Azaphosphatranes as Hydrogen‐Bonding Organocatalysts for the Activation of Carbonyl Groups: Investigation of Lactide Ring‐Opening Polymerization

Zhang, Dawei; Jardel, Damien; Peruch, Frédéric; Calin, Nathalie; Dufaud, Véronique; Dutasta, Jean‐Pierre; Martinez, Alexandre; Bibal, Brigitte

doi:10.1002/ejoc.201600080

Cited by 11 publications

(8 citation statements)

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“…[6,7] Their conjugated acids, the azaphosphatranes (2; Figure 1), have been also used as organocatalysts, for instance in the Strecker or the ring-opening polymerization (ROP) reactions and CO 2 conversion. [8,9,10] Moreover, once included in self-assembled cages, this motif is capable of anions recognition and extraction in water. [11] Haloazaphosphatranes are the halogenated version of the azaphosphatranes where the hydrogen atom has been replaced by a halogen one (3; Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterizations and Applications of Fluoroazaphosphatranes

Manick

Dutasta

Nava

et al. 2022

Chemistry An Asian Journal

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Haloazaphosphatranes are the halogenated parents of proazaphosphatranes, also known as Verkade's superbase. While the synthesis of iodo-, bromo-and chloroazaphosphatranes was reported more than thirty years ago by J. G. Verkade, the first synthesis of fluoroazaphosphatranes was only described in 2018 by Stephan et al. Currently, no common and versatile procedure exists to access fluoroazaphosphatranes platform with different structural characteristics. In this report, a new and simple synthesis of this class of compounds was developed based on the nucleophilic attack of the fluoride anion on chloroazaphosphatrane derivatives with good to high isolated yields for the corresponding fluoroazaphosphatranes (70-92%). The scope of the reaction was widened to fluoroazaphosphatranes bearing various substituents and X-ray molecular structures of two of them are reported. The stability of fluoroazaphosphatranes toward nucleophilic solvents like water has been investigated. As they revealed much more robust cations than their chloroazaphosphatrane parents, their chloride salts were tested as organocatalysts for the formation of cyclic carbonates from epoxides and CO 2 . Fluoroazaphosphatranes proved to be both efficient and stable catalytic systems for CO 2 conversion with catalytic activities similar to those of azaphosphatranes, and no decomposition of the cation was observed at the end of reaction.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterizations and Applications of Fluoroazaphosphatranes

Manick

Dutasta

Nava

et al. 2022

Chemistry An Asian Journal

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“…[6] Benefiting from the robustness and hydrophobicity of these azaphosphatrane cations, our group employed them as phase transfer catalysts for the alkylation of enolates, generation of carbene and oxidation of an electrophilic alkene. [7] More recently, we have demonstrated that they also can act as effective catalysts in lactide ring-opening polymerization, [8] and in the synthesis of cyclic carbonates from epoxides and CO 2 . In both cases, activity efficiency was found to rely on better activation of the substrates through hydrogen-bond interactions.…”

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confidence: 99%

Azaphosphatranes Catalyzed Strecker Reaction in the Presence of Water

Yang

Manick

et al. 2020

ChemistrySelect

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Azaphosphatranes were found to act as efficient organocatalysts in the presence of water for the cyanation of differently substituted imines. A relatively safer source of cyanide, trimethylsilyl cyanide (TMSCN), was used, and excellent yields could be obtained with only 0.05 mol % of catalyst. The influence of acidity of azaphosphatranes on catalytic activity as well as the role of azaphosphatranes in the mechanism of the reaction were also investigated.

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“…The azaphosphatrane (27) cocatalyzed (with sparteine) ROP of cyclic esters is the perfect example, Figure 1.8. 125 These structures suggest a new catalytic handle to provide monomer activation with attenuated cocatalyst binding. 125,126 Further, they are highly modular and have multiple sites available for optimization.…”

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospmentioning

confidence: 98%

“…125 These structures suggest a new catalytic handle to provide monomer activation with attenuated cocatalyst binding. 125,126 Further, they are highly modular and have multiple sites available for optimization. 125 Electrostatic Monomer Activation by Cations H-bondsa very poor name for the phenomenonrequire no orbital overlap and are a type of electrostatic interaction.…”

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospmentioning

confidence: 98%

“…125,126 Further, they are highly modular and have multiple sites available for optimization. 125 Electrostatic Monomer Activation by Cations H-bondsa very poor name for the phenomenonrequire no orbital overlap and are a type of electrostatic interaction. 106 bifunctional, mechanism was also envisaged.…”

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospmentioning

confidence: 99%

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Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

Datta¹

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The overarching theme of my research work involves understanding the mechanistic aspects of dually activated hydrogen-bonding catalyst systems and applying that knowledge to synthesize polymers from some of the less explored monomers. This entailed a thorough approach to some of the already hypothesized mechanisms in the polymer community and building on that with additional perspective on catalytic interactions. The other aspect of my research encompassed the application of these H-bond mediated catalysts in controlled ring-opening polymerization (ROP) of sulfur-based lactones. This allowed the growth in monomer scope using these catalysts for the first time. H-bonding catalysis, particularly the ones involving ureas and thioureas, began about a decade or so ago. The tremendous rise in organocatalytic ring-opening polymerization has sparked a wide range of catalysts developments in the past few years. Due to their lower cost, reduced toxicity and greener approach, the field has been booming vii

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Azaphosphatranes as Hydrogen‐Bonding Organocatalysts for the Activation of Carbonyl Groups: Investigation of Lactide Ring‐Opening Polymerization

Abstract: International audienc

Cited by 11 publications

References 53 publications

Synthesis, Characterizations and Applications of Fluoroazaphosphatranes

Synthesis, Characterizations and Applications of Fluoroazaphosphatranes

Azaphosphatranes Catalyzed Strecker Reaction in the Presence of Water

Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

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