Gold-Catalyzed Polymerization Based on Carbene Polycyclopropanation

Nzulu, Frida; Bontemps, Alexis; Robert, J.; Barbazanges, Marion; Fensterbank, Louis; Goddard, Jean‐Philippe; Malacrìa, Max; Ollivier, Cyril; Petit, Marc; Rieger, Jutta; Stoffelbach, François

doi:10.1021/ma501516s

Cited by 18 publications

(15 citation statements)

References 51 publications

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“… [20–22] Significant advancements in catalyst and methodology development have resulted in improved yields, turn‐over frequencies (TOF), and functionality tolerance, enabling the synthesis of structurally diverse and complex organic molecules. Access to new macromolecular chemistries could be obtained directly from aryl‐containing building blocks and various alkyne comonomers if an analogous polymerization chemistry was developed; however, the use of Au as a polymerization catalyst remains essentially unexplored [23–27] …”

Section: Methodsmentioning

confidence: 99%

“…Access to new macromolecular chemistries could be obtained directly from aryl-containing building blocks and various alkyne comonomers if an analogous polymerization chemistry was developed; however, the use of Au as a polymerization catalyst remains essentially unexplored. [23][24][25][26][27] This motivated our investigation of Au as a polymerization catalyst, in which we envisioned sequential intermolecular hydroarylation reactions (polyhydroarylations) could occur between bifunctional comonomers containing aromatic C(sp 2 ) À H and C C bonds (Scheme 1 B). We evaluated the model reaction between 1,2,4,5-tetramethylbenzene (1) and 1,4-diethynylbenzene (2) toward poly[(tetramethyl-1,4-phenylene)ethene-1,1-diyl-1,4-phenyleneethene-1,1-diyl] (P1, Table 1).…”

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confidence: 99%

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Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

et al. 2020

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Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs. A principal strategy to achieve materials with robust mechanical, chemical, electronic, and thermal properties involves the incorporation of planar, rigid aromatic, or pseudo-aromatic units within the polymer backbone. [1-3] These aromatic polymers form the basis for many highperformance materials applied in demanding applications. While these materials are primarily derived from traditional step-growth polymerizations, late transition metal (i.e., Ni, Pd, Ru, Rh) mediated polycondensations have matured to high levels in recent years, enabling the synthesis of novel aromatic polymers which impact an innumerable number of emerging technologies. [4-7] In order to broaden the scope of polymers that can be prepared, there remains an ongoing need for new catalytic approaches that overcome limitations that define these reactions such as multistep monomer syntheses, harsh reaction conditions, stoichiometric byproduct generation, and intolerance toward oxygen and water. Consequently, widespread efforts have focused on metal catalyzed C À H activation and functionalization processes, where C À C bond formation occurs directly between C(sp 2) À

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Section: Methodsmentioning

confidence: 99%

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Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

et al. 2020

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“…33 Notably, we developed a new polymerization process by polycyclopropanations 34 of styryl propargyl acetates. 35 In collaboration with the Ryu's group in Osaka, we also considered the possibility to incorporate CO into the Rautenstrauch rearrangement. In the first case, 1,3-O-acyl migration, as we will also see later, leads to rhodacyclopentenes E, which insert CO to give 19.…”

Section: Scheme 4 Total Synthesis Of Sabina Ketonementioning

confidence: 99%

“…33 Notably, we developed a new polymerization process by polycyclopropanations 34 of styryl propargyl acetates. 35 In collaboration with the Ryu's and Fukuyama's group in Osaka, we also considered the possibility to incorporate CO into the Rautenstrauch rearrangement. 36 While the platinum and gold carbene intermediate complexes D could not trap CO, rhodium(I) catalysis proved to be the right option.…”

Section: Account Syn Lettmentioning

confidence: 99%

The Invention of New Methodologies: An Opportunity for Dating Natural Products

Barbazanges¹,

Fensterbank²

2018

Synlett

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This Account surveys almost two decades of methodological developments and their straightforward applications to the total synthesis of simple natural products. The main directions covered include radical chemistry and cascades, electrophilic catalysis based on coinage metals, and asymmetric synthesis based on bis(sulfoxides) auxiliaries.1 Introduction2 Radical Cascades2.1 N-Cyanamides2.2 Homolytic Substitution at Sulfur Atom to Give Sultines3 Electrophilic Catalysis Based on Platinum(II) and Gold(I) Complexes4 From Alkylydene Bis(sulfoxides) to Chiral Carboxylic Acids5 Conclusion and Perspectives

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“…A polymer chain reaction was reported where chain growth is due to intermolecular cyclopropanation using a carboxylate shift-generated carbene complex (e.g. 1318) [1212]. A computational study was reported for selectafluor-mediated gold-catalyzed oxidative bond forming reactions of propargylic carboxylates [1213].…”

Section: Scheme 101 Formation Of Ring-fused Cyclopropanes Using Metamentioning

confidence: 99%

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

Herndon

2016

Coordination Chemistry Reviews

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Gold-Catalyzed Polymerization Based on Carbene Polycyclopropanation

Cited by 18 publications

References 51 publications

Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

The Invention of New Methodologies: An Opportunity for Dating Natural Products

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

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