Reaction on Water: A Greener Approach for the Thia Michael Addition on<i>N</i>-Aryl Maleimides

Mitra, Rangan; Bhattarai, Sanjay; Nair, Vipin A.

doi:10.1080/00397910903576651

Cited by 8 publications

(9 citation statements)

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“…A similar water‐assisted thia‐Michael addition on N ‐phenylmaleimide was reported by Nair et al. in 2011 [12] . The authors examined the conjugate addition of thiols to N ‐arylmaleimide with different aromatic thiols, aliphatic thiols, and heteroaromatic thiols in water.…”

Section: Introductionmentioning

confidence: 57%

“…Indeed, several research groups obtained excellent computational results using such water‐reactant complexes as the reference point of calculating reaction free energy barriers, although they did not investigate the effect of the number of water molecules involved [33–34] . We also noted that the reaction products do not mix well with water solvent and they separate into an organic layer [10,12] . In other words, the hydrogen bonded water molecules would be stripped out of the reacting complexes into the aqueous portion of the reaction mixture at some point along the reaction.…”

Section: Resultsmentioning

confidence: 92%

“…However, for the uncatalyzed thia-Michael reaction in aqueous solution, cyclohexenone, which reacted with thiophenol in 5 minutes to give 90% yield, [10] seems to react faster than the more electro- philic N-(4-fluorophenyl)maleimide, which gave 85% yield after 15 mins. [12] To understand the reactivity trend, we first calculated the Parr's electrophilicity index ω [50] of the three Michael acceptors studied for thia-Michael additions, namely cyclohexenone, methyl acrylate, and N-phenylmaleimide (Table 2). The calculated electrophilicity index of methyl acrylate at 1.51 eV matches very well with literature value.…”

Section: Reactivity Of Thia-michael Acceptorsmentioning

confidence: 99%

“…To this end, we investigated the catalytic role of water in six representative water‐assisted hetero‐Michael addition reactions (see Scheme 2) using density functional theory (DFT) calculations. These conjugate addition reactions were chosen based on available experimental studies for direct comparison to computational results [10,12–14] . Most theoretical studies on water‐assisted organic reactions in literature employed single water in their investigations.…”

Section: Introductionmentioning

confidence: 99%

“…These conjugate addition reactions were chosen based on available experimental studies for direct comparison to computational results. [10,[12][13][14] Most theoretical studies on waterassisted organic reactions in literature employed single water in their investigations. Here, we focused on the effect of multiple water molecules on the reaction pathways.…”

Section: Introductionmentioning

confidence: 99%

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Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Hui

Wong

2021

Asian J Org Chem

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The reaction mechanism of six catalyst‐free hetero‐Michael addition reactions in water has been investigated using DFT calculations. Our theoretical results revealed the direct involvement of multiple water molecules in the transition states. The water molecules play a catalytic role in lowering the activation barrier for the three thia‐Michael reactions. Concerted transition state with two bridging water molecules yields the lowest energy barrier. The formation of a hydrogen bonding network via one or more water molecules in the transition state facilitates proton shuttling from the nucleophile to the electrophile. For the aza‐Michael reactions considered, they follow a stepwise mechanism involving the formation of a stable zwitterionic intermediate. In these cases, water influences the reactions via strong (nonspecific) solvent effect and the catalytic role of water is less important for enones that adopt a stable s‐cis conformation. The calculated low reaction barriers (44–83 kJ/mol) of the six studied reactions are in excellent accord with the observed facile hetero‐Michael reactions in water.

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Section: Introductionmentioning

confidence: 57%

Section: Resultsmentioning

confidence: 92%

Section: Reactivity Of Thia-michael Acceptorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Hui

Wong

2021

Asian J Org Chem

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Thia‐Michael Addition: An Emerging Strategy in Organic Synthesis

2018

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The thia-Michael addition reactionh as been demonstrated to be ah ighly powerful tool in organic synthesis. Indeed, the influential natureo ft his reactionh as been wellestablished in the fields of medicinal chemistry,c atalysis, drug discovery,a nd materials science. The emergence of numerous synthetic strategies that take advantage of thia-Michael addition reactions of electron-deficienta lkenes has unleashed countless opportunities for the design and synthesis of diverse biologically relevant organosulfurc ompounds. However,d espite myriad potential synthetic applications, there has not been anye xclusive reviewso ft he thia-Michael addition reaction. Therefore, this Focus Review plots the journeyo ft he thia-Michael addition reaction in organic synthesis, and is categorized according to catalyzed and catalyst-free thia-Michael addition reactions. Figure 1. Summary of the applicationsoft hia-Michael adducts.[a] Dr.Scheme1.Catalyzed pathways for the thia-Michael addition reaction.EW-G = electron-withdrawing group.Scheme2.Acetic-acid-catalyzed thia-Michael additionr eaction proposed by Allen et al. [24] AsianJ.O rg.Scheme3.Indium-bromide-catalyzed thia-Michael addition reaction.Scheme4.Thia-Michael addition reaction followed by a1 ,2-addition of TMSCN in one pot. TMSCN = trimethylsilyl cyanide.Scheme5.Bi III -catalyzedt hia-Michael additionreactiono fa,b-unsaturated carbonyl compounds. Tf = trifluoromethanesulfonyl.Scheme6.Bismuth-triflate-catalyzed synthesis of bis-thioether compounds. Bn = benzyl.Scheme7.Iron-/copper-catalyzed thia-Michael additionr eaction.Scheme8.VO(OTf) 2 -mediated synthesis of b-mercapto ketones. Np = naphthyl.Scheme9.Substrate scope for the synthesis of 3-sulfanyl-substituted 1-(arylamino)-pyrrolidine-2,5-diones.Scheme10. Regio-and enantioselective addition at the d position of conjugated systems.Scheme11. Mechanistic modelf or the enantioselective d addition of at hiol to an a,b,g,d-unsaturated dienone,catalyzed by achiral Fe III Àsalenc omplex.Scheme12. Chemoselectivesynthesis of 2-amino-3,1-benzothiazines (15) and 3,4-dihydroquinazoline-2-thiones (16)byu sing ortho-aminocinnamate (13)a nd isothiocyanates 14.Scheme13. Reactionmechanism for the chemoselective synthesis of 2amino-3,1-benzothiazines (15)and 3,4-dihydroquinazoline-2-thiones (16).Scheme14. ZrCl 4 -assisted three-component reactionf or the synthesiso fbaryl-b-mercapto ketones.Scheme15. LiF-nanocube-mediated thia-Michael addition reaction.Scheme57. Ni II -catalyzed enantioselective synthesiso f2-aryl-3-nitrothiochroman-4-ols.Scheme58. Te ntative reaction mechanism for the Ni II -catalyzed asymmetric synthesis of 2-aryl-3-nitrothiochroman-4-ols.Scheme59. Pepsin-catalyzed synthesis of functionalized chiral dihydrothiophenes.Scheme69. Mechanistic aspects of the stereoselectives ynthesis of tetrahydrothioxanthenones.Scheme70. Enantioselectivesynthesis of methyl 2-((R)-2-nitro-1-(aryl/heteroaryl)ethylthio)acetatesa nd thiomorpholin-3-ones.Scheme71. Water-accelerated thia-Michael additionr eaction proposedb y Chakraborti and co-work...

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Antibacterial Mechanism of N‐PMI and the Characteristics of PMMA‐Co‐N‐PMI Copolymer**

Han

Zhuang

Zheng

et al. 2022

Chemistry & Biodiversity

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Aiming at the excellent killing effect of N‐phenylmaleimide (N‐PMI) on microorganisms, this article used structural simulation analysis, fluorescence analysis, confocal laser scanning microscope and SEM to find that the double bond in N‐PMI could interact with the sulfur groups in the membrane protein, changing its conformation, rupturing the plasma membrane of the cell, leaking the contents, and ultimately causing the death of the microorganisms. Therefore, once the double bond participated in the polymerization, N‐PMI lost its antimicrobial function. N‐PMI could achieve azeotropic copolymerization with MMA through reactive extrusion polymerization. N‐PMI with a content of 5 % can be evenly inserted into the PMMA chain segment during the copolymerization reaction, thereby increasing the Tg of pure PMMA by up to 15 °C, which provided the PMMA‐co‐PMI copolymer with resistance to boiling water sterilization advantageous conditions. In addition, N‐PMI with a content of 5 % has little effect on the transparency of PMMA after participating in the copolymerization. Moreover, the trace amount of residual N‐PMI made the material have excellent antimicrobial function, and the bacteriostatic zone is extremely small, which provided an excellent guarantee for the safety and durability of the material. As a medical biological material, the PMMA‐co‐PMI copolymer has a good industrialization application prospects.

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Reaction on Water: A Greener Approach for the Thia Michael Addition onN-Aryl Maleimides

Abstract: A greener, economical, and efficient methodology for the Michael addition of thiols to N-aryl maleimides has been developed.

Cited by 8 publications

References 10 publications

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Water‐Assisted and Catalyst‐Free Hetero‐Michael Additions: Mechanistic Insights from DFT Investigations

Thia‐Michael Addition: An Emerging Strategy in Organic Synthesis

Antibacterial Mechanism of N‐PMI and the Characteristics of PMMA‐Co‐N‐PMI Copolymer**

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