First mechanosynthesis of piperlotines A, C, and derivatives through solvent-free Horner-Wadsworth-Emmons reaction

Ramírez-Marroquín, Oscar Abelardo; Manzano-Pérez, Flavio; López-Torres, Adolfo; López, Alejandro Hernández; Cortés-Pacheco, Abimelek; Reyes-González, Miguel Ángel

doi:10.1080/00397911.2018.1550204

“…[47][48][49][50] Despite its potential, solvent-free or LAG Wittig-type reactions are relatively underexplored in the literature (Figure 1). Most reports focus on stabilized phosphonium ylides in the Horner-Wadsworth-Emmons (HWE) modification of the Wittig reaction [51][52][53][54][55][56] or semi-stabilized ylides from benzyl phosphonium salts. [57][58][59][60] While these reactions are conducted under neat conditions, some protocols still require external heating, such as conventional heating via an oil bath or microwave irradiation, to provide the necessary energy.…”

Section: Introductionmentioning

confidence: 99%

“…51,53 Reports relying solely on mechanical force to drive the reaction are scarce. 52,54,[57][58][59]61 In 2018, Mack explored the diastereoselectivity of the Wittig reaction on benzaldehyde under LAG using benzyltriphenylphosphonium bromide. 57 And very recently Friščić reported a hexameric supramolecular cage assembly constructed from (dibromomethyl)triphenylphosphonium bromide units.…”

Section: Introductionmentioning

confidence: 99%

High-speed Ball Milling Enables an Ultra-fast Wittig Olefination Under Ambient and Solvent-free Conditions Without Ylide Pre-formation

Templ,

Schnürch

2024

Preprint

0

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30 Seconds to success! – The Wittig reaction, a fundamental and extensively utilized reaction in organic chemistry, enables the efficient conversion of carbonyl compounds to olefins using phosphonium salts. Traditionally, meticulous reaction setup, including the pre-formation of a reactive ylide species via deprotonation of a phosphonium salt, is crucial for achieving high-yielding reactions under classical solution-based conditions. In this report, we present an unprecedented protocol for an ultra-fast mechanochemically driven Wittig reaction under solvent-free and ambient conditions, eliminating the need for tedious ylide pre-formation under strict air and moisture exclusion. A range of aldehydes and ketones were reacted with diverse phosphonium salts under high-speed ball milling conditions, giving access to the respective olefins in only 30 seconds.

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“…[47][48][49][50] Despite its potential, solvent-free or LAG Wittig-type reactions are relatively underexplored in the literature (Figure 1). Most reports focus on stabilized phosphonium ylides in the Horner-Wadsworth-Emmons (HWE) modification of the Wittig reaction [51][52][53][54][55][56] or semi-stabilized ylides from benzyl phosphonium salts. [57][58][59][60] While these reactions are conducted under neat conditions, some protocols still require external heating, such as conventional heating via an oil bath or microwave irradiation, to provide the necessary energy.…”

Section: Introductionmentioning

confidence: 99%

High-speed Ball Milling Enables an Ultra-fast Wittig Olefination Under Ambient and Solvent-free Conditions Without Ylide Pre-formation

Templ,

Schnürch

2024

Preprint

0

View full text Add to dashboard Cite

30 Seconds to success! – The Wittig reaction, a fundamental and extensively utilized reaction in organic chemistry, enables the efficient conversion of carbonyl compounds to olefins using phosphonium salts. Traditionally, meticulous reaction setup, including the pre-formation of a reactive ylide species via deprotonation of a phosphonium salt, is crucial for achieving high-yielding reactions under classical solution-based conditions. In this report, we present an unprecedented protocol for an ultra-fast mechanochemically driven Wittig reaction under solvent-free and ambient conditions, eliminating the need for tedious ylide pre-formation under strict air and moisture exclusion. A range of aldehydes and ketones were reacted with diverse phosphonium salts under high-speed ball milling conditions, giving access to the respective olefins in only 30 seconds.

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“…WE reaction is used in ring-closing reactions, synthetic segments, asymmetric reactions, carbon chain elongation, and tandem reactions, including HWE olefination as reported by Kobayashi et al A green method of piperlotines was developed using Horner–Wadsworth–Emmons (HWE) reaction by mechanochemical activation operated under solvent-free conditions. Piperlotines are important natural compounds formed via the α,β-unsaturated amide moiety . Bilska-Markowska and Kaźmierczak reported the HWE reaction as a reliable, stereoselective, and simple olefination method.…”

Section: Introductionmentioning

confidence: 99%

Wadsworth–Emmons Reaction by Using the Fluorapatite Catalyst: Kinetic Studies

Vishwakarma

¹

,

Vinod

²

,

Rathod

³

et al. 2023

Ind. Eng. Chem. Res.

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Wadsworth−Emmons reaction was successfully carried out by using the fluorapatite (FAP) catalyst. The reaction of 2methoxybenzaldehyde and triethylphosphonoacetate using FAP afforded α,β-unsaturated ester with 100% conversion and 80% selectivity. A kinetic model was validated at different temperatures by Langmuir− Hinshelwood−Hougen−Watson (LHHW), and the absence of mass transfer resistance was verified by the Weisz Prater criterion. The effect of different catalysts, temperature, catalyst loading, solvent, mole ratio, and speed of stirring was studied. The FAP catalyst was characterized by Fourier transform infrared spectroscopy, Brunauer−Emmett−Teller method, nitrogen adsorption−desorption, transmission electron microscopy, energy-dispersive X-ray spectroscopy, temperature programmed desorption (TPD-NH 3 ), X-ray diffraction, and X-ray photoelectron spectroscopy. The FAP catalyst was found to be stable up to three recycles with no loss in activity.

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First mechanosynthesis of piperlotines A, C, and derivatives through solvent-free Horner-Wadsworth-Emmons reaction

Cited by 13 publications

References 38 publications

High-speed Ball Milling Enables an Ultra-fast Wittig Olefination Under Ambient and Solvent-free Conditions Without Ylide Pre-formation

High-speed Ball Milling Enables an Ultra-fast Wittig Olefination Under Ambient and Solvent-free Conditions Without Ylide Pre-formation

High-speed Ball Milling Enables an Ultra-fast Wittig Olefination Under Ambient and Solvent-free Conditions Without Ylide Pre-formation

Wadsworth–Emmons Reaction by Using the Fluorapatite Catalyst: Kinetic Studies

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