Nickel-Catalyzed Decarbonylative Suzuki–Miyaura Coupling of Amides To Generate Biaryls

Shi et al. have reported a nickel-catalyzed decarbonylative Suzuki–Miyaura reaction which uses an N-aroylpiperidine-2,6-dione as the coupling partner for the boronic acid ( Angew. Chem., Int. Ed. 2016, 55, 6959−6963).

The method is attractive from the point of view of the stability of N-aroylpyrrolidine-2,5-diones toward storage and manipulation and the flexibility they add to the chemist’s toolbox, given their preparation from a different group of precursors to aryl halides or triflates.

Notably, the reaction uses an air-stable and inexpensive nickel catalyst, and the reactions tolerate the presence of water. While a standard reaction temperature of 150 °C is quoted, the use of temperatures as low as 80 °C also seem to be possible. Coupling efficiency is reported to be adversely affected when the aromatic rings of both of the coupling partners bear electron-donating substituents.

Ortho substituents on the aromatic rings seem to be beneficial as they facilitate decarbonylation as part of the cross-coupling. Oxidative addition into the N–C(aroyl) bond of the amide is proposed as initiating the catalytic cycle and is possible on account of a reduction in the resonance stabilization of the N-aroyl functionality versus a conventional aromatic amide.

Suzuki–Miyaura Coupling

Synthesis of Biaryls through Nickel-Catalyzed Suzuki–Miyaura Coupling of Amides by Carbon–Nitrogen Bond Cleavage (pages 6959–6963)Shicheng Shi, Guangrong Meng and Prof. Dr. Michal Szostak
Version of Record online: 21 APR 2016 | DOI: 10.1002/anie.201601914

Breaking and making: The first nickel-catalyzed Suzuki–Miyaura coupling of amides for the synthesis of biaryl compounds through N−C amide bond cleavage is reported. The reaction tolerates a wide range of sensitive and electronically diverse substituents on both coupling partners.

1H NMR (500 MHz, CDCl3) δ 7.70 (s, 4 H), 7.61 (d, J = 7.3 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 2 H), 7.42 (t, J = 7.3 Hz, 1 H).


13C NMR (125 MHz, CDCl3) δ 144.87, 139.92, 129.48 (q, J F = 32.5 Hz), 129.13, 128.32, 127.56, 127.42, 125.83 (q, J F = 3.8 Hz), 124.46 (q, J F = 270.0 Hz).

19F NMR (471 MHz, CDCl3) δ -62.39.

Michal Szostakemail: michal.szostak@rutgers.edu office: Olson 204 E-mail address:michal.szostak@rutgers.edu ORCID:orcid.org/0000-0002-9650-9690 Department of Chemistry, Rutgers University, Newark, NJ, USA

Research Interests

The central theme of our research is synthetic organic and organometallic chemistry with a focus on the development of new synthetic methods based on transition metal catalysis and various aspects of transition metal mediated free radical chemistry and their application to the synthesis of biologically active molecules.

Selected Publications

1. Graphene-Catalyzed Direct Friedel-Crafts Alkylation Reactions: Mechanism, Selectivity and Synthetic Utility. Hu, F.; Patel, M.; Luo, F.; Flach, C.; Mendelsohn, R.; Garfunkel, E.; He, H.; Szostak, M. J. Am. Chem. Soc. 2015, 137 [doi]
2. General Olefin Synthesis by the Palladium-Catalyzed Heck Reaction of Amides: Sterically-Controlled Chemoselective N-C Activation. Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2015, 54[doi]
3. Aminoketyl Radicals in Organic Synthesis: Stereoselective Cyclization of 5- and 6-Membered Cyclic Imides to 2-Azabicycles using SmI₂-H₂O. Shi S.; Szostak, M. Org. Lett. 2015, 17, 5144 [doi]
4. Sterically-Controlled Pd-Catalyzed Chemoselective Ketone Synthesis via N-C Cleavage in Twisted Amides. Meng, G.; Szostak, M. Org. Lett. 2015, 17 [doi]
5. Recent Developments in the Synthesis and Reactivity of Isoxazoles: Metal Catalysis and Beyond.Hu, F.; Szostak, M. Adv. Synth. Catal. 2015, 357, 2583. [doi]
6. Determination of Structures and Energetics of Small- and Medium-Sized One-Carbon Bridged Twisted Amides using ab Initio Molecular Orbital Methods. Implications for Amidic Resonance along the C-N Rotational Pathway. Szostak, R.; Aubé, J.; Szostak, M. J. Org. Chem. 2015, 80, 7905. [doi]
7. An Efficient Computational Model to Predict Protonation at the Amide Nitrogen and Reactivity along the C-N Rotational Pathway. Szostak, R.; Aubé, J.; Szostak, M. Chem. Commun. 2015, 51, 6395.[doi]
8. Pd-Catalyzed C-H Activation: Expanding the Portfolio of Metal-Catalyzed Functionalization of Unreactive C-H Bonds by Arene-Chromium π-Complexation. Hu, F.; Szostak, M. ChemCatChem2015, 7, 1061. [doi]
9. Highly Chemoselective Reduction of Amides (Primary, Secondary and Tertiary) to Alcohols using SmI₂/H₂O/Amine under Mild Conditions. Szostak, M.; Spain, M.; Eberhart, A. J.; Procter, D. J. J. Am. Chem. Soc. 2014, 136, 2268. [doi]
10. Substrate-Directable Electron Transfer Reactions. Dramatic Rate Enhancement in the Chemoselective Reduction of Cyclic Esters using SmI₂-H₂O: Mechanism, Scope and Synthetic Utility. Szostak, M.; Spain, M.; Choquette, K. A.; Flowers, R. A., II; Procter, D. J. J. Am. Chem. Soc.2013, 135, 15702. [doi]
11. Selective Reduction of Barbituric Acids using SmI₂-H₂O: Synthesis, Reactivity and Structural Analysis of Tetrahedral Adducts. Szostak, M.; Spain, M.; Behlendorf, M; Procter, D. J. Angew. Chem. Int. Ed. 2013, 52, 12559. [doi]
12. Non-Classical Lanthanide(II) Iodides: Uncovering the Importance of Proton Donors in TmI₂-Promoted Electron Transfer. Facile C-N Bond Cleavage in Unactivated Amides. Szostak, M.; Spain, M.; Procter, D. J. Angew. Chem. Int. Ed. 2013, 52, 7237. [doi]
13. Chemistry of Bridged Lactams and Related Heterocycles. Szostak, M.; Aubé, J. Chem. Rev. 2013,113, 5701. [doi]

For more detail, please see the Szostak Group Web Site 

GROUP

Prof. Michal Szostak

Assistant Professor

Ph.D., University of Kansas (2009) with Jeffrey Aubé

Postdoctoral, Princeton University (2010) with David MacMillan

Postdoctoral, University of Manchester (2011-2014) with David Procter 

Postdoctoral Researchers

Dr. Feng Hu

Ph.D., Nanjing University, 2009 (Z. Huang)

Postdoctoral, Shanghai Institute of Materia Medica (Y. Hu)

Research Assistant Professor, SIOC (Q. Shen)

Postdoctoral, Lamar University (X. Lei) 

Dr. Pradeep Nareddy

Ph.D., University of Geneva, 2013 (C. Mazet)

Postdoctoral, Leipzig University (C. Schneider) 

Graduate Students

Shicheng Shi

M.S., SIOC, 2013 (R. Wang)

B.S., Nanjing Agriculture University, 2010 

Guangrong Meng

M.S., Fudan University, 2014 (Q. Zhang)

B.S., Dalian Medical University, 2011 

Chengwei Liu

M.S., Soochow University, 2014 (Y. Yao)

B.S., Zaozhuang University, 2011 

Undergraduate Students

Syed Huq (Rutgers, Chemistry, 2014-present)

Marcel Achtenhagen (Rutgers, Chemistry, 2015-present) 

Visiting Students

Yongmei Liu (Yangzhou University, R. Liu)

//////Nickel-Catalyzed,  Decarbonylative Suzuki–Miyaura Coupling,  Amides, Biaryls

Highlights
Modification of BHT has a significant multivariate effect on antioxidant efficiency.

BDE is the key to rational design and development of antioxidants.

Antioxidant performance of BHT is mainly depending on 13 very crucial parameters.

MPAO is a promising way to increase antioxidant and pharmacological activities.

---

Abstract

Hindered phenols find a wide variety of applications across many different industry sectors. Butylated hydroxytoluene (BHT) is a most commonly used antioxidant recognized as safe for use in foods containing fats, pharmaceuticals, petroleum products, rubber and oil industries. In the past two decades, there has been growing interest in finding novel antioxidants to meet the requirements of these industries. To accelerate the antioxidant discovery process, researchers have designed and synthesized a series of BHT derivatives targeting to improve its antioxidant properties to be having a wide range of antioxidant activities markedly enhanced radical scavenging ability and other physical properties. Accordingly, some structure–activity relationships and rational design strategies for antioxidants based on BHT structure have been suggested and applied in practice. We have identified 14 very sensitive parameters, which may play a major role on the antioxidant performance of BHT. In this review, we attempt to summarize the current knowledge on this topic, which is of significance in selecting and designing novel antioxidants using a well-known antioxidant BHT as a building-block molecule. Our strategy involved investigation on understanding the chemistry behind the antioxidant activities of BHT, whether through hydrogen or electron transfer mechanism to enable promising anti-oxidant candidates to be synthesized.

European Journal of Medicinal Chemistry

Volume 101, 28 August 2015, Pages 295–312

Review article

Understanding the chemistry behind the antioxidant activities of butylated hydroxytoluene (BHT): A review

• Wageeh A. Yehye^{a, ,} ,
• Noorsaadah Abdul Rahman^b,
• Azhar Ariffin^b,
• Sharifah Bee Abd Hamid^a,
• Abeer A. Alhadi^b,
• Farkaad A. Kadir^c,
• Marzieh Yaeghoobi^d

• ^aNanotechnology & Catalysis Research Centre, (NANOCAT), University of Malaya, Block 3A, Institute of Postgraduate Studies Building, 50603 Kuala Lumpur, Malaysia
• ^bDepartment of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
• ^cDivision of Human Biology, Faculty of Medicine, International Medical University, 57000 Kuala Lumpur, Malaysia
• ^dDrug Design and Development Research Group, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
• http://www.sciencedirect.com/science/article/pii/S022352341530101X

doi:10.1016/j.ejmech.2015.06.026

• 
  

  1st Wageeh Yehye

  University of Malaya
• 
  

  2nd Noor Rahman

  University of Malaya
• 
  

  3rd Azhar Ariffin

  University of Malaya
• 
  

  4th Sharifah Bee Abd Hamid

   University of Malaya
• 
  

  5th Abeer Abdulhadi Abdulqader

  University of Malaya
• 
  

  6th Farkaad A Kadir

  International Medical University (IMU)
• 
  

  7th Marzieh Yaeghoobi

   University of Malaya

SEE
https://www.researchgate.net/publication/278050005_ChemInform_Abstract_Understanding_the_Chemistry_Behind_the_Antioxidant_Activities_of_Butylated_Hydroxytoluene_BHT_A_Review/figures












///////////Antioxidant, Butylated hydroxytoluene, Free radical, Reactive oxygen species, Phenol

Multicomponent Multicatalyst Reactions (MC)2R:  One-Pot Synthesis of 3,4-Dihydroquinolinones Lei Zhang, Lorenzo Sonaglia, Jason Stacey, and Mark Lautens Org. Lett. 2013, 15, 2128-2131. DOI:10.1021/ol4006008 . A Rh/Pd/Cu catalyst system led to an efficient synthesis of dihydroquinolinones in one-pot, two operations. The reaction features the first triple metal-catalyzed transformations in one reaction vessel, without any intermediate workup. The conjugate-addition/amidation/amidation reaction sequence is highly modular, divergent, and practical. Multicomponent Multicatalyst Reactions (MC)2R: One-Pot Synthesis of 3,4-Dihydroquinolinones Lei Zhang, Lorenzo Sonaglia, Jason Stacey, and Mark Lautens* Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada Org. Lett., 2013, 15 (9), pp 2128–2131 DOI: 10.1021/ol4006008 Publication Date (Web): April 19, 2013 Copyright © 2013 American Chemical Society mlautens@chem.utoronto.ca http://pubs.acs.org/doi/abs/10.1021/ol4006008 Mark Lautens Mark Lautens , O.C. University Professor J. Bryan Jones Distinguished Professor AstraZeneca Professor of Organic Chemistry NSERC/Merck-Frosst Industrial Research Chair Department of Chemistry Davenport Chemical Laboratories 80 St. George St. University of Toronto Toronto, Ontario M5S 3H6 Tel: (416) 978-6083 Fax: (416) 946-8185 E-Mail: mlautens@chem.utoronto.ca Curriculum Vitae Personal Place and Date of Birth Hamilton, Ontario, Canada July 9, 1959 Education Harvard University NSERC PDF with D. A. Evans 1985 - 1987 University of Wisconsin-Madison Ph.D. with B. M. Trost 1985 University of Guelph B.Sc. - Distinction 1981 Academic Positions J. Bryan Jones Distinguished Professor University of Toronto 2013 - 2018 University Professor University of Toronto 2012 - present NSERC/Merck Frosst Industrial Research Chair NSERC/Merck Frosst 2003 - 2013 AstraZeneca Professor of Organic Synthesis University of Toronto 1998 - present Professor University of Toronto 1995 - 1998 Associate Professor University of Toronto 1992 - 1995 Assistant Professor University of Toronto 1987 - 1992 Awards & Honors University of Toronto Alumni Faculty Award University of Toronto 2016 CIC Catalysis Award CSC 2016 Officer of the Order of Canada Governor General 2014 Killam Research Fellowship Canada Council for the Arts 2013-2015 CIC Medal Chemical Institute of Canada 2013 Fellow of the Royal Society of UK Royal Society of Chemistry 2011 Pedler Award Royal Society of Chemistry 2011 Senior Scientist Award Alexander von Humboldt Foundation Berlin, Aachen and Gottingen 2009-2014 Visiting Professor University of Berlin 2009 Visiting Professor Université de Marseilles 2008 ICIQ Summer School ICIQ Tarragona, Spain 2008 Attilio Corbella Summer School Professor Italian Chemical Society 2007 Arthur C. Cope Scholar Award American Chemical Society 2006 Alfred Bader Award Canadian Society for Chemistry 2006 R. U. Lemieux Award Canadian Society for Chemistry 2004 Solvias Prize Solvias AG 2002 Fellow of the Royal Society of Canada Royal Society of Canada 2001 Areas of Research Interest and Expertise new synthetic methods metal catalyzed cycloaddition and annulation reactions asymmetric catalysis with focus on rhodium, nickel and palladium catalysts cyclopropane synthesis and reactions hydrometallation reactions reactions of organosilicon and organotin compounds fragmentation reactions new routes to medicinally/biologically interesting compounds heterocycle synthesis using metal catalysts ////////////

Heterogeneous catalytic approaches in C-H activation reactions

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00385K, Critical Review

Stefano Santoro, Sergei I. Kozhushkov, Lutz Ackermann, Luigi Vaccaro
This review summarizes the development of user-friendly, recyclable and easily separable heterogeneous catalysts for C-H activation during the last decade until December 2015.

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00385K?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Despite the undisputed advances and progress in metal-catalyzed C–H functionalizations, this atom-economical approach had thus far largely been developed with the aid of various metal catalysts that were operative in a homogeneous fashion. 

While thereby major progress was accomplished, these catalytic systems featured notable disadvantages, such as low catalyst recyclability. This review summarizes the development of user-friendly, recyclable and easily separable heterogeneous catalysts for C–H activation.

This strategy was characterized by a remarkably broad substrate scope, considerable levels of chemo- and site-selectivities and proved applicable to C–C as well as C–heteroatom formation processes. 

Thus, recyclable catalysts were established for arylations, hydroarylations, alkenylations, acylations, nitrogenations, oxygenations, or halogenations, among others. The rapid recent progress in selective heterogeneous C–H functionalizations during the last decade until December 2015 is reviewed.

Heterogeneous catalytic approaches in C–H activation reactions

Stefano Santoro,^a   Sergei I. Kozhushkov,^b  Lutz Ackermann*^b and   Luigi Vaccaro*^a  

*

Corresponding authors

^a

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto, 8 – 06123 Perugia, Italy 
E-mail: luigi.vaccaro@unipg.it
Web: http://www.dcbb.unipg.it/greensoc

^b

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstrasse 2, 37077 Göttingen, Germany 
E-mail: Lutz.Ackermann@chemie.uni-goettingen.de
Web: http://www.ackermann.chemie.uni-goettingen.de

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00385K     

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto, 8 – 06123 Perugia, Italy 
E-mail: luigi.vaccaro@unipg.it
Web: http://www.dcbb.unipg.it/greensoc

Extra clips
 C-H Activation :: Wiley-VCH Hot Topics

www.wiley-vch.de

 
 The Yu Lab

www.scripps.edu

"Ligand-Enabled Triple C-H Activation Reactions: One-Pot Synthesis of Diverse 4-Aryl-2-quinolinones from Propionamides" Angew. Chem. Int. Ed. 2014, 53, ...

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N-Butylpyrrolidinone as a dipolar aprotic solvent for organic synthesis

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00932H, Paper

James Sherwood, Helen L. Parker, Kristof Moonen, Thomas J. Farmer, Andrew J. Hunt
N-Butylpyrrolidinone (NBP) has been demonstrated as a suitable safer replacement solvent for N-Methylpyrrolidinone (NMP) in selected organic syntheses.

N-Butylpyrrolidinone as a dipolar aprotic solvent for organic synthesis

N-Butylpyrrolidinone as a dipolar aprotic solvent for organic synthesis

James Sherwood,^a   Helen L. Parker,^a   Kristof Moonen,^b  Thomas J. Farmer^a and   Andrew J. Hunt*^a  

*Corresponding authors

^aGreen Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
E-mail: andrew.hunt@york.ac.uk

^bEastman Chemical Company, Pantserschipstraat 207 – B-9000, Gent, Belgium

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00932H

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00932H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

 

Dipolar aprotic solvents such as N-methylpyrrolidinone (or 1-methyl-2-pyrrolidone (NMP)) are under increasing pressure from environmental regulation. NMP is a known reproductive toxin and has been placed on the EU “Substances of Very High Concern” list. Accordingly there is an urgent need for non-toxic alternatives to the dipolar aprotic solvents. N-Butylpyrrolidinone, although structurally similar to NMP, is not mutagenic or reprotoxic, yet retains many of the characteristics of a dipolar aprotic solvent. This work introduces N-butylpyrrolidinone as a new solvent for cross-coupling reactions and other syntheses typically requiring a conventional dipolar aprotic solvent.

////N-Butylpyrrolidinone, dipolar aprotic solvent , organic synthesis

Dehydrogenative [2 + 2 + 1] Heteroannulation Using a Methyl Group as a One-Carbon Unit: Access to Pyrazolo[3,4-c]quinolines

 

Dehydrogenative [2 + 2 + 1] Heteroannulation Using a Methyl Group as a One-Carbon Unit: Access to Pyrazolo[3,4-c]quinolines

Guo-Bo Deng^†, Hai-Bing Li^†, Xu-Heng Yang^†, Ren-Jie Song^*†, Ming Hu^†, and Jin-Heng Li^*†‡

^† State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China

^‡ State Key Laboratory of Applied Organic Chemistry Lanzhou University, Lanzhou 730000, China

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.6b00618

Publication Date (Web): April 28, 2016

Copyright © 2016 American Chemical Society

*E-mail: srj0731@hnu.edu.cn., *E-mail: jhli@hnu.edu.cn.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.6b00618

 A practical and straightforward access to pyrazolo[3,4-c]quinolines by molecular sieve mediated dehydrogenative [2 + 2 + 1] heteroannulation of N-(o-alkenylaryl)imines with aryldiazonium salts is described using a sp³-hybrid carbon atom as a one-carbon unit. The reaction enables the formation of three new chemical bonds, a C–C bond and two C–N bonds, in a single reaction and features simple operation and excellent functional group tolerance.

/////////Dehydrogenative [2 + 2 + 1] Heteroannulation,   Pyrazolo[3,4-c]quinolines

A continuous-flow process for the preparation of m-nitrothioanisole has been set up. The starting material m-nitroaniline was diazotized to give diazonium chloride, followed by azo-coupling with sodium thiomethoxide to give 1-(methylthio)-2-(3-nitrophenyl)diazene, then dediazoniated to gain m-nitrothioanisole in high yield. The continuous-flow process minimized accumulation of the energetic intermediate diazonium salt and has a better capacity for adapting large-scale production. A solvent was introduced in the azo-coupling section to create a biphasic flow system. Side products were inhibited eminently in this flow process.

Continuous-Flow Process for the Synthesis of m-Nitrothioanisole

Zhiqun Yu^†, Xiaoxuan Xie^†, Hei Dong^†, Jiming Liu^‡, and Weike Su^*†‡

^† National Engineering Research Center for Process Development of Active Pharmaceutical Ingredients, Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou 310014, P. R. China

^‡ Key Laboratory for Green Pharmaceutical Technologies and Related Equipment of Ministry of Education, College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. China

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00023

Publication Date (Web): March 24, 2016

Copyright © 2016 American Chemical Society

*Tel.: (+86)57188320899. E-mail: pharmlab@zjut.edu.cn.

http://pubs.acs.org/doi/abs/10.1021/acs.oprd.6b00023
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