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

  

MORE........

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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(2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one

CAS 1672658-93-3

C24 H25 F O6 S, 460.52

D-Glucopyranose, 1-C-[3-[[5-(4-fluorophenyl)-2-thienyl]methyl]-4-methylphenyl]-

 

 

CAS 1809403-04-0

C24 H25 F O6 S, 460.52

D-Glucose, 1-C-[3-[[5-(4-fluorophenyl)-2-thienyl]methyl]-4-methylphenyl]-

WO2017/93949

 

 

 

(2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one    12

From the FT-IR spectra of 12 contain a signal at 1674 cm–1, this signal is strongly indicative of a carbonyl ketone being present in 12

In 13C NMR and HMBC correlations spectra, the chemical shift at 199.75 ppm was observed. Analysis of the NMR data  confirmed that the structure of 12 is a ring-opened keto form

Synthesis of (2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one 12

title compound 12 (84.23% yield) and having 99.4% purity by HPLC;

 

DSC: 160.84–166.44 °C;

 

Mass: m/z 459 (M+–H);

 

IR (KBr, cm–1): 3313, 2982, 1674.7, 1601, 1507.5, 1232.7;

 

1H NMR (600 MHz, DMSO-d6) δ 7.87 (s, 1H), 7.80 (dd, J = 1.8 Hz, 1H), 7.61–7.58 (m, 2H), 7.33 (d, J = 8.4 Hz, 1H), 7.29 (d, J = 3.6 Hz, 1H), 7.21–7.18 (m, 2H), 6.84 (d, J = 3.6 Hz, 1H), 5.17 (dd, J = 3.6, 3.0 Hz, 1H), 5.02 (d, J = 6.6 Hz, 1H), 4.57 (d, J = 4.8 Hz, 1H), 4.43–4.39 (m, 3H), 4.22 (s, 2H), 4.02–4.01 (m, 1H), 3.53–3.51 (m, 3H), 3.38–3.37 (m, 1H), 2.35 (s, 3H);

 

13C NMR (101 MHz, DMSO-d6) δ 199.7, 162.6, 160.2, 142.8, 142.1, 140.5, 138.8, 133.3, 130.5, 130.4, 130.4, 129.3, 127.2, 127.0, 127.0, 126.7, 123.5, 116.0, 115.8, 75.2, 72.3, 71.8, 71.3, 63.2, 33.2, 19.2.

 

HRMS (ESI): calcd m/zfor [C24H25FO6S + Na]+ = 483.1248, found m/z 483.1244.

 

 

 

 

 

 

 

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00281

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Synthesis of highly functional carbamates through ring-opening of cyclic carbonates with unprotected α-amino acids in water

 

Synthesis of highly functional carbamates through ring-opening of cyclic carbonates with unprotected [small alpha]-amino acids in water

Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC02862H, Paper

Peter Olsen, Michael Oschmann, Eric V. Johnston, Bjorn Akermark
Ring opening of cyclic carbonates with unprotected amino acids in water - a route to highly functional carbamates.

Synthesis of highly functional carbamates through ring-opening of cyclic carbonates with unprotected α-amino acids in water

 

Peter Olsén,*^a  Michael Oschmann,^a  Eric V. Johnston*^a  and  Björn Åkermark*^a 

 Author affiliations

*Corresponding authors

^aDepartment of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE 106 91, Stockholm, Sweden
E-mail: peter.olsen@su.se, eric@sigridthx.com, bjorn.akermark@su.se

Abstract

The present work shows that it is possible to ring-open cyclic carbonates with unprotected amino acids in water. Fine tuning of the reaction parameters made it possible to suppress the degree of hydrolysis in relation to aminolysis. This enabled the synthesis of functionally dense carbamates containing alkenes, carboxylic acids, alcohols and thiols after short reaction times at room temperature. When Glycine was used as the nucleophile in the ring-opening with four different five membered cyclic carbonates, containing a plethora of functional groups, the corresponding carbamates could be obtained in excellent yields (>90%) without the need for any further purification. Furthermore, the orthogonality of the transformation was explored through ring-opening of divinylenecarbonate with unprotected amino acids equipped with nucleophilic side chains, such as serine and cysteine. In these cases the reaction selectively produced the desired carbamate, in 70 and 50% yield respectively. The synthetic design provides an inexpensive and scalable protocol towards highly functionalized building blocks that are envisioned to find applications in both the small and macromolecular arena.
link  http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C7GC02862H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

 

 

 

Affiliation

Stockholm University

Location

• Stockholm, Sweden

Department

• Department of Organic Chemistry

Position

• PostDoc Position

Research experience

• Jun 2010–Feb 2016

  PhD Student

  KTH Royal Institute of Technology · Department of Fibre and Polymer Technology
  Sweden · Stockholm

 

 

 

 

Björn Åkermark

Education

• Jan 1962–Jun 1967

  KTH Royal Institute of Technology

  Organic Chemistry and Catalysis · PhD
  Sweden · Stockholm

Awards & achievements

• Jun 2009
   
  Award: Bror Holmberg Medal, Swedish Chemical Society
• Feb 2009
   
  Award: Ulla and Stig Holmquists Prize, Uppsala University
• Oct 1997
   
  Award: Dr hc, University D´Aix-Marseille
• Oct 1991
   
  Award: KTH Prize for Excellence in Teaching
• Oct 1978
   
  Award: Arrhenius Medal, Swedish Chemical Society
• Aug 1977
   
  Scholarship: Zorn Fellowship, Swden America Foundation
• Nov 1976
   
  Award: Letterstedt Award, Roy Swed. Acad. of Science

 

 

 

Dr. Eric Johnston, Ph.D.

Chief Technology Officer
Dr. Eric V. Johnston obtained his Master of Science degree in 2008 at the Department of Organic Chemistry, Stockholm University, Sweden. In the same year, he started his graduate studies under the supervision of Prof. Jan-Erling Bäckvall. During his PhD, he worked on the development of new homogeneous and heterogeneous transition-metal catalysts.
After receiving his PhD in 2012, he joined Prof. Samuel J. Danishefskys research group at Memorial Sloan-Kettering Cancer Center, New York, USA as a postdoctoral fellow supported by The Swedish Research Council. Here he was engaged in the total chemical synthesis of glycolsylated proteins that play important roles in modern cancer treatment.
In 2014 he returned to the Department of Organic Chemistry at Stockholm University to establish his own group. The goal of his research is to contribute new advances to the strategy and methodology for the preparation of synthetic macromolecules such as proteins, glycopeptides, sequence and length-controlled polymers. He is also a Co-Supervisor for Prof. Björn Åkermarks research group, which aims at studying and developing new homogeneous, as well as heterogeneous, water oxidation catalysts.

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