Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC02627G, Paper

Kathiravan Murugesan, Thirusangumurugan Senthamarai, Manzar Sohail, Muhammad Sharif, Narayana V. Kalevaru, Rajenahally V. Jagadeesh
Nanoscale Fe₂O₃-catalyzed environmentally benign synthesis of nitriles and amides has been performed from easily accessible aldehydes and ammonia using O₂.

http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C7GC02627G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Stable and reusable nanoscale Fe₂O₃-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

 

Kathiravan Murugesan,^a  Thirusangumurugan Senthamarai,^a  Manzar Sohail,^b  Muhammad Sharif,^b  Narayana V. Kalevaru^a  and  Rajenahally V. Jagadeesh*^a 

Author affiliations

* Corresponding authors

^a Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
E-mail:Jagadeesh.Rajenahally@catalysis.de

^b The Center of Research Excellence in Nanotechnology (CENT) and Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

Abstract

The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O₂ or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.

1H NMR (300 MHz, Chloroform-d) δ 7.17 – 6.96 (m, 2H), 6.93 – 6.70 (m, 1H), 4.33 – 4.11 (m, 4H). 13C NMR (75 MHz, Chloroform-d) δ 147.75 , 143.80 , 125.87 , 121.21 , 118.91 , 118.25 , 104.38 , 64.59 , 64.12 . Off white solid

  

cas 19102-07-9

• 1,4-Benzodioxan-6-carbonitrile (8CI)
• 2,3-Dihydro-1,4-benzodioxin-6-carbonitrile
• 1-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)nitrile

MP

Melting Point, °C
105 - 106 Tetrahedron, 2015, vol. 71,  29, p. 4883 - 4887

NMR PREDICTS

1H NMR

13C NMR PREDICT

More................

Journal of the American Chemical Society, 2001, vol. 123, 49, p. 12202 - 12206

More.............

RSC Advances, 2013, vol. 3, 44, p. 22389 - 22396

http://www.rsc.org/suppdata/ra/c3/c3ra44386h/c3ra44386h.pdf

  

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Organic Letters, 2017, vol. 19,  12, p. 3095 - 3098

http://pubs.acs.org/doi/suppl/10.1021/acs.orglett.7b01199/suppl_file/ol7b01199_si_001.pdf

2,3-Dihydrobenzo[b][1,4]dioxine-6-carbonitrile (Scheme 1, 2n) According to the general procedure A, the reaction of 1n (0.20 mmol), zinc cyanide (2.0 equiv), PCyPh2 (0.20 equiv) and Pd(OAc)2 (0.05 equiv) in dioxane (0.25 M) for 16 h at 150 °C, afforded after work-up and chromatography the title compound in 75% yield (24.2 mg). White solid. 1H NMR (500 MHz, CDCl3) δ 7.17-7.11 (m, 2H), 6.91 (d, J = 8.1 Hz, 1H), 4.32-4.31 (m, 2H), 4.30- 4.26 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 147.84, 143.91, 126.04, 121.37, 119.01, 118.37, 104.62, 64.71, 64.24.

 

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Sulfurative self-condensation of ketones and elemental sulfur: a three-component access to thiophenes catalyzed by aniline acid-base conjugate pairs

Sulfurative self-condensation of ketones and elemental sulfur: a three-component access to thiophenes catalyzed by aniline acid-base conjugate pairs

Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC03437G, Communication

Thanh Binh Nguyen, Pascal Retailleau
An aniline/acid-catalyzed method for constructing thiophenes 2 from inexpensive ketones 1 and elemental sulfur is reported.

Sulfurative self-condensation of ketones and elemental sulfur: a three-component access to thiophenes catalyzed by aniline acid–base conjugate pairs

 

Thanh Binh Nguyen*^a  and  Pascal Retailleau^a 

Author affiliations

* Corresponding authors

^a Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av de la Terrasse, 91198 Gif-sur-Yvette, France
E-mail: nguyen@icsn.cnrs-gif.fr

Abstract

A sulfurative self-condensation method for constructing thiophenes 2 by a reaction between ketones 1 and elemental sulfur is reported. This reaction, which is catalyzed by anilines and their salts with strong acids, starts from readily available and inexpensive materials, and releases only water as a by-product.


2,4-Di-p-tolylthiophene (2b)2
2 M. Arisawa, T. Ichikawa, and M. Yamaguchi, Chem. Commun. 2015, 51, 8821

Eluent heptane:toluene 9:1. 190 mg, 72%.
1 H NMR (300 MHz, CDCl3) δ 7.60-7.54 (m, 5H), 7.34 (s, 1H), 7.27-7.23 (m, 4H), 2.42 (s, 6H).
13C NMR (75 MHz, CDCl3) δ 145.3, 143.3, 137.8, 137.2, 133.5, 131.9, 129.9, 129.8, 126.5, 126.0, 122.1, 118.9, 21.5, 21.5.
 

Binh Thanh Nguyen

CV Binh Nguyen

CNRS Research Associate CR1 ( ORCID , ResearchGate )
ICSN-CNRS Bât. 27
1, avenue de la Terrasse
91190 Gif-sur-Yvette France
thanh-binh.nguyen_at_cnrs.fr
+33 1 69 82 45 49

 Education and work experience2015: Habilitation to Direct Research (HDR)
2011 - present: CNRS research associate at ICSN - Paris-Saclay University
2009 - 2011: Post-doctoral Fellow at ICSN (Dr. Françoise Guéritte and Dr. Qian Wang)
2003 - 2006: Ph.D. student at the UCO2M Organic Synthesis Laboratory (University of Maine, Le Mans, France, Dr. Gilles Dujardin, Dr. Arnaud Martel, Professor Robert Dhal)
 Research Interests
Green chemistry (Atom, step and redox economic transformation), green synthetic tools: O2, S8, photochemistry, iron catalyst
Elemental sulfur as a synthetic tool (building block, oxidant, reductant, catalyst)
Iron-sulfur catalysts
Heterocycle synthesis
 Scientific Communications
47 publications
 Selected recent publications ( complete list )
[1] Adv. Synth. Catal. 2017 , 359 , 1106.
[2] Asian J. Org. Chem. 2017 , 6 , 477.
[3] Org. Lett. 2016 , 18 , 2177.
[4] Org. Process Res. Dev. 2016 , 20 , 319.
[5] Angew. Chem. Int. Ed. 2014 , 53 , 13808.
[6] J. Am. Chem. Soc. 2013 , 135 , 118.

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Benzyl (5-methylpyrazin-2-yl)carbamate

2-(Cbz-Amino)-5-methylpyrazine

Molecular Formula:	C13H13N3O2
Molecular Weight:	243.266 g/mol

 

 

Benzyl (5-methylpyrazin-2-yl)carbamate

CAS 1033418-57-3

Mp 191.4 °C.

IR 1719, 1567, 1353, 1226, 1054, 759, 744, 706 cm–1.

1H NMR (DMSO-d6, 500 MHz) 10.45 (br, 1H), 8.93 (s, 1H), 8.20 (s, 1H), 7.42–7.32 (m, 5H), 5.18 (s, 2H), 2.41 (s, 3H).

13C NMR (DMSO-d6, 125.7 MHz) 153.6, 147.7, 146.7, 141.7, 136.5, 134.3, 128.7 (2C), 128.4, 128.2 (2C), 66.5, 20.4.

HRMS elemental calculated for C13H14N3O2 (MH+): 244.1086; found: 244.1080.

NMR PREDICT

1H NMR

13 C NMR PREDICT

Use of a Curtius Rearrangement as Part of the Multikilogram Manufacture of a Pyrazine Building Block

Alan Steven*†  and Phillip Hopes‡

† Pharmaceutical Technology & Development, AstraZeneca, Charter Way, Macclesfield, SK10 2NA, United Kingdom

‡ Cyton Biosciences Ltd., 68 Macrae Road, Bristol, BS20 0DD, United Kingdom

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00340

 

*E-mail: Alan.Steven@astrazeneca.com.

http://pubs.acs.org/doi/10.1021/acs.oprd.7b00340

 

 

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A modular flow reactor for performing Curtius rearrangements as a continuous flow process

Marcus Baumann,a  Ian R. Baxendale,a  Steven V. Ley,*a  Nikzad Nikbin,a  Christopher D. Smitha  and Jason P. Tierneyb 

*Corresponding authors

aInnovative Technology Centre, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK
E-mail: svl1000@cam.ac.uk
Fax: +44 1223 336442
Tel: +44 1223 336398

bNeurology Lead Discovery Chemistry, Neurology CEDD, GlaxoSmithKline R and D, New Frontiers Science Park (North), Third Avenue, Harlow, UK

Abstract

The use of a mesofluidic flow reactor is described for performing Curtius rearrangement reactions of carboxylic acids in the presence of diphenylphosphoryl azide and trapping of the intermediate isocyanates with various nucleophiles.

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O=C(OCc1ccccc1)Nc2cnc(C)cn2

Ruthenium-Catalyzed Tandem C–H Fluoromethylation/Cyclization of N-Alkylhydrazones with CBr3F: Access to 4-Fluoropyrazoles

4-Fluoropyrazoles are accessible in a single step from readily available aldehyde-derived N-alkylhydrazones through double C–H fluoroalkylation with tribromofluoromethane (CBr3F). RuCl2(PPh3)3 has been proven to be the most efficient catalyst for this transformation when compared to a range of other Cu-, Pd-, or Fe-based catalyst systems.

Alexis Prieto

Alexis Prieto, Didier Bouyssi*, and Nuno Monteiro* 

Univ Lyon, Université Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS, CNRS UMR 5246), F-69622 Villeurbanne, France

J. Org. Chem., 2017, 82 (6), pp 3311–3316

DOI: 10.1021/acs.joc.7b00085

*E-mail: didier.bouyssi@univ-lyon1.fr., *E-mail: nuno.monteiro@univ-lyon1.fr.

Ruthenium-Catalyzed Tandem C–H Fluoromethylation/Cyclization of N-Alkylhydrazones with CF3BR: Access to 4-Fluoropyrazoles

http://pubs.acs.org/doi/10.1021/acs.joc.7b00085

---

The importance of fluorine-containing pyrazoles to the pharmaceutical and agrochemical industries has been steadily increasing in recent years. As a consequence, the development of methods suitable for the incorporation of fluorine or fluoroalkyl groups into the pyrazole ring continues to be the subject of intense research.

Predicated on their previous copper-catalyzed synthesis of 4-substituted pyrazoles, Bouyssi, Monteiro and their co-worker from the Institut de Chemie et Biochemie Moléculaires et Supramoléculaires reported a ruthenium-catalyzed synthesis of substituted-4-fluoropyrazoles ( J. Org. Chem. 2017, 82, 3311). The requisite starting materials, aldehyde derived N,N-dialkylhydrazones, were readily synthesized. Tribromofluoromethane served as the source of fluorine.

The commercially available and inexpensive ruthenium complex, RuCl2(PPh3)3, was discovered to be a very effective catalyst for this transformation. Diglyme was the preferred solvent for the reaction. The reaction displayed good tolerance for a variety of functional groups, including cyano, ester, formyl, and halide.

In general, higher yields were obtained with electron-withdrawing substituents. This novel methodology affords substituted-4-fluoropyrazoles in good yields in one step from readily available starting materials.

                                                 2K

3-(Benzo[d][1,3]dioxol-5-yl)-4-fluoro-1-methyl-1H-pyrazole (2k)

Chromatography using ethyl acetate/cyclohexane (gradient elution 30:70 to 50:50) gave the title compound as a pale yellow solid (79 mg, 60%).

Mp = 82–85 °C.

1H NMR (400 MHz, CDCl3) δ 7.35–7.31 (m, 2H), 7.27 (d, J = 4.8 Hz, 1H), 6.85 (d, J = 8.5 Hz, 1H), 5.97 (s, 2H), 3.83 (s, 3H).

13C NMR (101 MHz, CDCl3) δ 148.0, 147.2, 146.8 (d, J = 248.0 Hz), 136.7 (d, J = 6.2 Hz), 125.3 (d, J = 4.2 Hz), 119.8 (d, J = 4.7 Hz), 117.5 (d, J = 28.6 Hz), 108.6, 106.6 (d, J = 3.7 Hz), 101.1, 40.0 (s).

19F NMR (282 MHz, CDCl3) δ −178.2 (s). HRMS (ESI): Calcd for C11H10FN2O2 [M + H+]: 221.0721, found 221.0728.

Alexis prieto

Chercheur postdoctoral chez Melchiorre group, ICIQ

Melchiorre group, ICIQ

Didier Bouyssi

Univ Lyon, Université Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS, CNRS UMR 5246), F-69622 Villeurbanne, France

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“ALL FOR DRUGS” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This is a compilation for educational purposes only. P.S. : The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent

2,4-dimorpholinocyclopent-2-enone

1465003-25-1 cas

2,4-dimorpholinocyclopent-2-enone (1b):

1H NMR (300 MHz, CDCl3) 6.24 (d, J = 2.9 Hz, 1H, COC=CH), 3.78 (t, J = 4.7 Hz, 4H, morpholine), 3.73 (t, J = 4.7 Hz, 4H, morpholine), 3.73-3.72 (m, 1H, COCH2CHN), 3.15-3.14 (m, 4H, morpholine), 2.54-2.52 (m, 4H, morpholine), 2.49-2.48 (m, 1H, COCH2), 2.46-2.45 (m, 1H, COCH2);

13C NMR (75 MHz, CDCl3) 38.1, 48.1, 50.0, 60.3, 66.6, 67.1, 129.5, 151.7, 202.0.

Water excellent solvent for the synthesis of bifunctionalized cyclopentenones from furfural

M. Nardi,*ab  P. Costanzo,c  A. De Nino,a  M. L. Di Gioia,d  F. Olivito,c  G. Sindonaa  and  A. Procopioc 

*Corresponding authors

aDipartimento di Chimica, Università della Calabria, Cubo 12C, 87036-Arcavacata di Rende, Italy
E-mail: monica.nardi@unical.it
Fax: +39 0984493307
Tel: +39 0984 492850

bDipartimento di Agraria, Università Telematica San Raffaele, 247, Roma Via di Val Cannuta, Italy

cDipartimento di Scienze della Salute, Università Magna Graecia, Viale Europa, 88100-Germaneto, Italy

dDipartimento di Farmacia e Scienze della Salute e della Nutrizione, Edificio Polifunzionale, Università della Calabria, 87030 Arcavacata di Rende, Italy

Abstract

Chiral cyclopentenones are important precursors in the asymmetric synthesis of target molecules. In particular, C-2 amino cyclopentenones could be utilised as intermediates towards antitumor natural products. On the basis of our previous experience, we report an environmentally friendly protocol for the synthesis of bifunctionalized cyclopentenones in water from furfural. The use of water and MW gives high regioselectivity and good to excellent yields. The reaction can be realized in short times with various nucleophiles.

Monica Nardi

PostDoc

Università della Calabria , Rende · Dipartimento di Chimica e Tecnologie Chimiche - CTC

Università della Calabria

Department

• Dipartimento di Chimica e Tecnologie Chimiche - CTC

• Research experience

  • Oct 2014–present

    Visiting Lectur

    The School of Pharmacy · School of Pharmacy · Prof Steve Brocchini
    United Kingdom · London
  • Jan 2014–present

    PostDoc Position

    Università della Calabria · Department of Pharmacy, Health and Nutritional Sciences
    Italy · Rende
  • Mar 2001–Sep 2014

    PostDoc

    Università della Calabria · Department of Management
    Italy · Rende
  • Mar 2001–Dec 2013

    PostDoc Position

    Università della Calabria · Dipartimento di Chimica e Tecnologie Chimiche - CTC · Prof Giovanni Sindona
    Italy · Rende

Dipartimento di Chimica, Università della Calabria

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1 Estevão, Mónica S.; Afonso, Carlos A.M.; Tetrahedron Letters; vol. 58; nb. 4; (2017); p. 302 - 304

2  Green Chemistry; vol. 19; nb. 1; (2017); p. 164 - 168



“ORG SPECT INT” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This is a compilation for educational purposes only. P.S. : The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent