatalysts for the oxygen reduction reaction , 2017 .

[2]  Shengqian Ma,et al.  Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer. , 2016, Journal of the American Chemical Society.

[3]  K. Han,et al.  Use of steric encumbrance to develop conjugated nanoporous polymers for metal-free catalytic hydrogenation. , 2016, Chemical communications.

[4]  S. Dai,et al.  Substitution Effect Guided Synthesis of Task-Specific Nanoporous Polycarbazoles with Enhanced Carbon Capture , 2016 .

[5]  Jun Hu,et al.  Rational design and synthesis of a porous, task-specific polycarbazole for efficient CO2 capture. , 2016, Chemical communications.

[6]  Partha Sarathi Mukherjee,et al.  Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides. , 2016, Journal of the American Chemical Society.

[7]  Zhi Ma,et al.  Metalated Mesoporous Poly(triphenylphosphine) with Azo Functionality: Efficient Catalysts for CO2 Conversion , 2016 .

[8]  F. Xiao,et al.  Porous polymer catalysts with hierarchical structures. , 2015, Chemical Society reviews.

[9]  F. Xiao,et al.  Task-Specific Design of Porous Polymer Heterogeneous Catalysts beyond Homogeneous Counterparts , 2015 .

[10]  Jian Zhang,et al.  Carbazolic Porous Organic Framework as an Efficient, Metal-Free Visible-Light Photocatalyst for Organic Synthesis , 2015 .

[11]  S. Buchwald,et al.  Mild Palladium-Catalyzed Cyanation of (Hetero)aryl Halides and Triflates in Aqueous Media , 2015, Organic letters.

[12]  A. Bhaumik,et al.  A triazine functionalized porous organic polymer: excellent CO2 storage material and support for designing Pd nanocatalyst for C–C cross-coupling reactions , 2014 .

[13]  T. Chatterjee,et al.  ZnO-supported Pd nanoparticle-catalyzed ligand- and additive-free cyanation of unactivated aryl halides using K4[Fe(CN)6]. , 2014, The Journal of organic chemistry.

[14]  B. Han,et al.  An efficient palladium catalyst on bentonite for Suzuki–Miyaura reaction at room temperature , 2013 .

[15]  A. Nagai,et al.  Conjugated microporous polymers: design, synthesis and application. , 2013, Chemical Society reviews.

[16]  S. Buchwald,et al.  A general, practical palladium-catalyzed cyanation of (hetero)aryl chlorides and bromides. , 2013, Angewandte Chemie.

[17]  Wei Wang,et al.  Covalent organic frameworks (COFs): from design to applications. , 2013, Chemical Society reviews.

[18]  Sukbok Chang,et al.  Synthesis of aromatic nitriles using nonmetallic cyano-group sources. , 2012, Angewandte Chemie.

[19]  Sukbok Chang,et al.  Synthese aromatischer Nitrile mithilfe nichtmetallischer CN‐Quellen , 2012 .

[20]  Bao-hang Han,et al.  Microporous polycarbazole with high specific surface area for gas storage and separation. , 2012, Journal of the American Chemical Society.

[21]  Yugen Zhang,et al.  Functional porous organic polymers for heterogeneous catalysis. , 2012, Chemical Society reviews.

[22]  M. Beller,et al.  Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: synthesis of benzonitriles. , 2011, Chemical Society reviews.

[23]  SonBinh T. Nguyen,et al.  Porous organic polymers in catalysis: Opportunities and challenges , 2011 .

[24]  P. Hesemann,et al.  Palladium containing nanostructured silica functionalized with pyridine sites: a versatile heterogeneous catalyst for Heck, Sonogashira, and cyanation reactions , 2007 .

[25]  M. Beller,et al.  Potassium hexacyanoferrate(II)--a new cyanating agent for the palladium-catalyzed cyanation of aryl halides. , 2004, Chemical communications.

[26]  Saad Makhseed,et al.  Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials. , 2004, Chemical communications.