An expeditious method for the selective cyclotrimerization of isocyanates initiated by TDAE

Giuglio-Tonolo, Alain Gamal; Spitz, Cédric; Terme, Thierry; Vanelle, Patrice

doi:10.1016/j.tetlet.2014.03.045

Cited by 21 publications

(13 citation statements)

References 32 publications

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“…Because of their important applications, the synthesis of isocyanurates is a remarkable topic in organic chemistry. Many various catalysts have been used for the synthesis of isocyanurates, such as amine bases; 53 alkoxyallenes; 68 sulfide anion and phase transfer catalysts; 54 hexamethyldisilazane; 69 proazaphosphatranes; 70,71 organometallic catalysts containing Ti, Co, Zr, Pd, Pr, Ln, Sn, W, Li, and Nb metals; 72−84 ketene cyclic N,O-acetals; 85 fluoride anions; 86 carbamate anions; 87 phosphines; 88 N-heterocyclic carbenes; 89,90 and tetrakis (dimethylamino)ethylene (TDAE). 91 We were previously interested in the synthesis of electron-rich olefins and their derivatives.…”

Section: Introductionmentioning

confidence: 99%

The catalytic effects of in situ prepared N-heterocyclic carbenes from benzimidazole salts in Suzuki–Miyaura cross-coupling reaction and uses in catalytic preparation of 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione from phenyl isocyanate

Yılmaz¹,

Küçükbay²

2018

Turk J Chem

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Many benzimidazole salts bearing a 3-phenylpropyl substituent (1a-1h) were synthesized and their structures were identified by 1 H NMR, 13 C NMR, and IR spectroscopic methods and elemental analysis. These N-heterocyclic carbene (NHC) precursors were used as a part of a catalytic system including Pd(OAc) 2 and the base in the Suzuki-Miyaura cross-coupling reaction under microwave irradiation. They were also used as catalysts in the cyclotrimerization of phenyl isocyanate to yield 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione. It has been observed that benzimidazole salts made a positive contribution to both catalytic reactions as a NHC precursor.

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Section: Introductionmentioning

confidence: 99%

The catalytic effects of in situ prepared N-heterocyclic carbenes from benzimidazole salts in Suzuki–Miyaura cross-coupling reaction and uses in catalytic preparation of 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione from phenyl isocyanate

Yılmaz¹,

Küçükbay²

2018

Turk J Chem

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“…The most commonly used catalysts in industrial applications are based on carboxylates, such as potassium acetate, potassium 2-ethylhexanoate, trimethyl hydroxypropyl ammonium formate, or phenolate such as 2,4,6-tris(dimethylaminomethyl)phenol. ,− The various industrial and commercial applications of isocyanurate-based polyurethane materials have attracted much attention in developing more effective catalysts for isocyanate trimerization. A number of catalysts for the trimerization of isocyanates have been extensively studied and reported in academic literature, including among others tetrabutylammonium fluoride (TBAF), 2-phosphaethynolate anion (OCP – ), sodium p -toluenesulfinate ( p -TolSO 2 Na)/tetrabutylammonium iodide (TBAI), , tetrakis(dimethylamino)ethylene (TDAE), proazaphosphatrane, − N-heterocyclic carbenes, olefins, , etc. With more and more catalysts being reported, the exact nature of the cyclotrimerization mechanism has raised much interest.…”

Section: Introductionmentioning

confidence: 99%

Role of Acetate Anions in the Catalytic Formation of Isocyanurates from Aromatic Isocyanates

et al. 2021

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The formation of isocyanurates via cyclotrimerization of aromatic isocyanates is widely used to enhance the physical properties of a variety of polyurethanes. The most commonly used catalysts in industries are carboxylates for which the exact catalytically active species have remained controversial. We investigated how acetate and other carboxylates react with aromatic isocyanates in a stepwise manner and identified that the carboxylates are only precatalysts in the reaction. The reaction of carboxylates with an excess of aromatic isocyanates leads to irreversible formation of corresponding deprotonated amide species that are strongly nucleophilic and basic. As a result, they are active catalysts during the nucleophilic anionic trimerization, but can also deprotonate urethane and urea species present, which in turn catalyze the isocyanurate formation. The current study also shows how quantum chemical calculations can be used to direct spectroscopic identification of reactive intermediates formed during the active catalytic cycle with predictive accuracy.

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“…Since 2003, our laboratory has been developing original synthetic methods based on neutral, ground-state organic reducing agents [9,10,11,12,13,14], aimed at preparing new, potentially bioactive compounds [9]. Tetrakis(dimethylamino)ethylene (TDAE), as shown in Figure 1 [15,16,17], is a powerful tool in modern organic chemistry because it allows reduction under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Original Synthesis of Fluorenyl Alcohol Derivatives by Reductive Dehalogenation Initiated by TDAE

2016

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Abstract:We report here a novel and easy-to-handle reductive dehalogenation of 9-bromofluorene in the presence of arylaldehydes and dicarbonyl derivatives to give the corresponding fluorenyl alcohol derivatives and Darzens epoxides as by-products in tetrakis(dimethylamino)ethylene (TDAE) reaction conditions. The reaction is believed to proceed via two successive single electron transfers to generate the fluorenyl anion which was able to react with different electrophiles. A mechanistic study was conducted to understand the formation of the epoxide derivatives.

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An expeditious method for the selective cyclotrimerization of isocyanates initiated by TDAE

Cited by 21 publications

References 32 publications

The catalytic effects of in situ prepared N-heterocyclic carbenes from benzimidazole salts in Suzuki–Miyaura cross-coupling reaction and uses in catalytic preparation of 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione from phenyl isocyanate

The catalytic effects of in situ prepared N-heterocyclic carbenes from benzimidazole salts in Suzuki–Miyaura cross-coupling reaction and uses in catalytic preparation of 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione from phenyl isocyanate

Role of Acetate Anions in the Catalytic Formation of Isocyanurates from Aromatic Isocyanates

Original Synthesis of Fluorenyl Alcohol Derivatives by Reductive Dehalogenation Initiated by TDAE

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