Conjugate Addition of 3-Buytn-2-one to Anilines in Ethanol: Alkene Geometric Insights through In Situ FTIR Monitoring

Chisholm, David; Valentine, Roy; Pohl, Ehmke; Whiting, Andrew

doi:10.1021/acs.joc.6b01110

Cited by 26 publications

(28 citation statements)

References 53 publications

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“…The quantitative reaction finished at less than 30 min. Based on the 1 H-NMR analysis, the resulting enamine product exhibited a mixture of E -and Z -configuration, in which the Z ratio was over ~92%, due to the probable intramolecular hydrogen bonding (b) [35–37]. The resulting enamine product was further characterized by 13 C-NMR and HRMS analysis ().…”

Section: Resultsmentioning

confidence: 99%

A Simple Approach to Bioconjugation at Diverse Levels: Metal-Free Click Reactions of Activated Alkynes with Native Groups of Biotargets without Prefunctionalization

Zhao

et al. 2018

Research

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The efficient bioconjugation of functional groups/molecules to targeted matrix and bio-related species drives the great development of material science and biomedicine, while the dilemma of metal catalysis, uneasy premodification, and limited reaction efficiency in traditional bioconjugation has restricted the booming development to some extent. Here, we provide a strategy for metal-free click bioconjugation at diverse levels based on activated alkynes. As a proof-of-concept, the abundant native groups including amine, thiol, and hydroxyl groups can directly react with activated alkynes without any modification in the absence of metal catalysis. Through this strategy, high-efficient modification and potential functionalization can be achieved for natural polysaccharide, biocompatible polyethylene glycol (PEG), synthetic polymers, cell penetrating peptide, protein, fast whole-cell mapping, and even quick differentiation and staining of Gram-positive bacteria, etc. Therefore, current metal-free click bioconjugation strategy based on activated alkynes is promising for the development of quick fluorescence labeling and functional modification of many targets and can be widely applied towards the fabrication of complex biomaterials and future in vivo labeling and detection.

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Section: Resultsmentioning

confidence: 99%

A Simple Approach to Bioconjugation at Diverse Levels: Metal-Free Click Reactions of Activated Alkynes with Native Groups of Biotargets without Prefunctionalization

Zhao

et al. 2018

Research

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“…The two enaminone derivatives, BrE and HE, were readily synthesized in good yields by conjugate addition between aniline and ynone derivatives in methanol at room temperature according to the literature method . Both molecules were soluble in common organic solvents such as n ‐hexane, toluene, tetrahydrofuran (THF), dichloromethane (DCM), and dimethyl formamide (DMF).…”

Section: Methodsmentioning

confidence: 99%

Aggregation‐Induced Emission of Highly Planar Enaminone Derivatives: Unexpected Fluorescence Enhancement by Bromine Substitution

Shu

Liu

et al. 2019

Advanced Optical Materials

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F…S, can be served as "conformational lock" to limit the free rotation of aromatic rings, which is a widely used approach to designing organic thin film transistor (OTFT) and organic photo voltaics (OPV) materials. [17][18][19] However, the planar π-conjugated molecules are always resulting fluorescence quenched in the solid state due to the tightly π-π stacking. For better application in the field of luminescence, it is urgently need to develop planar organic π-conjugated molecules with AIE-active. [20,21] For example, Yang et al. introduced S…O or Se…O noncovalent intramolecular interactions into ACQ molecules, which stabilized planar structure and restricted the photoisomerization in solid state, resulting in interesting AIE effects. [20] Halogen bonding as noncovalent interaction has been widely adopted in supramolecular chemistry for self-assembly of liquid crystals, magnetic and conducting materials and biological systems, whereas drew relatively less attention in the design of organic solid fluorescent materials. [22][23][24][25] In recent years, the incorporation of heavy bromide atom has been utilized extensively for the construction of pure organic materials with roomtemperature phosphorescence. [26][27][28] The well-known heavy atom effect of bromide can promote both singlet-to-triplet and triplet-to-singlet intersystem crossing by enhanced spin-orbit coupling. [29,30] Furthermore, the rigidification effect of halogen bonding in solid states will suppress nonradiative relaxation of triplets, and thus strengthen the phosphorescent emission. [31,32] For example, Bolton et al. revealed the importance of intermolecular short contact halogen bonding (CO⋅⋅⋅BrAr) on the bright phosphorescence from crystals or cocrystals of 2,5-dihexyloxy-4-bromobenzaldehyde and its analogs. [33] Shi et al. also demonstrated that the formation of multiple Br⋅⋅⋅Br halogen bonding in solid states could enhance phosphorescence quantum yields for a series of dibromobenzene derivatives. [34] At the same time, the heavy-atom effect always leads to significant fluorescent quenching of bromine-substituted organic fluorophores compared with their hydrogen analogs. [35,36] However, tunable multicolor solid-state fluorescence has been observed in organic cocrystals with the supramolecular arrangements governed by halogen bonding. [37] In another example, several metal-organic cages equipped with halogen bonding interactions exhibited brighter solid state emission than their organic fluorescent ligands. [38] Therefore, halogen bonding may also have a great potential for the construction of organic solid fluorescent materials.Unlike typical aggregation-induced-emission (AIE) molecules with twist/rotor structures, two AIE-active enaminone derivatives with highly planar conformations are herein reported. Interestingly, the bromine-substituted enaminone fluorophore (BrE) exhibits unexpected stronger emission in solid states than unsubstituted enaminone fluorophore (HE), which is seldom observed for organic fluorophores. Remarkably, the fluo...

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“…Whiting reported that the reaction between aniline and ynone afforded the corresponding ( Z )‐enaminone at room temperature within 20 min in ethanol as the solvent . Later Legros found out trans ‐4‐methoxy‐3‐buten‐2‐one can be a convenient, effective and inexpensive surrogate for 3‐butyn‐2‐one, to afford ( Z )‐enaminones (Scheme ) .…”

Section: Michael Additions On Watermentioning

confidence: 99%

Recent Advances and Prospects of Organic Reactions “On Water”

et al. 2019

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Organic reactions “On water” is a rapidly developing area over the past few years. Many important classes of reactions like cross‐coupling reactions, pericyclic reactions, C−H activations etc. were performed on water and have shown tremendous increase in the reaction rates due to the potential hydrogen bonding capacity of water. This review focuses on the recent trends and developments in the field of on water reactions applied to organic synthesis and covers literature from 2016–2019.

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Conjugate Addition of 3-Buytn-2-one to Anilines in Ethanol: Alkene Geometric Insights through In Situ FTIR Monitoring

Cited by 26 publications

References 53 publications

A Simple Approach to Bioconjugation at Diverse Levels: Metal-Free Click Reactions of Activated Alkynes with Native Groups of Biotargets without Prefunctionalization

A Simple Approach to Bioconjugation at Diverse Levels: Metal-Free Click Reactions of Activated Alkynes with Native Groups of Biotargets without Prefunctionalization

Aggregation‐Induced Emission of Highly Planar Enaminone Derivatives: Unexpected Fluorescence Enhancement by Bromine Substitution

Recent Advances and Prospects of Organic Reactions “On Water”

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