Organocatalyzed synthesis of functionalized vinylphosphonates in water

Seingeot, Adeline; Charmasson, Yolande; Attolini, Mireille; Maffei, Michel

doi:10.1002/hc.21352

Cited by 9 publications

(8 citation statements)

References 9 publications

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“…A more exotic literature example where 4 is used as nucleophilic catalyst is the allylic substitution of vinyl phosphonates with N-and S-nucleophiles (Table 1 -reaction 14). 132 Besides tertiary amines, primary amines can also function as nucleophilic organocatalysts in water. A commonly applied primary amine organocatalyst is aniline 32 (see ref.…”

Section: Nucleophilic and General/specific Base Catalysismentioning

confidence: 99%

Organocatalysis in aqueous media

2019

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Section: Nucleophilic and General/specific Base Catalysismentioning

confidence: 99%

Organocatalysis in aqueous media

2019

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“…From ITC, we learned that the binding constant of DABCO ( C2 ) with CB[7] is 3.6×10 5 M −1 (Table 1), which is in a similar range as C1 and a suitable value for reaction rate control. Moreover, DABCO was reported to accelerate the allylic substitution reaction between diethyl(α‐acetoxymethyl) vinylphosphonate SM3 and nitrogen‐based nucleophiles in aqueous solvents [33, 34] . Hence, we used glycine ( SM4 ; 100 mM) as nucleophile in phosphate buffer (100 mM, pH 7.4) to react with SM3 (10 mM), giving the double substituted compound as the major product (Figure 2).…”

Section: Resultsmentioning

confidence: 99%

Tuneable Control of Organocatalytic Activity through Host–Guest Chemistry

Trausel

Helm

et al. 2021

Angew Chem Int Ed

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Dynamic regulation of chemical reactivity is important in many complex chemical reaction networks,s uch as cascade reactions and signal transduction processes.S ignal responsive catalysts could play acrucial role in regulating these reaction pathways.R ecently,s upramolecular encapsulation was reported to regulate the activities of artificial catalysts.W e present ahost-guest chemistry strategy to modulate the activity of commercially available synthetic organocatalysts.T he molecular container cucurbit[7]uril was successfully applied to change the activity of four different organocatalysts and one initiator,enabling up-or down-regulation of the reaction rates of four different classes of chemical reactions.I nm ost cases CB[7] encapsulation results in catalyst inhibition, however in one case catalyst activation by binding to CB[7] was observed. The mechanism behind this unexpected behavior was explored by NMR binding studies and pKa measurements.The catalytic activity can be instantaneously switched during operation, by addition of either supramolecular host or competitive binding molecules,and the reaction rate can be predicted with akinetic model. Overall, this signal responsive system proves apromising tool to control catalytic activity.

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“…Competing S or Nterminal nucleophiles can perform a second allylic substitution on the activated intermediate 32,33 , which reverses the quaternary nitrogen to the neutral amine adduct, forming the allylic reaction product (waste) and thus completing the reaction cycle (Figure 1a). In this cycle, the allyl substrate diethyl(α-acetoxymethyl) vinylphosphonate (DVP) 34 acts as a fuel, enabling a reversible switch between charge states of the nitrogen centre. We are able to manipulate the CRN and the subsequent material response by delicate design of the allylation reaction (activation) and its successive substitution reaction in the presence of nucleophiles (deactivation).…”

Section: Resultsmentioning

confidence: 99%

Temporally programmed polymer - solvent interactions using a chemical reaction network

Klemm

Lewis

Piergentili

et al. 2021

Preprint

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Chemical reaction networks (CRNs) that operate under constant influx of energy enable artificial materials to autonomously respond to their environment by activation and deactivation of intermolecular interactions. Generally, their activation can be driven by various energy sources, yet their deactivation to non-interacting building blocks remains largely limited to hydrolysis and internal pH change. To achieve control over deactivation, we developed a new CRN that enables reversible formation of positive charges on a tertiary amine substrate, which are removed using nucleophilic signals that control the deactivation kinetics. Incorporation of the CRN in a polymer material leads to a temporally programmed transition from collapsed and hydrophobic to solvated, hydrophilic polymer chains by controlling polymer-solvent interactions. Depending on the layout of the CRN, we can create stimuli-responsive or autonomously responding materials. This concept will not only offer new opportunities in molecular cargo delivery but also pave the way for next-generation interactive materials.

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Organocatalyzed synthesis of functionalized vinylphosphonates in water

Cited by 9 publications

References 9 publications

Organocatalysis in aqueous media

Organocatalysis in aqueous media

Tuneable Control of Organocatalytic Activity through Host–Guest Chemistry

Temporally programmed polymer - solvent interactions using a chemical reaction network

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