Transition‐Metal‐Free Synthesis of Conjugated Polymers from Bis‐Grignard Reagents by Using TEMPO as Oxidant

Maji, Modhu Sudan; Pfeifer, Thorben; Studer, Armido

doi:10.1002/chem.201000236

Cited by 66 publications

(45 citation statements)

References 24 publications

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“…Indeed, transition-metal-free multiple homocoupling reactions of 2,7-dimagnesiated fluorenes with TEMPO provided polyfluorenes with a mean molecular weight M n of up to 9000 g mol À1 (Scheme 28). [167] The method also allowed formation of copolymers containing the butadiynylene or butadienylene moiety as alternating building blocks with the fluorene unit in the polymer backbone. Polymers with M n values of up to 17 000 g mol À1 were formed by this novel polymerization method.…”

Section: H Abstraction By Nitroxidesmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

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Section: H Abstraction By Nitroxidesmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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“…[43,40] Building block 10 was obtained by using a literature procedure starting from 4-iodoaniline (9). [45] Assembling masked OPE 12 by using a divergent approach gave an overall yield of 58 %. [45] Assembling masked OPE 12 by using a divergent approach gave an overall yield of 58 %.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Solid‐State Investigations of Oligo‐Phenylene–Ethynylene Structures with Halide End‐Groups

Jenny¹,

Wang²,

Neuburger³

et al. 2012

Eur J Org Chem

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In the field of material science functionalization of substrate surfaces (e.g. metal, graphite) with organic molecules is of increasing interest. Desirable targets are molecules with functional groups providing for two‐dimensional assembly and three‐dimensional crystal growth. We have synthesized a series of halogen‐end‐capped oligo‐phenylene‐ethynylenes (OPEs) to study the interactions at the solid/liquid interface and in crystal structures. Organohalides can be involved in a wide variety of intermolecular interactions such as C–X···H, C–X···X–C and C–X···π‐orbitals. The range of halogen‐based interactions and the diversity of intermolecular forces along different crystal axes makes the investigation of such structures particular interesting and challenging. Here we probe the interplay of halide end‐groups and the backbone of an OPE to investigate the intermolecular interactions in both solution depositions (2D) and X‐ray crystal structures (3D). The STM images and the crystal structures of each OPE reveal striking packing similarities. For each molecule, a plane in the crystal structure with an arrangement of molecules resembling its two‐dimensional packing on a flat surface was found. These results support the hypothesis of sheet‐by‐sheet crystal growth and suggest that flat surfaces would be ideal interfaces to promote crystal growth for halide‐end‐capped OPEs.

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“…An application of this approach for the synthesis of polyfluorenes 7 from the diaryl, dialkenyl, or dialkynyl Grignard precursors 6 was also described (Scheme 4, b). 10 Moreover, the homocoupling of RMgBr compounds using catalytic amounts of TEMPO (10-18 mol%) has been developed under aerobic conditions by a continuous stepwise procedure consisting in the renewed addition of RMgBr (1:1 to TEMPO to reach 1 equiv of substrate) followed by purging with O 2 as the terminal oxidant.…”

Section: Homocouplingmentioning

confidence: 99%

TEMPO Derivatives as Alternative Mild Oxidants in Carbon-Carbon Coupling Reactions

Mancheño

Stopka

2013

Synthesis

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TEMPO-type oxidants are fundamentally associated with polymer chemistry, radical trapping processes, or the oxidation of alcohols to carbonyl compounds. However, in the past few years new exciting transformations using these kinds of oxidants in the area of C-C and C-heteroatom coupling have emerged. This review focuses on the application of TEMPO and its derivatives as mild reagents or catalysts in oxidative C-C coupling reactions. The review is divided into two main sections: i) the direct coupling of C-H bonds and ii) the use of organometallic reagents such as Grignard or boron species to generate the new C-C bond. In the last section, oxidative C-C/C-O tandem-coupling reactions, in which the TEMPO derivatives are incorporated in the final product, are also briefly described.

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Transition‐Metal‐Free Synthesis of Conjugated Polymers from Bis‐Grignard Reagents by Using TEMPO as Oxidant

Cited by 66 publications

References 24 publications

Nitroxides: Applications in Synthesis and in Polymer Chemistry

Nitroxides: Applications in Synthesis and in Polymer Chemistry

Synthesis and Solid‐State Investigations of Oligo‐Phenylene–Ethynylene Structures with Halide End‐Groups

TEMPO Derivatives as Alternative Mild Oxidants in Carbon-Carbon Coupling Reactions

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