1267779-24-7

Upstream product

• 5703-26-4 4-Methoxyphenylacetaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 
• 4097-89-6 2,2',2''-triaminotriethylamine 
• 1267779-26-9 C₃₀H₃₉N₄O₃P*ClH 

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• 1332889-28-7 C₃₉H₆₀N₇O₆PSi 

Relevant academic research and scientific papers

Superbases in confined space: Control of the basicity and reactivity of the proton transfer

Endohedral functionalization of the molecular cavity of host molecules is in high demand in many areas of supramolecular chemistry. When highly reactive species are incarcerated in the confined space of a molecular cavity, deep changes of their chemical properties are expected. Here, we show that the superbasic properties of proazaphosphatranes can be improved in the confined space of the molecular cavity of hemicryptophane hosts. A general and modular procedure is described to prepare supramolecular superbases with various cavity sizes. The rate of proton transfer is strongly dependent on the shape and size of the inner cavity of the designed superbasic structure. Kinetic and thermodynamic data are strongly correlated to the space available around the basic center as revealed by the X-ray molecular structures analyses.

Encaging the Verkade's superbases: Thermodynamic and kinetic consequences

Proazaphosphatranes, also known as Verkade's superbases, are nonionic species, which exhibit catalytic properties for a wide range of reactions. The properly designed host molecule 3 and its protonated counterpart [3·H]+Cl- were synthesized to study how confinement can modify the stability and the reactivity of a Verkade's superbase. The results show that the encapsulation does not alter the strong basicity of the proazaphosphatrane, but dramatically decreases the rate of proton transfer.

The Chloroazaphosphatrane Motif for Halogen Bonding in Solution

Chloroazaphosphatranes, the corresponding halogenophosphonium cations of the Verkade superbases, were evaluated as a new motif for halogen bonding (XB). Their modulable synthesis allowed for synthetizing chloroazaphosphatranes with various substituents on the nitrogen atoms. The binding constants determined from NMR titration experiments for Cl-, Br-, I-, AcO-, and CN- anions are comparable to those obtained with conventional iodine-based monodentate XB receptors. Remarkably, the protonated azaphosphatrane counterparts display no affinity for anions under the same conditions. The strength of the XB interaction is, to some extent, related to the basicity of the corresponding Verkade superbase. The halogen bonding abilities of this new class of halogen donor motif were also revealed by the Δδ(31P) NMR shift observed in CD2Cl2 solution in the presence of triethylphosphine oxide (TEPO). Thus, chloroazaphosphatranes constitute a new class of halogen bond donors, expanding the repertory of XB motifs mainly based on CAr-I bonds.

Verkade's Superbase as an Organocatalyst for the Strecker Reaction

Proazaphosphatranes -Verkade's superbases- proved to be efficient organocatalysts for the Strecker reaction between protected imines and trimethylsilyl cyanide (TMSCN). Excellent to quantitative yields were reached and, compared to other systems, only low

A new step towards solid base catalysis: Azidoproazaphosphatranes immobilized in nanopores of mesoporous silica

Heterogeneous basic catalysts derived from proazaphosphatranes, known as Verkade's superbases, were prepared for the first time by covalent immobilization onto SBA-15 silica. In order to introduce the tether to the surface, three siloxane-containing azido derivatives of the proazaphosphatranes were first synthesized (2a-c) which after post-synthetic grafting onto silica support led to the formation of hybrid materials of different basicity and steric properties, 2a-c@SBA-15. These latter were fully characterized using a wide variety of molecular and solid-state techniques to determine their structural and textural properties. These new solid base catalysts were then evaluated in the Diels-Alder reactions of anthrone and 3-hydroxy-2-pyrone with two electron-deficient dienophiles, N-methylmaleimide and dimethyl fumarate. In general, high activity and selectivity were obtained depending on the catalytic species, the performance decreasing in the order methoxybenzyl>neopentyl> methyl azidophosphatrane. Catalyst recycling was studied for the best catalyst, the methoxybenzyl derivative, 2c@SBA-15, and it was shown that the catalyst could be re-used up to 3 cycles before any loss of activity could be detected. Copyright