Electrostatically enhanced catalytic phase transfer hydrogenation of acetophenone under low external electric field

Wang, Nan; Kamiński, K.; Petera, J.; Allgeier, Alan M.; Weatherley, L.R.

doi:10.1016/j.cej.2019.04.148

Cited by 8 publications

(15 citation statements)

References 26 publications

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“…Based on the observations, a stepwise mechanism for the phase trans- 37 Finally, the alkoxide picks up a proton from water to form the product, 37 and the generated hydroxide further reacts with CO 2 to form bicarbonate as observed in our previous study. 25 The stoichiometry and rate expression consistent with the proposed mechanism are summarized in Equations (5)- (11), assuming that the coordination of formate and decarboxylation are reversible and equilibrated prior to hydrogen transfer, 26 where K 1 is the equilibrium constant, and k 1 , k 2 , k 3 are the respective reaction rate constants.…”

Section: Proposed Mechanismmentioning

confidence: 98%

“…Details of the experimental unit may be found elsewhere. 25 Briefly, the biphasic system was set up with a sodium formate/water solution as the more dense aqueous phase and acetophenone/organic solvents as the less dense organic phase in…”

Section: Experimental Apparatus and Proceduresmentioning

confidence: 99%

“…24 This has been validated in our previous study that the reaction rate can be either promoted or inhibited by simply flipping the orientation of the external electric field. 25 To further explore the possibilities of controlling reaction rate and even selectivity with external electric field on bulk scales, catalytic transfer hydrogenation of acetophenone was studied in a biphasic liquid system. Previous studies showed that the phase transfer hydrogenation of acetophenone with sodium formate as hydrogen source is a mass transfer limited reaction happening at the organic-aqueous interface.…”

Section: Introductionmentioning

confidence: 99%

“…Previous studies showed that the phase transfer hydrogenation of acetophenone with sodium formate as hydrogen source is a mass transfer limited reaction happening at the organic-aqueous interface. 25,26 When an external electric field was applied, the charged reactive species could be either transferred to the interface to promote the reaction or constrained in the corresponding liquid phases decelerating the reaction by the electrostatic forces. 25…”

Section: Introductionmentioning

confidence: 99%

“…25,26 When an external electric field was applied, the charged reactive species could be either transferred to the interface to promote the reaction or constrained in the corresponding liquid phases decelerating the reaction by the electrostatic forces. 25…”

Section: Introductionmentioning

confidence: 99%

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Controlling reaction rate of phase transfer hydrogenation of acetophenone by application of low external electric field

2020

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The controllable mass transfer and reaction rate for phase transfer hydrogenation of acetophenone across a well‐defined boundary were investigated. The effect of solvent was found important and 1‐butanol exhibited the best performance among the five investigated homologous alcohol solvents, consistent with its higher solubility in water and greater dielectric constant. Initial reaction rates increased with increasing electric potential, consistent with enhanced mass transfer across the aqueous/organic boundary. At longer reaction times, deactivation was apparent. It correlated with increasing voltage and is ascribed to lower equilibrium concentration of reactive species at the interface. External control over reaction rate was demonstrated by switching the applied electric potential over the course of the reaction. Effects of external electric field on enantioselectivity were also explored with reversal field direction. The changes correlate with catalyst decomposition.

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