A Multicomponent Route to Functionalized Amides and Oxazolidinones

McPherson, Christopher G.; Cooper, Alasdair; Bubliauskas, Andrius; Mulrainey, Paul; Jamieson, Craig; Watson, Allan J. B.

doi:10.1021/acs.orglett.7b03470

Cited by 8 publications

(5 citation statements)

References 40 publications

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“…3‐Benzyl‐5‐(phenoxymethyl)oxazolidin‐2‐one (4o) : The reaction was carried out according to the general procedure mentioned above on a 2 mmol scale, at 100 °C for 24 h. The crude product was purified by flash chromatography ( n ‐hexanes/ethyl acetate, 100:0 → 70:30, R f 0.15 (85:15)) to yield 4o (465 mg, 1.64 mmol, 82 % yield) as a white solid. 1 H NMR and 13 C NMR spectra were in agreement with the previously reported spectrum . M.p.…”

Section: Methodssupporting

confidence: 90%

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Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides

et al. 2020

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Squaramide–quaternary ammonium salt is illustrated as a simple, tunable, and competent metal‐free binary catalytic platform for the atom‐economic conversion of epoxides and isocyanates into oxazolidinones. Although, various metal catalysts have been employed for the title reaction, application of organocatalysis is scarce. At first, a rational survey of catalytic activity of several air‐stable and architecturally distinct squaramides was undertaken. Thereafter, the impact on catalytic capability of different parameters, such as temperature, catalyst loading, and nature of nucleophiles, was examined. This binary organocatalytic system for the oxazolidinone synthesis, composed of a squaramide entity along with a suitable halide anion, was applied to the challenging conversion of a plethora of alkyl‐ and aryl‐substituted epoxides– including disubstituted and enantioenriched ones– and isocyanates into the corresponding oxazolidinones in high‐to‐excellent yields. The time‐dependent formation of oxazolidinone from epoxide and isocyanate was monitored by FTIR‐ATR and 1H NMR spectroscopy and the scalability of this process was also described. In light of 1H NMR experiment, a hydrogen‐bonding/anion‐binding mechanism was proposed wherein the nucleophilic ring‐opening operation, and oxo‐ and carbamate‐anions stabilization occur cooperatively towards isocyanate fixation.

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Section: Methodssupporting

confidence: 90%

“…1 H NMR and 13 C NMR spectra were in agreement with the previously reported spectrum. [45] M.p. 63-64°C; IR (neat) 3060, 2925, 1734 cm -1 ; 1 H NMR (600 MHz, CDCl 3 ) δ H = 7.…”

Section: -Benzyl-5-(phenoxymethyl)oxazolidin-2-one (4o)mentioning

confidence: 99%

Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides

et al. 2020

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“…Bulkier α‐substituted benzyl amines, i. e ., 1‐phenylethan‐1‐amine and 2‐phenylpropan‐2‐amine, reacted sluggishly, and generated oxazolidinones 3 p and 3 q in yields of 54 % and 19 %, respectively. The latter yield was improved to 60 % through increasing catalyst loading to 8 mol %, whereas the BEMP‐based system did not show any activity . Reactions of 2‐phenylethan‐1‐amine and 3‐phenylpropan‐1‐amine gave comparable yields of 92 % ( 3 r ) and 84 % ( 3 s ), respectively.…”

Section: Resultsmentioning

confidence: 99%

A Multicomponent Approach to Oxazolidinone Synthesis Catalyzed by Rare‐Earth Metal Amides

et al. 2019

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Three-component reaction of epoxides, amines, and dimethyl carbonate catalyzed by rare-earth metal amides has been developed to synthesize oxazolidinones. 47 examples of 3,5disubstituted oxazolidinones were prepared in 13-97 % yields. This is a simple and most practical method which employs easily available substrates and catalysts, and is applicable to a wide range of aromatic and aliphatic amines, as well as monosubstituted epoxides. Scope of disubstituted epoxides is rather limited, which requires further study. Preliminary mechanistic study reveals two possible reaction pathways through intermediates of β-amino alcohols or amides. using ethyl acetate/petroleum ether = 1/3-1/0, and the resulting oxazolidinone was characterized by 1 H and 13 C NMR spectroscopy and HR MS.

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“…In 2017, Jamieson et al . successfully developed oxazolidinones via the three‐component cycloaddition of dimethyl carbonate, epoxide, and primary aliphatic amines mediated by phosphazene base BEMP in MeCN [7] . A three component reaction of epoxides, amines and dialkyl carbonates catalyzed by readily available rare‐earth metal amides was also reported by Yuan and Yao groups (Scheme 2a) [8] .…”

Section: Introductionmentioning

confidence: 90%

A Greener Approach to Oxazolidinone Synthesis Using a Ternary Deep Eutectic Solvent

et al. 2022

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By employing a ternary and environmentally benign deep eutectic solvent comprising choline chloride, glycerol, and aluminum chloride hexahydrate(ChCl/Glycerol/AlCl3.6H2O) as the catalyst and reaction media, three component reaction of epoxides, amines and dimethyl carbonate has been accomplished, which allows for the efficient construction of various 3,5‐disubstituted oxazolidinones, important scaffolds in small molecule drug discovery. Simple reaction conditions and the use of green and sustainable materials and reagents make this a straightforward and practical methodology for obtaining various oxazolidinones.

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A Multicomponent Route to Functionalized Amides and Oxazolidinones

Cited by 8 publications

References 40 publications

Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides

Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides

A Multicomponent Approach to Oxazolidinone Synthesis Catalyzed by Rare‐Earth Metal Amides

A Greener Approach to Oxazolidinone Synthesis Using a Ternary Deep Eutectic Solvent

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