Efficient Cross‐Coupling of Dioxazaborocanes with α‐Phosphate Enamides

Gigant, Nicolas; Honraedt, Aurélien; Gras, Emmanuel; Gillaizeau, Isabelle

doi:10.1002/ejoc.201402927

Cited by 9 publications

(5 citation statements)

References 43 publications

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“…This process is more conducive to the precise control of vitrimer structures. Although boronic esters with internal N → B interaction have been applied in cross-coupling reactions, 32 or employed as a curing agent for epoxy resin, 33 the thermodynamic and kinetic characteristics, as well as the dynamic nature of nitrogen-coordinating cyclic boronic diester (NCB) linkages, have not yet been systematically explored.…”

Section: ■ Introductionmentioning

confidence: 99%

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron–Nitrogen Coordination

et al. 2020

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Boron-containing polymers have many applications resulting from their prominent properties. Organoboron species with reversible B–O bonds have been successfully employed for the fabrication of various self-healing/healable and reprocessable polymers. However, the application of the polymers containing boronic ester or boroxine linkages is limited because of their instability to water. Herein, we report the hydrolytic stability and dynamic covalent chemistry of the nitrogen-coordinating cyclic boronic diester (NCB) linkages, and a new class of vitrimers based on NCB linkages is developed through the chemical reactions of reactive hydrogen with isocyanate. Thermodynamic and kinetic studies demonstrated that NCB linkages exhibit enhanced water and heat resistance, whereas the exchange reactions between NCB linkages can take place upon heating without any catalyst. The model compounds of NCBC-X1 and NCBC-X2 containing a urethane group and urea group, respectively, also showed higher hydrolytic stability compared to that of conventional boronic esters. Polyurethane vitrimers and poly(urea-urethane) vitrimers based on NCB linkages exhibited excellent solvent resistance and mechanical properties like general thermosets, which can be repaired, reprocessed, and recycled via the transesterification of NCB linkages upon heating. Especially, vitrimers based on NCB linkages presented improved stability to water and heat compared to those through conventional boronic esters because of the existence of N → B internal coordination. We anticipate that this work will provide a new strategy for designing the next generation of sustainable materials.

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Section: ■ Introductionmentioning

confidence: 99%

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron–Nitrogen Coordination

et al. 2020

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“…In contrast to diethyl phosphates, diphenyl phosphates are more common in the Suzuki reaction due to the higher reactivity of diphenyl phosphates. This is exemplified in a recent study presented in Scheme 16 [ 92 ]. Gigant and co-workers used dioxazaborocanes in a palladium-catalyzed reaction with phosphate enamides.…”

Section: Organophosphates As Electrophiles In Transition-metal-cataly...mentioning

confidence: 79%

Organophosphates as Versatile Substrates in Organic Synthesis

Oeser,

Tobrman

2024

Molecules

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This review summarizes the applications of organophosphates in organic synthesis. After a brief introduction, it discusses cross-coupling reactions, including both transition-metal-catalyzed and transition-metal-free substitution reactions. Subsequently, oxidation and reduction reactions are described. In addition, this review highlights the applications of organophosphates in the synthesis of natural compounds, demonstrating their versatility and importance in modern synthetic chemistry.

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“…(A) The investigated structures of dioxazaborocane for Suzuki–Miyaura cross‐couplings. Reproduced with permission: Copyright 2014, Wiley‐VCH Verlag GmbH & Co 58 . (B) Transesterification of dioxaborolane with representative 1,5‐diols at ambient temperature.…”

Section: Effect Of Dative B–n Coordination On the Property Of B–o Bondsmentioning

confidence: 99%

“…57 Furthermore, Gillaizeau et al applied various dioxazaborocanes with the internal B-N interactions as a broad substrate scope for the developed method of functionalized enamides (Figure 3A). 58 In the research about the stability of boronic esters by Brown and coworkers, the transesterification between dioxaborolane and diethanolamine with different substituents was evaluated by 11 B and 1 H NMR spectra. 49 The transesterification ratio sharply decreased as the diethanolamine was substituted by Nbutyldiethanolamine and 2,6-pyridinedimethanol (diols 23 and 24 in Figure 3B), suggesting that the boronic ester chelated with diethanolamine (diol 21 in Figure 3B) is the most stable complex.…”

Section: Effect Of Dative B-n Coordination On the Property Of B-o Bondsmentioning

confidence: 99%

Dynamic polymeric materials based on reversible B–O bonds with dative boron–nitrogen coordination

Zhao

Zuo

2023

SmartMat

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To minimize the environmental pollution caused by polymeric waste, materials based dynamic chemistry have attracted extensive attention around the world.Various dynamic covalent bonds or noncovalent interactions have been employed to design multifunctional polymers with recyclability, reprocessablility, and sustainability. Among them, polymers based on reversible boron-oxygen (B-O) bonds have been widely investigated because of their unique properties. Particularly, lots of scientists have demonstrated that the combination with boron-nitrogen (B-N) coordination can effectively accelerate the dynamicity as well as enhance the stability of B-O bonds. Therefore, numerous polymers containing dynamic B-O bonds with dative B-N coordination have been designed and synthesized in recent years. These polymers exhibit excellent versatility and great potential for diverse applications such as biosensors, battery electrolytes, and artificial skins. This review provides an overview of the comprehensive influence of dynamic B-N coordination chemistry on B-O bonds in organoboron species and highlights the developments in the area of constructing boron-containing polymeric materials with this interesting linkage. The design guidelines, existing challenges, and future perspectives in this burgeoning field are discussed and proposed.

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Efficient Cross‐Coupling of Dioxazaborocanes with α‐Phosphate Enamides

Cited by 9 publications

References 43 publications

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron–Nitrogen Coordination

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron–Nitrogen Coordination

Organophosphates as Versatile Substrates in Organic Synthesis

Dynamic polymeric materials based on reversible B–O bonds with dative boron–nitrogen coordination

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