Persulfurated Coronene: A New Generation of “Sulflower”

spectroscopy, SYNTHESIS, Uncategorized Comments Off

Dec 062017

2073844-77-4

C₂₄ S_{12, 673.04}

Coroneno[1,12-cd:2,3-c‘d‘:4,5-c”d”:6,7-c”’d”’:8,9-c””d””:10,11-c””’d””’]hexakis[1,2]dithiole

A persulfurated coronene, a molecule dubbed a “sulflower” for its resemblance to a sunflower, bloomed this year. It’s the first fully sulfur-substituted polycyclic aromatic hydrocarbon and only the second member of a new class of circular heterocyclic carbon sulfide compounds, after the synthesis of octathio[8]circulene a decade ago.

Chemists hope to create other class members, including the simplest one, persulfurated benzene, for use in battery cathodes and other electronic materials.

A team led by Xinliang Feng of Dresden University of Technology and Klaus Müllen of the Max Planck Institute for Polymer Research created the sulflower (J. Am. Chem. Soc. 2017, DOI: 10.1021/jacs.6b12630).

http://pubs.acs.org/doi/abs/10.1021/jacs.6b12630

Synthesis of persulfuratedcoronene (5, PSC)

5 (82 mg) as dark red solid in 61% yield. HR-MS (HR-MALDI-TOF) m/z: Calcd. for C24S12: 671.6629; Found 671.6648 [M]+; Elem. Anal. calcd. for C24S12: C, 42.83; S, 57.17. Found: C, 42.87; S, 57.13.

Persulfurated Coronene: A New Generation of “Sulflower”

Renhao Dong^†, Martin Pfeffermann^§, Dmitry Skidin^‡, Faxing Wang^†, Yubin Fu^†, Akimitsu Narita^§, Matteo Tommasini^∥, Francesca Moresco^‡

, Gianaurelio Cuniberti^‡

, Reinhard Berger^†, Klaus Müllen^*^§

, and Xinliang Feng^*^†

^† Department of Chemistry and Food Chemistry, Center for Advancing Electronics Dresden, Technische Universität Dresden, 01062 Dresden, Germany

^§ Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany

^‡ Institute for Materials Science, Max Bergmann Center of Biomaterials, and Center for Advancing Electronics Dresden, TU Dresden, 01069 Dresden, Germany

^∥ Dipartimento di Chimica, Materiali ed Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy

J. Am. Chem. Soc., 2017, 139 (6), pp 2168–2171

DOI: 10.1021/jacs.6b12630

Publication Date (Web): January 27, 2017

*muellen@mpip-mainz.mpg.de, *xinliang.feng@tu-dresden.de

We report the first synthesis of a persulfurated polycyclic aromatic hydrocarbon (PAH) as a next-generation “sulflower.” In this novel PAH, disulfide units establish an all-sulfur periphery around a coronene core. The structure, electronic properties, and redox behavior were investigated by microscopic, spectroscopic and electrochemical methods and supported by density functional theory. The sulfur-rich character of persulfurated coronene renders it a promising cathode material for lithium–sulfur batteries, displaying a high capacity of 520 mAh g^–1 after 120 cycles at 0.6 C with a high-capacity retention of 90%

Renhao Dong

Image result for Renhao Dong DRESDEN

Research Group Leader

Renhao received his PhD in Physical Chemistry from Shandong University in 2013. Since 01/2017, he is a research group leader at the Chair for Molecular Functional Materials in TUD. His current research interest focuses on synthesis of organic 2D crystals (2D polymers/COFs/MOFs) and their applications in electronics and energy technology.

Contact

Phone: +49 – 351 / 463-40401 or -34932
Email: renhao.dong@tu-dresden.de

Prof. Xinliang Feng

Work Biography:

This is a professorship in the context of the cluster of excellence cfaed.

Xinliang Feng received his Bachelor’s degree in analytic chemistry in 2001 and Master’s degree in organic chemistry in 2004. Then he joined Prof. Klaus Müllen’s group at the Max Planck Institute for Polymer Research for PhD thesis, where he obtained his PhD degree in April 2008. In December 2007 he was appointed as a group leader at the Max-Planck Institute for Polymer Research and in 2012 he became a distinguished group leader at the Max-Planck Institute for Polymer Research.

His current scientific interests include graphene, two-dimensional nanomaterials, organic conjugated materials, and carbon-rich molecules and materials for electronic and energy-related applications. He has published more than 370 research articles which have attracted more than 25000 citations with H-index of 75.

He has been awarded several prestigious prizes such as IUPAC Prize for Young Chemists (2009), Finalist of 3rd European Young Chemist Award, European Research Council (ERC) Starting Grant Award (2012), Journal of Materials Chemistry Lectureship Award (2013), ChemComm Emerging Investigator Lectureship (2014), Highly Cited Researcher (Thomson Reuters, 2014, 2015 and 2016), Fellow of the Royal Society of Chemistry (FRSC, 2014). He is an Advisory Board Member for Advanced Materials, Journal of Materials Chemistry A, ChemNanoMat, Energy Storage Materials, Small Methods and Chemistry -An Asian Journal. He is also one of the Deputy Leaders for European communitys pilot project Graphene Flagship, Head of ESF Young Research Group “Graphene Center Dresden”, and Working Package Leader of WP Functional Foams & Coatings of GRAPHENE FLAGSHIP.

Academic Employment

12/2007-12/2012: Group Leader, Max Planck Institute for Polymer Research in Mainz, Germany
06/2010: Director of the Institute of Advanced Organic Materials, Shanghai Jiao Tong University
03/2011: Distinguished Adjunct Professorship in Shanghai Jiao Tong University, Chin
12/2012-07/2014: Distinguished Group Leader, Max Planck Institute for Polymer Research in Mainz, Germany
08/2014: W3 Chair Professor, Technische Universität Dresden, Germany

Honors and Duties

Marie Currie Fellowship (2005-2006)
Chinese Government Award for Outstanding Self-financed Students (2008)
IUPAC Prize for Young Chemists (2009)
Finalist of 3rd European Young Chemist Award (2010)
ISE (International Society of Electrochemistry) Young Investigator Award (2011)
Adjunct Professorship, China University of Geosciences (Wuhan) (2011)
Deputy Leader of one of the ten European representatives of the European community’s pilot project GRAPHENE FLAGSHIP (2012)
EU FET Young Explorer (2012)
ERC Starting Grant Award (2012)
Advisory Board Member for Advanced Materials (2013)
Journal of Materials Chemistry Lectureship Award (2013)
Advisory Board Member for Journal of Materials Chemistry A (2014)
Editorial Board Member of Chemistry – An Asian Journal (2014)
ChemComm Emerging Investigator Lectureship (2014)
Highly Cited Researcher (Thomson Reuters, 2014)
Fellow of the Royal Society of Chemistry (2014)
Highly Cited Researcher (Chemistry and Materials Science) (2015)
International Advisory Board of Energy Storage Materials (2015)
International Advisory Board of ChemNanoMat (2015)
Highly Cited Researcher (Chemistry and Materials Science, Thomson Reuters) (2016)
Head of ESF Young Research Group “Graphene Center Dresden” (2016)
Working Package Leader of WP Functional Foams & Coatings of GRAPHENE FLAGSHIP (2016)
International Advisory Board of Small Methods (2016)
Path Leader of 2.5D path within the cluster of excellence CFAED (2016)
ERC Proof-of-Concept Project Award (2017)
Small Young Innovator Award (2017)
Hamburg Science Award (2017)

Referee for:

Nature, Science, Nature Materials, Nature Nanotechnology, Nature Chemistry, Journal of the American Chemical Society, Angewandte Chemie International Edition, Nano Letters, Advanced Materials, Chemical Society Reviews, ACS Nano, Small, Chemical Communications, Chemistry of Materials, Organic Letters, Journal of the Organic Chemistry, Chemistry – A European Journal, ChemSusChem, ChemPhysChem, Macromolecular Rapid Communications, Journal of Material Chemistry, New Journal of Chemistry, Chemistry – An Asian Journal, ACS Applied Materials & Interfaces, Energy & Environmental Science, Organic Electronics and so on

Referee for research grants in NSF, US Department of Energy, ESF, ISF and Fondazione Cariparo and Fondazione CariModena.

Publications

Click to open publications list

Contact (Secretariat)

Phone: +49 351 / 463-43251
Fax: +49 351 / 463-43268
Email: sabine.strecker@tu-dresden.de

Klaus Müllen
Max-Planck-Institute for Polymer Research, Mainz, 55128, Germany

Research into energy technologies and electronic devices is strongly governed by the available materials. We introduce a synthetic route to graphenes which is based upon the cyclodehydrogenation (“graphitization”) of well-defined dendritic (3D) polyphenylene precursors. This approach is superior to physical methods of graphene formation such as chemical vapour deposition or exfoliation in terms of its (i) size and shape control, (ii) structural perfection, and (iii) processability (solution, melt, and even gas phase). The most convincing case is the synthesis of graphene nanoribbons under surface immobilization and in-situ control by scanning tunnelling microscopy.
Columnar superstructures assembled from these nanographene discs serve as charge transport channels in electronic devices. Field-effect transistors (FETs), solar cells, and sensors are described as examples.
Upon pyrolysis in confining geometries or “carbomesophases”, the above carbon-rich 2D- and 3D- macromolecules transform into unprecedented carbon materials and their carbon-metal nanocomposites. Exciting applications are shown for energy technologies such as battery cells and fuel cells. In the latter case, nitrogen-containing graphenes serve as catalysts for oxygen reduction whose efficiency is superior to that of platinum.

Müllen, K., Rabe, J.R., Acc. Chem. Res. 2008, 41, (4), 511-520;
Wang, X., Zhi, L., Müllen, K. Nano. Lett. 2008, 8, 323-327;
Feng, X.; Chandrasekhar, N.; Su, H. B.; Müllen, K., Nano. Lett. 2008, 8, 4259.;
Pang, S.; Tsao, H. N.; Feng, X.; Müllen, K., Adv. Mater. 2009, 31, 3488;
Feng, X., Marcon, V., Pisula, W., Hansen, M.R., Kirkpatrick, I., Müllen, K., Nature Mater. 2009, 8, 421;
Cai, J., Ruffieux, P., Jaafar, R., Bieri, M., Braun, T., Blankenburg, S., Muoth, M., Seitsonen, A. P., Saleh, M., Feng, X., Müllen, K., Fasel, R., Nature 2010, 466, 470-473;
Yang, S., Feng, X., Zhi, L., Cao, Q., Maier, J., Müllen, K., Adv. Mater. 2010, 22, 838; Liu, R., Wu, D., Feng, X., Müllen, K., Angew. Chem. Int. Ed. 2010, 49, 2565;
Käfer, D., Bashir, A., Dou, X., Witte, G., Müllen, K., Wöll, C., Adv. Mater. 2010, 22, 384;
Diez-Perez, I., Li, Z., Hihath, J., Li, J., Zhang, C., X., Zang, L., Dai, Y., Heng, X., Müllen, K., Tao, N. J. Nature Commun. 2010, DOI: 10.1038.

Prof. Dr. Klaus Müllen
joined the Max-Planck-Society in 1989 as one of the directors of the Max-Planck Institute for Polymer Research. He obtained a Diplom-Chemiker degree at the University of Cologne in 1969 after work with Professor E. Vogel. His Ph.D. degree was granted by the University of Basel, Switzerland, in 1972 where he undertook research with Professor F. Gerson on twisted pi-systems and EPR spectroscopic properties of the corresponding radical anions. In 1972 he joined the group of Professor J.F.M. Oth at the Swiss Federal Institute of Technology in Zürich where he worked in the field of dynamic NMR spectroscopy and electrochemistry. He received his habilitation from the ETH Zürich in 1977 and was appointed Privatdozent. In 1979 he became a Professor in the Department of Organic Chemistry, University of Cologne, and accepted an offer of a chair in Organic Chemistry at the University of Mainz in 1983. He received a call to the University of Göttingen in 1988.

////////////////////

S1Sc6c8c1c9SSc%10c2SSc%13c2c%11c4c3c%13SSc3c%12SSc7c%12c4c(c5c7SSc56)c8c%11c9%10

http://pubs.acs.org/doi/abs/10.1021/jacs.6b12630

https://cen.acs.org/articles/95/i49/molecules-of-the-year-2017.html?utm_source=Twitter&utm_medium=Social&utm_campaign=CEN&hootPostID=ea1deb5464b6231122901a3321f4ff5e

“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

Highly active, separable and recyclable bipyridine iridium catalysts for C–H borylation reactions

spectroscopy, SYNTHESIS, Uncategorized Comments Off

Nov 212017

Graphical abstract: Highly active, separable and recyclable bipyridine iridium catalysts for C–H borylation reactions

Highly active, separable and recyclable bipyridine iridium catalysts for C–H borylation reactions

Hind Mamlouk,^a Jakkrit Suriboot,^b Praveen Kumar Manyam,^a Ahmed AlYazidi,^a David E. Bergbreiter*^b and Sherzod T. Madrahimov*^a

*Corresponding authors

^aDepartment of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
E-mail: sherzod.madrahimov@qatar.tamu.edu

^bDepartment of Chemistry, Texas A&M University, College Station, USA
E-mail: bergbreiter@tamu.edu

Abstract

Iridium complexes generated from Ir(I) precursors and PIB oligomer functionalized bpy ligands efficiently catalyzed the reactions of arenes with bis(pinacolato)diboron under mild conditions to produce a variety of arylboronate compounds. The activity of this PIB bound homogeneous catalyst is similar to that of an original non-recyclable catalyst which allows it to be used under milder conditions than other reported recyclable catalysts. This oligomer-supported Ir catalyst was successfully recovered through biphasic extraction and reused for eight cycles without a loss of activity. Biphasic separation after the initial use of the catalyst led to an insignificant amount of iridium leaching from the catalyst to the product, and no iridium leaching from the catalyst was observed in the subsequent recycling runs. Arylboronate products obtained after extraction are sufficiently pure as observed by ¹H and ¹³C-NMR spectroscopy that they do not require further purification.

Hind MAMLOUK, PhD

R&D in Organic Materials Chemistry Looking for a New Challenge

3-Chloro-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)anisole (5). Transparent oil. Yield: 87%.

1H NMR (600 MHz, CDCl3) δ 7.37 (s, 1H), 7.22 – 7.16 (m, 1H), 6.99 (s, 1H), 3.82 (s, 3H), 1.34 (s, 12H);

13C NMR (101 MHz, CDCl3) δ 159.88, 134.57, 126.84, 117.71, 117.43, 84.15, 55.52, 24.82.

GCMS: RT=14.55 min, M+ = 268.1 vs MW= 268.54 g.mol-1 .

Sherzod Madrahimov

Asst. Prof.

Texas A&M University at Qa… , Doha · Science

Research experience

Aug 2015–present

Asst. Prof.

Texas A&M University at Qatar · Chemistry

Qatar · Doha
Jul 2012–Jul 2015

PostDoc Position

Northwestern University · Department of Chemistry

United States · Evanston
Aug 2007–Jul 2012

Graduate student

University of Illinois, Urbana-Champaign · Department of Chemistry

United States · Urbana

Texas A&M University at Qatar

David Bergbreiter
Professor

Contact

Department of Chemistry
Texas A&M University
College Station, TX 77843-3255

P: 979-845-3437
F: 979-845-4719
bergbreiter@chem.tamu.edu

Current Activities

Our group explores new chemistry related to catalysis and polymer functionalization using the tools and precepts of synthetic organic chemistry to prepare functional oligomers or polymers that in turn are used to either effect catalysis in a greener, more environmentally benign way or to more efficiently functionalize polymers. Often this involves creatively combining the physiochemical properties of a polymer with the reactivity of a low molecular weight compound to form new materials with new functions. These green chemistry projects involve undamental research both in synthesis and catalysis but has practical aspects because of its relevance to practical problems.

A common theme in our catalysis studies is exploring how soluble polymers can facilitate homogeneous catalysis. Homogeneous catalysts are ubiquitously used to prepare polymers, chemical intermediates, basic chemicals and pharmaceuticals. Such catalysts often use expensive or precious metals or expensive ligands or are used at relatively high catalyst loadings. The products often contain traces of these catalysts or ligands – traces that are undesirable for esthetic reasons or because of the potential toxicity of these impurities. Both the cost of these catalysts of these issues require catalyst/product separation – separations that often are inefficient and lead to chemical waste. These processes also use volatile organic solvents – solvents that have to be recovered and separated. Projects underway in our lab explore how soluble polymers can address each of these problems. Examples of past schemes that achieve this goal in a general way as highlighted in the Figure below.

We also use functional polymers to modify existing polymers. Ongoing projects involve molecular design of additives that can more efficiently modify polymers’ physical properties. We also use functional polymers in covalent layer-by-layer assembly to surface polymers’ surface chemistry. An example of this work is our use of ‘smart’ polymers that reversibly change from being water soluble cold to being insoluble and hydrophobic on heating. Such polymers’ have been used by us to prepare ‘smart’ catalysts, ‘smart’ surfaces and membranes, and to probe fundamental chemistry underlying temperature and salt-dependent protein solvation.

Jakkrit Suriboot

Research Assistant at Texas A&M University

Image result for Praveen Kumar Manyam TEXAS

Dr. Praveen Kumar

Title: Research Assistant Professor

Education: M.S., I.I.T. Roorkee
Ph.D., Panjab University Chandigarh (2008)
Visiting Fellow (w/ Prof. G. G. Balint-Kurti), Bristol University, UK
Postdoctoral Research Associate (w/ Prof. Svetlana Malinovskaya), Stevens Institute of Technology, Hoboken, NJ
Senior Postdoctoral Research Associate (w/ Prof. Seogjoo Jang), Queens College of CUNY, NY

Office: Chemistry 010

Phone: 806-742-3124

Email: praveen.kumar@ttu.edu

///////////////

“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

amcrasto@gmail.com

Gram-Scale Synthesis of Amines Bearing a gem-Difluorocyclopropane Moiety

organic chemistry, spectroscopy, SYNTHESIS Comments Off

Nov 102017

Image result for National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

Ukraine

Abstract

The synthesis of monocyclic, spirocyclic and fused bicyclic secondary amines bearing a gem-difluorocyclopropane moiety via difluorocyclopropanation of unsaturated N-Boc derivatives using the trifluoromethyl(trimethyl)silane/sodium iodide [CF₃SiMe₃-NaI] system is described. The relative order of the substrate reactivity is established. It is shown that for the reactive alkenes the standard reaction conditions can be used, whereas for the substrates with low reactivity, slow addition of the Ruppert–Prakash reagent is necessary.

Gram-Scale Synthesis of Amines Bearing a gem-Difluorocyclopropane Moiety

Authors., Pavel S. Nosik,

DOI: 10.1002/adsc.201700857

Pavel S. Nosik,a.b Andrii O. Gerasov,a Rodion O. Boiko,a Eduard Rusanov,b Sergey V. Ryabukhin,c Oleksandr O. Grygorenko,c * Dmitriy M. Volochnyukb

a Spectrum Info Ltd., Life Chemicals Inc., Murmanska Street 5, Kyiv 02094, Ukraine

b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, Ukraine

c National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

Image result for National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

* Corresponding author. E-mail: gregor@univ.kiev.ua.

Oleksandr Grygorenko

Ph D

Professor (Associate)

National Taras Shevchenko Univ… , Kiev · Faculty of Chemistry

National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

National Taras Shevchenko University of Kyiv

Department

Faculty of Chemistry

Image result for National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

Dmitriy M. Volochnyuk

Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, Ukraine

Dmitriy M. Volochnyuk was born in 1980 in Irpen, Kyiv region, Ukraine. He graduated from Kyiv State Taras Shevchenko University in 2002 and was awarded his M.S. degree in chemistry. He received his Ph.D. in organic chemistry in 2005 from the Institute of Organic Chemistry, National Academy of Sciences of Ukraine under the supervision of Dr. A. Kostyuk for research on the chemistry of enamines. At present, he divides his time between the Institute of Organic Chemisty, as Deputy Head of Organophosphorus Department and Senior Researcher, and Enamine Ltd (Kyiv, Ukraine), as Director of Chemistry. His main scientific interests are related to fluoroorganic, organophosphorus, heterocyclic and combinatorial chemistry, and multistep organic synthesis. He is a coauthor of more than 80 papers

Given that the incorporation of small fluorinated fragments in drug-like molecules continues to rise, this has created an onus on the synthetic community to provide robust, scalable routes to these molecules of interest. Grygorenko and co-workers have reported on a synthesis of amines featuring a gem-difluorocyclopropane moiety using the readily available Ruppert–Prakash reagent ( Adv. Synth. Catal. 2017, 10.1002/adsc.201700857).
Evaluating a series of olefins under the standard reaction conditions in refluxing THF indicated that only the most reactive olefins (gem-disubstituted) provided good yields of the desired cyclopropane, while other solvents proved to be ineffective. Conducting a control experiment omitting the substrate demonstrated that the key issue herein was competitive decomposition of the TMSCF₃ to a series of gaseous byproducts under the reaction conditions.
Whereas continuous flow provides a potential to mitigate against this, the current report demonstrated that slow addition of the reagent to the reaction mixture also provided a practical solution to this problem.
Employing this approach enabled not only excellent conversions and yields to be realized but also allowed reactivity trends to be identified. In general, gem-disubstituted are the most reactive with the trend correlating with steric hindrance.
For other classes of olefins, electronics are the major factor with the ability of the substituents to stabilize a positive charge in the transition state consistent with a nonsynchronous formation of the two sigma bonds in the cycloaddition the key consideration. The removal of the Boc-protecting group under standard acidic conditions provided the amines as their hydrochloride salts.
Eduard Rusanov

PhD

Head of Crystallographic Lab./Director of the crystallographic facility Nat. Acad. of Sci. Ukraine ‘Single Mjlecule Crystallography’ at IOC

Institute of Organic Chemistry… · DEPARTMENT OF PHYSICOCHEMICAL INVESTIGATIONS

tert-Butyl 1,1-difluoro-6-azaspiro[2.5]octane-6-carboxylate (10a):

Yield: 66.7 g (91%) (Method A); off-white crystalline powder: mp 46–48 8C;

1H NMR (CDCl3 , 400 MHz): d= 3.57–3.42 (m, 2H), 3.40–3.27 (m, 2H), 1.66–1.47 (m, 4H), 1.44 (s, J=2.3 Hz, 9H), 1.08 (t, J=8.3 Hz, 2H);

13C NMR (CDCl3, 101 MHz): d=154.2, 115.4 (t, J=288.1 Hz), 79.3, 42.8, 28.4, 28.1, 26.8 (t, J=10.0 Hz), 21.0 (t, J=10.1 Hz);

19F NMR (CDCl3 , 376 MHz): d=@140.6;

MS (EI): m/z= 247 (M+ ), 192 (M+@t-Bu), 174 (M+@t-BuO), 147 (M+@Boc), 127 (M+@Boc@HF);

Anal. calcd. for C12H19F2NO2 : C 58.29, H 7.74, N 5.66; found: C 58.49, H 8.02, N 5.30.

//////////////

2-Phenylfuran

spectroscopy, SYNTHESIS Comments Off

Nov 092017

2-Phenylfuran

17113-33-6 cas

2-Phenylfuran (3v) [15]: According to the general procedure I and purification by column chromatography (100% PE) yielded 3v (35.9 mg, 50%) and the general procedure II yielded 3s (35.1 mg, 49%) as a white solid . 1 H NMR (400 MHz, CDCl3) δ 7.68-7.66 (m 2H), 7.46 (s, 1H), 7.40-7.35 (m, 2H), 7.26-7.23 (m, 1H), 6.645-6.639 (m, 1H), 6.461-6.457 (m, 1H). LRMS (ESI) calcd for [M+H]+ C10H9O 145.1, found 145.1.

15 Zhou, C.-Y.; Chan, P. W. H.; Che, C.-M. Org. Lett. 2006, 8, 325.

Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides

Yannan Cheng, Xiangyong Gu, and Pixu Li*

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, 199 RenAi Road, Suzhou, Jiangsu 215123, China

Org. Lett., 2013, 15 (11), pp 2664–2667

DOI: 10.1021/ol400946k

lipixu@suda.edu.cn

Abstract

Direct arylation of unactivated arenes or heteroarenes with aryl halides could be carried out in the presence of potassium tert-butoxide and dimethyl sulfoxide under visible-light irradiation. Ir(ppy)₃was found to be an effective photoredox catalyst for this reaction. The reactions of aryl iodides occurred at room temperature. Elevated temperature was required for aryl bromides. Homolytic aromatic substitution was proposed to be the operative reaction pathway.

Predicts

1H NMR

13C NMR

//////////////////

http://pubs.acs.org/doi/10.1021/ol400946k

more info

1H NMR spectrum of C10H8O in CDCL3 at 400 MHz. Click to toggle size.

Shifts

Index	Name	Shift (ppm)
19	H7	6.582
1	H1	7.655
5	H5	7.655
15	H6	6.885
11	H2	7.415
7	H4	7.415
9	H3	7.362
17	H8	7.471

“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

Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents

spectroscopy, SYNTHESIS, Uncategorized Comments Off

Nov 092017

Zhong-Xia WANG

N,N-dimethyl-4-biphenylamine

(1) N,N-dimethyl-[1,1′-biphenyl]-4-amine (3a) 5,6

Elute: EtOAc/petroleum ether: 1/100 (v/v), white solid, yield 97.8 mg (99%).

1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 8.8 Hz, 2H), 7.40 (t, J = 7.7 Hz, 2H), 7.30–7.21 (m, 1H), 6.81 (d, J = 8.8 Hz, 2H), 3.00 (s, 6H).

13C NMR (101 MHz, CDCl3): δ 150.09, 141.34, 129.37, 128.78, 127.84, 126.43, 126.12, 112.90, 40.97.

5 Yang, X.; Wang, Z.-X. Organometallics 2014, 33, 5863.

(6) Stibingerova, I.; Voltrova, S.; Kocova, S.; Lindale, M.; Srogl, J. Org. Lett. 2016, 18, 312.

Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents

Bo Yang^† and Zhong-Xia Wang^*^†^‡

^† CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

^‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.7b03145

*E-mail: zxwang@ustc.edu.cn.

Abstract

Cross-coupling of (hetero)arylthiols with arylzinc reagents via C–S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg²⁺ and Li⁺ ions were demonstrated to facilitate the reaction.

In summary, we developed a transition-metal-free coupling reaction of (hetero)arylthiols with arylzinc reagents to form bi(hetero)aryls. The reaction exhibited wide substrate scope and good compatibility of functional groups. Electron-rich and -poor aryl or heteroaryl thiols can be converted. Various arylzinc reagents, including electron-rich and electron-poor reagents, can be employed as the coupling partners. Preliminary mechanistic studies suggest a nucleophilic aromatic substitution pathway, and Mg²⁺ and Li⁺ ions play important roles in the process of reaction. This study provides an example of S^2– as a leaving group in an aromatic system and an effective methodology for the synthesis of bi(hetero)aryls including pharmaceutical molecules without transition-metal impurities.

Zhong-Xia WANG


	Department：	Department of Chemistry
	Mailing Address：	Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Rd, Hefei, Anhui, 230026, PR China
	Postal Code：	230026
	Phone：	+86-551-63603043
	Fax：
	Homepage：	http://chem.ustc.edu.cn/szdw_16/bd/201210/t20121023_142877.html

Zhong-Xia Wang is a professor in the Department of Chemistry at the University of Science and Technology 
of China. He received his BS degree (1983) and MS degree (1986) from Nankai University, 
and PhD degree (1997) from the University of Sussex, UK. Since July 1986, Wang has been working 
at the University of Science and Technology of China (USTC) successively as Assistant, 
Lecturer, Associate Professor, and Professor. From Aug. 1993 to Oct. 1996, he pursued his doctoral 
studies at the University of Sussex, UK, and from Oct. 1999 to Oct. 2000, he was a Research Associate 
at the Chinese University of Hong Kong.

 学 系
Department of Chemistry

Predicts

////////////

http://pubs.acs.org/doi/10.1021/acs.orglett.7b03145

“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

An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite

spectroscopy, SYNTHESIS, Uncategorized Comments Off

Nov 032017

Image result for Kalpana C. Maheria sv

1-benzyl-2, 4, 5-triphenyl-1H-imidazole

. 1-Benzyl-2,4,5-triphenyl-1H-imidazole (5a, n = 1).

Off-white solid; m.p.: 160–162 °C;

anal. calcd. for C28H22N2: C, 87.01, H, 5.74, N, 7.25%. Found: C, 87.13, H, 5.70, N, 7.19%;

UV (λmax, ethanol) = 280 nm;

FT-IR (KBr, cm−1 ): 3060 (C–H stretch), 3031, 1600 (CN), 1497, 1483, 1447 (CC), 1352 (C–N stretch), 769, 697 (C–H band);

1 H NMR (400 MHz, DMSO): 5.16 (s, 2H, CH2), 6.74–7.67 (m, 20H, Ar–H) ppm;

13C NMR (100 MHz, DMSO): 47.6 (CH2, C8), 125.1 (CHarom, C28), 126.0 (CHarom, C26), 126.2 (CHarom, C30), 126.4 (CHarom, C11), 127.0 (CHarom, C15), 127.1 (CHarom, C16), 127.7 (CHarom, C20), 128.0 (CHarom, C21), 128.1 (CHarom, C25), 128.4 (CHarom, C13), 128.5 (CHarom, C18), 128.6 (CHarom, C27), 128.8 (C1), 128.8 (CHarom, C12), 128.9 (CHarom, C14), 130.1 (CHarom, C17), 130.3 (CHarom, C19), 130.5 (CHarom, C22), 130.7 (CHarom, C24), 131.0 (CHarom, C29), 134.4 (CHarom, C9), 135.1 (CHarom, C23), 136.8 (CHarom, C7), 137.0 (CHarom, C10), 137.2 (CHarom, C6), 145.4 (C2), 147.0 (C4) ppm;

MS: m/z = 387.5 (M + H)+

An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite

Jenifer J. Gabla,^a Sunil R. Mistry^b and Kalpana C. Maheria*^a

Jenifer J Gabla

S V National Institute of Technology, India

Jenifer J Gabla has obtained her MSc degree in Organic Chemistry, in the year 2013 from Uka Tarsadia University, Bardoli, Gujarat. She is currently pursuing her PhD in the area of solid acid catalyzed multicomponent reactions for the synthesis of biologically active drug molecules, at Applied Chemistry Department (ACD), S. V. National Institute of Technology (SVNIT) under the guidance of Kalpana Maheria, Assistant Professor & Head, ACD, SVNIT, Surat, Gujarat, India. Her research focuses on development of novel zeolite based catalytic materials and exploring their utility in the green process development for the synthesis of medicinal compounds. She has presented her research in several national and international conferences.

Kalpana C. Maheria

*Corresponding authors

^aApplied Chemistry Department, S. V. National Institute of Technology, Ichchhanath, Surat – 395007, India
E-mail:kcmaheria@gmail.com

^bMandvi Science College, Mandvi – 394160, Surat, India

Abstract

In the present study, the catalytic activity of various medium (H-ZSM-5) and large pore (H-BEA, H-Y, H-MOR) zeolites were studied as solid acid catalysts. The zeolite H-BEA is found to be an efficient catalyst for the synthesis of 1-benzyl-2,4,5-triphenyl-1H-imidazoles through one-pot, 4-component reaction (4-CR) between benzil, NH₄OAc, substituted aromatic aldehydes and benzyl amine. The hydrophobicity, Si/Al ratio and acidic properties of zeolite BEA were well improved by controlled dealumination. The synthesized materials were characterized by various characterization techniques such as XRD, ICP-OES, BET, NH₃-TPD, FT-IR, pyridine FT-IR, ²⁷Al and ¹H MAS NMR. It has been observed that the dealumination of the parent zeolite H-BEA (12) results in the enhanced strength of Brønsted acidity up to a certain Si/Al ratio which is attributed to the inductive effect of Lewis acidic EFAl species, leading to the higher activity of the zeolite BEA (15) catalyst towards the synthesis of 1-benzyl-2,4,5-triphenyl-1H-imidazoles under thermal solvent-free conditions with good to excellent yields. Using the present catalytic synthetic protocol, diverse tetra-substituted imidazoles, which are among the significant biologically active scaffolds, were synthesized in high yield within a shorter reaction time. The effect of polarity, surface acidity and extra framework Al species of the catalysts has been well demonstrated by means of pyridine FT-IR, and ²⁷Al and ¹H MAS NMR. The solvent-free synthetic protocol makes the process environmentally benign and economically viable.

Image result for S. V. National Institute of Technology, Ichchhanath, Surat

S. V. National Institute of Technology, Ichchhanath, Surat

Mandvi Science College, Mandvi – 394160, Surat, India

////////

DISCLAIMER

“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

Isosorbide dimethyl ether

PROCESS, spectroscopy, SYNTHESIS Comments Off

Oct 162017

Image result for Isosorbide dimethyl ether

CAS Registry No.:	5306-85-4
Molecular Formula:	C₈H₁₄O₄	Molecular Weight:	174.2

Image result for Isosorbide dimethyl ether SYNTHESIS

13 C NMR

22.53 MHz
C₈ H₁₄ O₄	0.05 ml : 0.5 ml CDCl₃

1H NMR

IR NEAT

RAMAN

////////

Diethyl Isosorbide (DEI)

spectroscopy, SYNTHESIS, Uncategorized Comments Off

Oct 162017

Diethyl Isosorbide (DEI): []D 20 +95.9 (c 1, in MeOH);

1H NMR (400 MHz; CDCl3; Me4Si):  4.63 (t, J = 4.2 Hz, 1H, H-4), 4.51 (d, J = 4.1 Hz, 1H, H-3), 4.06–3.90 (m, 5H, H- 1, H-2, H-5, H-6), 3.80–3.69 (m, 1H, CH2-OC-5), 3.63–3.49 (m, 4H, H-6, CH2-OC-5, CH2- OC-2), 1.23 ppm (dt, J = 17.8, 7.0 Hz, 6H, CH3CH2O-C-2, CH3CH2O-C-5);

13C NMR (101 MHz; CDCl3; Me4Si):  86.57 (C-3), 84.45 (C-2), 80.36 (C-5), 80.27 (C-4), 73.64 (C-1), 69.81 (C-6), 66.28 (CH2-O-C-5), 65.24 (CH2-O-C-2), 15.49 ppm (CH3-CH2OC-5), 15.44 (CH3-CH2OC-2);

MS (70 eV): m/z 202 (M+ , 6%), 157 (1), 113 (17), 89 (33), 69 (100), 57 (11), 44 (39).

///////////

Total synthesis of (-)-aritasone via the ultra-high pressure hetero-Diels-Alder dimerisation of (-)-pinocarvone

organic chemistry, spectroscopy, SYNTHESIS Comments Off

Oct 102017

Total synthesis of (-)-aritasone via the ultra-high pressure hetero-Diels-Alder dimerisation of (-)-pinocarvone

Org. Biomol. Chem., 2017, Advance Article

DOI: 10.1039/C7OB02204B, Paper

Maliha Uroos, Phillip Pitt, Laurence M. Harwood, William Lewis, Alexander J. Blake, Christopher J. Hayes
The total synthesis of aritasone via the proposed biosyntheic hetero-Diels-Alder [4 + 2] cyclodimerisation of pinocarvove, has been achieved under ultra-high pressure (19.9 kbar) conditions

Total synthesis of (−)-aritasone via the ultra-high pressure hetero-Diels–Alder dimerisation of (−)-pinocarvone

Maliha Uroos,^a Phillip Pitt,^b Laurence M. Harwood,^b William Lewis,^a Alexander J. Blake^a and Christopher J. Hayes*^a

Author affiliations

*Corresponding authors

^aSchool of Chemistry, University of Nottingham, University Park, Nottingham, UK
E-mail:chris.hayes@nottingham.ac.uk
Fax: +44 (0)115951 3564
Tel: +44 (0)115 951 3045

^bChemical Sciences Division, University of Reading, Whiteknights, Reading, UK

Image of Christopher Hayes

Christopher Hayes

Abstract

This paper describes a total synthesis of the terpene-derived natural product aritasone via the hetero-Diels–Alder [4 + 2] cyclodimerisation of pinocarvove, which represents the proposed biosyntheic route. The hetero-Diels–Alder dimerisation of pinocarvone did not proceed under standard conditions, and ultra-high pressure (19.9 kbar) was required. As it seems unlikely that these ultra-high pressures are accessible within a plant cell, we suggest that the original biosynthetic hypothesis be reconsidered, and alternatives are discussed.

Aritasone (1) A solution of pinocarvone (()-2) (100 mg, 0.66 mmol) in dichloromethane (5 mL) was pressurized to 19.9 kbar for 120 h. The 1H NMR spectrum of the crude reaction mixture showed significant change in the composition as compared to the starting material. The solvent was evaporated and the residue was purified by column chromatography (pentane/Et2O; 25/1) to afford aritasone (1) (20 mg, 40%) as a white solid; mp 101- 103 C; (lit3 mp 105-106 °C); []D 26 26.1 (c 0.40 in CHCl3); (lit3 []D 9 118); max/cm-1 (CHCl3) 2926, 2359, 1722, 1689, 1601, 1467, 1372, 1305, 1152; H (400 MHz; CDCl3, 298 K) 2.67 (2H, app dd, J 4.8, 2.5, H-2a, H-2b), 2.45-2.32 (3H, m, H-7a, H-15a, H-3), 2.15-2.01 (4H, m, H-10, H-12, H-15b, H-16a), 1.91-1.80 (2H, m, H-4, H-16b), 1.66 (1H, ddd, J 13.8, 6.4, 3.4, H-7b), 1.38 (3H, s, CH3), 1.29-1.22 (7H, br s, CH3, H-13a, H-13b, H-8a, H- 8b), 0.90 (3H, s, CH3), 0.80 (3H, s, CH3); C (100 MHz; CDCl3, 298 K) 209.5 (C), 142.9 (C), 112.8 (C), 80.8 (C), 45.2 (CH), 44.3 (CH), 43.7 (CH2), 40.9 (CH), 40.5 (C), 39.4 (CH), 38.3 (C), 33.2 (CH2), 32.7 (CH2), 27.7 (CH3), 27.3 (CH2), 27.3 (CH3), 26.3 (CH3), 22.5 (CH2), 22.1 (CH2), 20.9 (CH3); HRMS m/z (ES+ ) found 301.2162 (M + H) C20H29O2 requires 301.2162 and 323.1981 (M + Na) C20H28O2Na requires 323.1982. These data were consistent to those previously reported, 5, 7 however the value of the specific rotation5 differs significantly from that measured during the original isolation work.3

Image of Christopher Hayes

Christopher Hayes

Contact

Room C16 School of Chemistry
University Park
Nottingham
NG7 2RD
UK
0115 951 3045
0115 951 3564
chris.hayes@nottingham.ac.uk
http://www.nottingham.ac.uk/~pczcjh/Homepage.html

Biography

Prof. Christopher Hayes began his academic career here in Nottingham with his B.Sc. in July 1992. Remaining at Nottingham, he completed his Ph.D. studies in organic chemistry, under the supervision of Professor Gerald Pattenden, in September 1995. In January 1996, on a NATO Postdoctoral Fellowship, he moved to the University of California at Berkeley where he worked in the group of Professor Clayton H. Heathcock. In September 1997, he returned to Nottingham as a Lecturer in Organic Chemistry, and has subsequently been promoted to Reader (2003), Associate Professor (2006) and Professor of Organic Chemistry (2011).

Research Summary

Research is centred in main-stream synthetic organic chemistry, focusing on the organic chemistry of biologically active molecules. His current research interests span a number of areas such as (i)… read more

Recent Publications

NICOLLE, SIMON M., LEWIS, WILLIAM, HAYES, CHRISTOPHER J. and MOODY, CHRISTOPHER J., 2016. Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N-H Insertion Reaction of Metallocarbenes with -Aminoketone Derivatives: Angewandte Chemie-International Edition Angewandte Chemie-International Edition. 55(11), 3749-3753
BARTON, NAOMI A., MARSH, BENJAMIN J., LEWIS, WILLIAM, NARRAIDOO, NATHALIE, SEYMOUR, GRAHAM B., FRAY, RUPERT and HAYES, CHRISTOPHER J., 2016. Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?: Chemical Science Chemical Science. 7(5), 3102-3107
PALFRAMAN, MATTHEW J., ALHARTHY, RIMA D., POWALOWSKA, PAULINA K. and HAYES, CHRISTOPHER J., 2016. Synthesis of triazole-linked morpholino oligonucleotides via Cu-I catalysed cycloaddition: Organic & Biomolecular Chemistry Organic & Biomolecular Chemistry. 14(11), 3112-3119
NICOLLE, SIMON M., HAYES, CHRISTOPHER J. and MOODY, CHRISTOPHER J., 2015. Alkyl Halide-Free Heteroatom Alkylation and Epoxidation Facilitated by a Recyclable Polymer-Supported Oxidant for the In-Flow Preparation of Diazo Compounds: Chemistry-a European Journal Chemistry-a European Journal. 21(12), 4576-4579

View all publications

//////////////(-)-aritasone

A green route for methanol carbonylation

spectroscopy, SYNTHESIS Comments Off

Oct 092017

A green route for methanol carbonylation

Catal. Sci. Technol., 2017, Advance Article
DOI: 10.1039/C7CY01621B, Paper

Youming Ni, Lei Shi, Hongchao Liu, Wenna Zhang, Yong Liu, Wenliang Zhu, Zhongmin Liu
Halide-free and noble metal-free pyridine-modified H-mordenites exhibit high stability and selectivity in methanol carbonylation to acetic acid.

http://pubs.rsc.org/en/Content/ArticleLanding/2017/CY/C7CY01621B?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2Fcy+%28RSC+-+Catalysis+Science+%26+Technology+latest+articles%29#!divAbstract

A green route for methanol carbonylation

Youming Ni,^a^b Lei Shi,^a^b Hongchao Liu,^a^b Wenna Zhang,^a^b^c Yong Liu,^a^b Wenliang Zhu*^a^b and Zhongmin Liu*^a^b

Author affiliations

*Corresponding authors

^aNational Engineering Laboratory for Methanol to Olefins, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
E-mail: wlzhu@dicp.ac.cn, liuzm@dicp.ac.cn

^bDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, PR China

^cUniversity of Chinese Academy of Sciences, Beijing 100049, PR China

Abstract

Acetic acid is one of the most important bulk commodity chemicals and is currently manufactured by methanol carbonylation reactions with rhodium or iridium organometallic complexes and halide-containing promoters named Monsanto or BP Cativa™ homogeneous processes, respectively. Developing a halide-free catalyst and a heterogeneous process for methanol carbonylation is of great importance and has recently attracted extensive research attention. Here, we report a green route for direct synthesis of acetic acid via vapor-phase carbonylation of methanol with a stable, selective, halide-free, and noble metal-free catalyst based on pyridine-modified H-mordenite zeolite. Methanol conversion and acetic acid selectivity can reach up to 100% and 95%, respectively. Only little deactivation is observed during the 145 hour reaction.

////////////