Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Nitrosobenzene: Reagent for the Mitsunobu Esterification Reaction.

ABSTRACT: Nitrosobenzene has been demonstrated to participate in the Mitsunobu reaction in an analogous manner to dialkyl azodicarboxylates. The protocol using nitrosobenzene and triphenylphosphine (1:1) under mild conditions (0 °C) provides the ester derivatives of aliphatic and aromatic acids using various alcohols in moderate yield and with good enantioselectivity, giving the desired products predominantly with an inversion of configuration. The proposed mechanism, which is analogous to that observed using dialkyl azodicarboxylates, involves a nitrosobenzene-triphenylphosphine adduct and an alkoxytriphenylphosphonium ion and was supported by density functional theory calculations, ³¹P NMR spectroscopy, and experiments conducted with isotopically labeled substrates.

SUBMITTER: Pokluda A

PROVIDER: S-EPMC6648318 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Nitrosobenzene: Reagent for the Mitsunobu Esterification Reaction.

Pokluda Adam A Kohout Michal M Chudoba Josef J Krupička Martin M Cibulka Radek R

ACS omega 20190307 3

Nitrosobenzene has been demonstrated to participate in the Mitsunobu reaction in an analogous manner to dialkyl azodicarboxylates. The protocol using nitrosobenzene and triphenylphosphine (1:1) under mild conditions (0 °C) provides the ester derivatives of aliphatic and aromatic acids using various alcohols in moderate yield and with good enantioselectivity, giving the desired products predominantly with an inversion of configuration. The proposed mechanism, which is analogous to that observed u ...[more]

PMID: 31459682

Similar Datasets

Triphenylphosphine Dibromide: A Simple One-pot Esterification Reagent.

Project description:We report a one-pot, expedient protocol for the conversion of carboxylic acids to their esters using excess triphenylphosphine dibromide, base, and the alcohol. The reaction gave the esterified product in moderate-to-high yields (30-95%). For chiral acids, the reaction proceeded with little or no racemization. Use of a chiral alcohol in this transformation gave the ester with retention of configuration of the stereogenic center. Information is presented indicating that esterification proceeds through the intermediate generation of an acyloxyalkoxyphosphorane and where steric interactions play an important role in the energetics of the reaction.

| S-EPMC2633481 | biostudies-literature

Stereoselective Synthesis of Selenium-Containing Glycoconjugates via the Mitsunobu Reaction.

Project description:A simple and efficient route for the synthesis of new glycoconjugates has been developed. The approach acts as a model for a mini-library of compounds with a deoxy-selenosugar core joined to a polyphenolic moiety with well-known antioxidant properties. An unexpected stereocontrol detected in the Mitsunobu key reaction led to the most attractive product showing a natural d-configuration. Thus, we were able to obtain the target molecules from the commercially available d-ribose via a shorter and convenient sequence of reactions.

| S-EPMC8123786 | biostudies-literature

Synthesis of N,N-Diethylbenzamides via a Non-Classical Mitsunobu Reaction.

Project description:The use of the Mitsunobu reaction for the synthesis of N,N-diethylbenzamides affords ortho-, meta-, and para-substituted benzamides, containing both electron-donating and electron-withdrawing groups. While the preparation of numerous functional groups has been efficiently demonstrated employing the Mitsunobu reaction, our methodology represents the first application of the Mitsunobu reaction for the construction of benzamides using benzoic acid and amine starting materials. Moreover, this synthetic transformation is believed to proceed via a non-classical mechanism involving the existence of an acyloxyphosphonium ion.

| S-EPMC4159177 | biostudies-literature

Unconventional application of the Mitsunobu reaction: Selective flavonolignan dehydration yielding hydnocarpins.

Project description:Various Mitsunobu conditions were investigated for a series of flavonolignans (silybin A, silybin B, isosilybin A, and silychristin A) to achieve either selective esterification in position C-23 or dehydration in a one-pot reaction yielding the biologically important enantiomers of hydnocarpin D, hydnocarpin and isohydnocarpin, respectively. This represents the only one-pot semi-synthetic method to access these flavonolignans in high yields.

| S-EPMC4901995 | biostudies-literature

Monomer-on-monomer (MoM) Mitsunobu reaction: facile purification utilizing surface-initiated sequestration.

Project description:A monomer-on-monomer (MoM) Mitsunobu reaction utilizing norbornenyl-tagged (Nb-tagged) reagents is reported, whereby purification was rapidly achieved by employing ring-opening metathesis polymerization, which was initiated by any of three methods utilizing Grubbs catalyst: (i) free catalyst in solution, (ii) surface-initiated catalyst-armed silica, or (iii) surface-initiated catalyst-armed Co/C magnetic nanoparticles.

| S-EPMC3271942 | biostudies-literature

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents.

Project description:Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.

| S-EPMC6020523 | biostudies-literature

Diversity-oriented synthesis of dihydrobenzoxazepinones by coupling the Ugi multicomponent reaction with a Mitsunobu cyclization.

Project description:An operationally simple protocol for the synthesis of 2,3-dihydrobenzo[f][1,4]oxazepin-3-ones, based on an Ugi reaction of an ortho-(benzyloxy)benzylamine, glycolic acid, an isocyanide and an aldehyde, followed by an intramolecular Mitsunobu substitution was developed. The required ortho-(benzyloxy)benzylamines have been in situ generated from the corresponding azides, in turn prepared in high yields from salicylic derivatives.

| S-EPMC3943941 | biostudies-literature

Assembling the prenylneoflavone system through a Pechmann condensation/Mitsunobu reaction/Claisen rearrangement/olefin cross-metathesis sequence.

Project description:AbstractThe multistep synthesis of a prenylneoflavone through a sequence of the Mitsunobu reaction/Claisen rearrangement/olefin cross-metathesis reaction has been accomplished in 5% yield over six steps starting from commercially available 3-methoxyacetophenone. The sequence is shown to be compatible with a Pechmann condensation which proved to be a robust and cost-effective method for the assembling of the α-pyrone core. The results open doors to a general approach to the prenylneoflavone system starting from phenol and acetophenone derivatives.Graphic abstract

| S-EPMC7186117 | biostudies-literature

Synergizing Sulfonated Hydrothermal Carbon and Microwave Irradiation for Intensified Esterification Reaction.

Project description:The synergy of sulfonated hydrothermal carbon and microwave (MW) irradiation was applied for the esterification of oleic acid with methanol (MeOH) to produce biodiesel. The effects of temperature, reaction time, ratio of oleic acid to methanol, and catalyst loading were investigated at a fixed MW power of 400 W. The addition of hexane, serving as a co-solvent and separator, was also investigated. The optimum conditions for the proposed process were oleic acid-to-methanol molar ratio of 1:5 and hexane-to-methanol ratio of 0.5 (v/v) in the presence of a 5 wt % catalyst, at 100 °C for 60 min, obtaining a 97% yield of oleic acid methyl ester. The addition of slight amounts of hexane resulted into an eightfold reduction in the amount of MeOH needed to obtain a yield above 90%, which normally required a MeOH-to-oil ratio of 40:1. This proposed novel approach could provide a more cost-effective method for the esterification of oil to produce biodiesel, that is, reactive separation utilizing carbon-based catalysts under MW irradiation.

| S-EPMC7512435 | biostudies-literature

Optimization of solvent-free enzymatic esterification in eutectic substrate reaction mixture.

Project description:The Candida rugosa lipase catalyzed esterification of (-)-menthol and lauric acid (LA) was studied in a eutectic mixture formed by both substrates((-)-menthol:LA 3:1, mol/mol). No additional reaction solvent was necessary, since the (-)-menthol:LA deep eutectic solvent (DES) acts as combined reaction medium and substrate pool. Therefore, the esterification is conducted under solvent-free conditions. The thermodynamic water activity (aw) was identified as a key parameter affecting the esterification performance in the (-)-menthol:LA DES. A response surface methodology was applied to optimize the esterification conditions in terms aw, amount of C. rugosa lipase (mCRL) and reaction temperature. Under the optimized reaction conditions (aw = 0.55; mCRL =60 mg; T =45 °C), a conversion of 95 ± 1% LA was achieved (one day), the final (-)-menthyl lauric acid ester concentration reached 1.36 ± 0.04 M (2.25 days). The experimental product formation rate agreed very well with the model prediction.

| S-EPMC6453777 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data