A robust and recyclable polyurea-encapsulated copper(I) chloride for one-pot ring-opening/Huisgen cycloaddition/CO2 capture in water

Green Chem., 2016, 18,6357-6366
DOI: 10.1039/C6GC01956K, Paper
Yun Chen, Wei-Qiang Zhang, Bin-Xun Yu, Yu-Ming Zhao, Zi-Wei Gao, Ya-Jun Jian, Li-Wen Xu
One-pot ring-opening/Huisgen cycloaddition reactions combined with CO2 capture were carried out successfully in the presence of polyurea-encapsulated CuCl.
A robust and recyclable polyurea-encapsulated copper(I) chloride for one-pot ring-opening/Huisgen cycloaddition/CO2 capture in water
Yun Chen,a Wei-Qiang Zhang,a Bin-Xun Yu,a Yu-Ming Zhao,a Zi-Wei Gao,*a Ya-Jun Jiana and Li-Wen Xu*ab
*Corresponding authors
aKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education (MOE) and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. China
E-mail: liwenxu@hznu.edu.cn, zwgao@snnu.edu.cn
bKey Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, No 1378, Wenyi West Road, Science Park of HZNU, Hangzhou 311121, P. R. China
Green Chem., 2016,18, 6357-6366
DOI: 10.1039/C6GC01956K
Multicomponent ring-opening/Huisgen cycloaddition reactions combined with CO2 capture with a polyurea-encapsulated copper salt as a catalyst that in situ formed from simple CuCl and soluble polyurea during the reaction were carried out successfully for the synthesis of β-hydroxytriazoles under exceptionally mild conditions, in which the polyurea-encapsulated copper(I) chloride proved to be a robust and recyclable catalyst system with high yields as well as excellent chemoselectivity in this reaction.
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////////A robust and recyclable,  polyurea-encapsulated, copper(I) chloride,  one-pot,  ring-opening/Huisgen cycloaddition/CO2 capture in water

Metal-free annulation/aerobic oxidative dehydrogenation of cyclohexanones with o-acylanilines: efficient syntheses of acridines

 

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02396G, Communication
Gopal Chandru Senadi, Ganesh Kumar Dhandabani, Wan-Ping Hu, Jeh-Jeng Wang
We have identified metal-free reaction conditions for the annulation/aerobic oxidative dehydrogenation of cyclohexanones with o-acylanilines to the corresponding acridine derivatives.
Metal-free annulation/aerobic oxidative dehydrogenation of cyclohexanones with o-acylanilines: efficient syntheses of acridines

Metal-free annulation/aerobic oxidative dehydrogenation of cyclohexanones with o-acylanilines: efficient syntheses of acridines

*Corresponding authors
aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, No. 100, Shiquan 1st Rd, Sanmin District, Kaohsiung City, Taiwan
E-mail: jjwang@kmu.edu.tw
bDepartment of Biotechnology, Kaohsiung Medical University, No. 100, Shiquan 1st Rd, Sanmin District, Kaohsiung City, Taiwan
Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02396G, http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02396G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

gopal chandru Senadi
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link……click

We have identified metal-free reaction conditions for the annulation/aerobic oxidative dehydrogenation of cyclohexanones with o-acylanilines to the corresponding acridine derivatives. The combination of trifluoroacetic acid (TFA), tert-butyl hydroperoxide (TBHP), dimethylsulfoxide (DMSO) and oxygen (O2) converted the cyclohexanone derivatives to an aromatic aryl product in moderate to good yields. The experimental results suggest that this process involves an aza-allyl oxidation intermediate.

Prof. Jeh-Jeng Wang

Professor
Department of Medicinal and Applied Chemistry
Kaohsiung Medical University
Kaohsiung, Taiwan

Lab: N842, Bioorganic chemistry Laboratory
Email: jjwang@kmu.edu.tw
Tel: +886-7-3121101
Fax: 886-7-3125339

Click here to see my official Faculty page at KMU

Click here to email me

Prof. Jeh-Jeng Wang

Education:

B.S., Chemistry, National Chung-Hsing University, Taiwan (1975-1979)

Ph.D., Chemistry, The Ohio State University, USA (1983-1989)

Career:

Teaching Assistant, National Chung-Hsing University, Taiwan (1981-1983)

Postdoctoral fellow, College of Pharmacy, University of Texas, Austin, USA (1989-1991)

Associate Professor, Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Taiwan (1991-2001)

Professor, Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Taiwan (since 2001)

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3aa as a pale yellow solid (234 mg, 92%); m.p. 181-182 ° C; IR (neat)max: 1362 cm -1; 1 H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.8 Hz, 2H), 7.76 (ddd, J = 8.0, 6.8, 1.6 Hz, 2H), 7.72 (d, J = 8.8 Hz, 2H), 7.66 – 7.56 (m, 3H), 7.49 – 7.41 (m, 4H);

13C NMR (101 MHz, CDCl3) δ 148.66, 147.24, 135.85, 130.37, 129.96, 129.45, 128.40, 128.31, 12

1H NMR

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//////////Metal-free annulatio, erobic oxidative dehydrogenation, cyclohexanones, o-acylanilines, acridines

Prof. J.J. Wang birthday party – October 21, 2016

 

Department of Medicinal and Applied Chemistry
Kaohsiung Medical University

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Asymmetric synthesis of (S)-phenylacetylcarbinol – closing a gap in C–C bond formation

 

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC01803C, Communication
Torsten Sehl, Saskia Bock, Lisa Marx, Zaira Maugeri, Lydia Walter, Robert Westphal, Constantin Vogel, Ulf Menyes, Martin Erhardt, Michael Muller, Martina Pohl, Dorte Rother
By the combination of biocatalyst design and reaction engineering, the so far not stereoselectively accessible (S)-phenylacetylcarbinol could be enzymatically synthesized with product concentrations >48 g L-1 and an enantiomeric excess up to 97%.
Asymmetric synthesis of (S)-phenylacetylcarbinol – closing a gap in C-C bond formation

Asymmetric synthesis of (S)-phenylacetylcarbinol – closing a gap in C–C bond formation

*Corresponding authors
aInstitute of Bio- and Geosciences, IBG-1: Biotechnology, Forschungszentrum Jülich GmbH, Leo-Brandt-Str. 1, 52425 Jülich, Germany
E-mail: do.rother@fz-juelich.de
bHERBRAND PharmaChemicals GmbH, Brambachstr. 31, 77723 Gegenbach, Germany
cAlbaNova University Center, Royal Institute of Technology – School of Biotechnology, Roslagstull 21, Stockholm, Sweden
d
Institute of Pharmaceutical Sciences, Albert-Ludwigs-University Freiburg, Albertstrasse 25, 79104 Freiburg, Germany
e
Merz Pharma GmbH & Co. KGaA, Am Pharmapark, D-06861 Dessau-Rosslau, Germany
f
Institute of Technical Biochemistry, University of Stuttgart, Allmandring 31, 70569 Stuttgart, Germany
g
TRUMPF GmbH+Co.KG, Ditzingen Johann-Maus-Straße 2, 71254 Ditzingen, Germany
h
Enzymicals AG, Walther-Rathenau-Str 49a, 17489 Greifswald, Germany
Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC01803C

(S)-Phenylacetylcarbinol [(S)-PAC] and its derivatives are valuable intermediates for the synthesis of various active pharmaceutical ingredients (APIs), but their selective synthesis is challenging. As no highly selective enzymes or chemical catalysts were available, we used semi-rational enzyme engineering to tailor a potent biocatalyst to be >97% stereoselective for the synthesis of (S)-PAC. By optimizing the reaction and process used, industrially relevant product concentrations of >48 g L−1 (up to 320 mM) were achieved. In addition, the best enzyme variant gave access to a broad range of ring-substituted (S)-PAC derivatives with high stereoselectivity, especially for meta-substituted products.
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///////////Asymmetric synthesis, (S)-phenylacetylcarbinol, C-C bond formation

Algae-mediated biosynthesis of inorganic nanomaterials as a promising route in nanobiotechnology – a review

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02346K, Critical Review
Si Amar Dahoumane, Mourad Mechouet, Kushlani Wijesekera, Carlos D. M. Filipe, Clemence Sicard, Dennis A. Bazylinski, Clayton Jeffryes
This review presents an exhaustive and in-depth description of inorganic nanoparticle biosynthesis from photosynthetic organisms, known mechanisms and bio-applications.

Algae-mediated biosynthesis of inorganic nanomaterials as a promising route in nanobiotechnology – a review

Algae-mediated biosynthesis of inorganic nanomaterials as a promising route in nanobiotechnology – a review

*Corresponding authors
aSchool of Biological Sciences & Engineering, Yachay Tech University, Hacienda San José, San Miguel de Urcuquí, Ecuador
E-mail: sdahoumane@yachaytech.edu.ec
bLaboratoire de Physique et Chimie des Matériaux, Université Mouloud Mammeri, Route de Hasnaoua, Tizi-Ouzou, Algeria
cDepartment of Chemical Engineering, McMaster University, 1280 Main St. W., Hamilton, Canada
dInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin-en-Yvelines, Université Paris Saclay, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France
eSchool of Life Sciences, University of Nevada at Las Vegas, 4505 S. Maryland Pkwy., Las Vegas, USA
fNanobiomaterials and Bioprocessing (NAB) Laboratory, Dan F. Smith Department of Chemical Engineering, Lamar University, PO Box 10009, Beaumont, USA
E-mail: cjeffryes@lamar.edu
Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02346K, http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02346K?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Promising nanotechnological platforms, based on inorganic nanoparticles and nanomaterials, have emerged in such fields as targeted drug delivery, bio- and chemical sensing, catalysis, antimicrobial coatings, and optoelectronic devices, among others. However, concerns regarding the sustainability of physicochemically-synthesized nanomaterials, which often require energy-intensive processes, high temperatures, toxic solvents or undesirable chemical wastes, have also emerged. Researchers have therefore looked to replace chemical syntheses by sustainable and environmentally friendly techniques. Biosynthesis of nanomaterials, i.e., the use of living organisms, their components, extracts or biomolecules, as catalysts for the sustainable production of nanomaterials, has experienced a tremendous expansion during the last two decades. Among these production platforms, the roles of algae have attracted increasing attention from research scientists worldwide. The aim of the present review, the first of its kind, is to provide important information to readers regarding the diversity of algal strains exploited in the booming field of nanobiotechnology and green chemistry, the various methodologies through which these diverse organisms are used, the variety of fabricated nanomaterials composed of noble metals, oxides and chalcogenides, and the significance of the large range of sizes and shapes of these nanomaterials that confer to them unique properties desirable for specific bio-applications.

 

////////Algae-mediated biosynthesis, inorganic nanomaterials, promising route, nanobiotechnology, review

Solvent- and halide-free synthesis of pyridine-2-yl substituted ureas through facile C-H functionalization of pyridine N-oxides

Solvent- and halide-free synthesis of pyridine-2-yl substituted ureas through facile C-H functionalization of pyridine N-oxides

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02556K, Paper

Valentin A. Rassadin, Dmitry P. Zimin, Gulnara Z. Raskil’dina, Alexander Yu. Ivanov, Vadim P. Boyarskiy, Semen S. Zlotskii, Vadim Yu. Kukushkin

A solvent- and halide-free atom-economical synthesis of practically useful pyridine-2-yl substituted ureas utilizes pyridine N-oxides and dialkylcyanamides.

Solvent- and halide-free synthesis of pyridine-2-yl substituted ureas through facile C–H functionalization of pyridine N-oxides

 *Corresponding authors

aInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russia

bUfa State Petroleum Technological University, Kosmonavtov 1, Ufa, Bashkortostan, Russia

cResearch Park SPbSU, Center for Magnetic Resonance, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russia

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02556K

A novel solvent- and halide-free atom-economical synthesis of practically useful pyridine-2-yl substituted ureas utilizes easily accessible or commercially available pyridine N-oxides (PyO) and dialkylcyanamides. The observed C–H functionalization of PyO is suitable for the good-to-high yielding synthesis of a wide range of pyridine-2-yl substituted ureas featuring electron donating and electron withdrawing, sensitive, or even fugitive functional groups at any position of the pyridine ring (63–92%; 19 examples). In the cases of 3-substituted PyO, the C–H functionalization occurs regioselectively providing a route for facile generation of ureas bearing a 5-substituted pyridine-2-yl moiety.

1,1-Dimethyl-3-(pyridin-2-yl)urea

1,1-Dimethyl-3-(pyridin-2-yl)urea (4a)3 : From pyridine 1-oxide (1a) (95.0 mg, 1.00 mmol) and dimethylcyanamide (2a) (105 mg, 1.50 mmol), compound 4a (147 mg, 89%) was obtained according to GP1 as a yellow oil, which was then crystalized in the freezer to give pale yellow solid, m.p. = 42.6–43.5 °C, lit.4 m.p. = 44–47 °C (EtOAc/hexane), Rf = 0.25 (EtOAc). 1H NMR (400 MHz, CDCl3): δ = 3.00 (s, 6 H, NCH3), 6.88 (ddd, J = 7.3, 5.0, 0.9 Hz, 1 H), 7.30 (br. s, 1 H), 7.60 (ddd, J = 8.5, 7.3, 1.9 Hz, 1 H), 8.02 (dt, J = 8.5, 0.9 Hz, 1 H), 8.14 (ddd, J = 5.0, 1.9, 0.9 Hz, 1 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 36.3 (2 С, CH3), 113.0 (CH), 118.1 (CH), 138.0 (CH), 147.3 (CH), 152.8 (C), 154.8 (C) ppm. NMR data are consistent with previously reported.3 HRMS (ESI), m/z: [M + H]+ calcd. for C8H12N3O+ : 166.0975; found: 166.0977.

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A catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles: an easy access to five-ring-fused tetrahydroisoquinolines

A catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles: an easy access to five-ring-fused tetrahydroisoquinolines

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02517J, Communication

Xihong Liu, Dongxu Yang, Kezhou Wang, Jinlong Zhang, Rui Wang

A catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles has been reported under mild conditions.

A catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles: an easy access to five-ring-fused tetrahydroisoquinolines

Xihong Liu,a   Dongxu Yang,a   Kezhou Wang,a  Jinlong Zhanga and   Rui Wang*ab  

*Corresponding authors

aSchool of Life Sciences, Institute of Biochemistry and Molecular Biology, Lanzhou University, Lanzhou 730000, P. R. China

bState Key Laboratory of Chiroscience, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Kowloon, P. R. China

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02517J

We have reported herein a catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles by which a series of five-ring-fused tetrahydroisoquinolines featuring an indoline scaffold were obtained as single diastereomers in moderate to high yields without any additives under mild conditions. Moreover, the current method provides a novel and convenient approach for the efficient incorporation of two biologically important scaffolds (tetrahydroisoquinoline and indoline).

ethyl 13b-nitro-8-tosyl-8,8a,13b,13c-tetrahydro-5H-indolo[2′,3′:3,4]pyrazolo[5,1- a]isoquinoline-9(6H)-carboxylate

ethyl 13b-nitro-8-tosyl-8,8a,13b,13c-tetrahydro-5H-indolo[2′,3′:3,4]pyrazolo[5,1- a]isoquinoline-9(6H)-carboxylate:

White solid, m.p. 153 – 154 oC; 94% yield; 1H NMR (300 MHz, CDCl3) δ 7.86 (d, J = 8.2 Hz, 2H), 7.78 (d, J = 7.9 Hz, 1H), 7.30 – 7.13 (m, 5H), 7.1 (s, 1H), 7.05 – 6.94 (m, 1H), 6.94 – 6.87 (m, 1H), 6.59 (t, J = 7.6 Hz, 3H), 6.28 (d, J = 7.6 Hz, 1H), 4.78 (s, 1H), 4.37 (q, J = 7.1 Hz, 2H), 2.80 – 2.58 (m, 2H), 2.33 (s, 3H), 2.31 – 2.11 (m, 2H), 1.41 (t, J = 7.1 Hz, 3H) ppm;

13C NMR (75 MHz, CDCl3) δ 152.1, 144.6, 142.6, 134.0, 132.1, 129.3, 129.0, 128.7, 128.3, 127.5, 127.3, 126.2, 122.8, 121.1, 115.5, 104.5, 84.9, 70.7, 62.8, 48.5, 29.1, 21. 6, 14.3 ppm;

HRMS (ESI): C27H26N4NaO6S [M + Na]+ calcd: 557.1465, found: 557.1476.

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Simultaneous rapid reaction workup and catalyst recovery

Simultaneous rapid reaction workup and catalyst recovery

Green Chem., 2016, 18,5769-5772

DOI: 10.1039/C6GC02448C, Communication

Zhichao Lu, Zofia Hetman, Gerald B. Hammond, Bo Xu

By combining reaction work-up and catalyst recovery into a simple filtration procedure we have developed a substantially faster technique for organic synthesis.

By combining reaction work-up and catalyst recovery into a simple filtration procedure we have developed a substantially faster technique for organic synthesis. Our protocol eliminates the time-consuming conventional liquid–liquid extraction and is capable of parallelization and automation. Additionally, it requires only minimal amounts of solvent.

Simultaneous rapid reaction workup and catalyst recovery

Zhichao Lu,a   Zofia Hetman,a   Gerald B. Hammond*a and  Bo Xu*b  

 *Corresponding authors

aDepartment of Chemistry, University of Louisville, Louisville, USA

bCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai 201620, China

E-mail: bo.xu@dhu.edu.cn

Green Chem., 2016,18, 5769-5772

DOI: 10.1039/C6GC02448C

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02448C?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

. General procedure for a reaction Step 1. Reaction setup. The reaction is conducted in the usual way with the supported catalyst. Porelite® (typically 1 mL for every 0.1 gram of product) is added to the reaction mixture under stirring, Step 2. Reaction quench and rigid solvent extraction. If needed, the reaction is quenched with a suitable aqueous solution (e.g. NaHCO3 solution). • If the solvent used in the reaction is water-miscible (eg., DMF, methanol, etc.), a minimum amount of water immiscible solvent (e.g. 3 mL ether for every 1 g of product) is added to help organic material become entrenched in Porelite. • If the reaction is conducted in a water immiscible solvent (e.g. toluene, DCM), no extra solvent is needed in most cases. The excess amount of solvent is removed by rotavapor or by nitrogen/air purging (no need to remove the water from the mixture). The reaction mixture is filtered to remove aqueous-soluble components (starting materials, by-products, etc.) and washed with water (or HCl or Na2CO3 solution to remove basic or acidic byproducts. Vacuum is applied to dry the filtrate for 2 minutes to remove any remaining aqueous and volatile solvents. (For automatic flash chromatographic separation, an empty loading cartridge can be used, which can be directly attached to the commercial system. For manual chromatographic separation, a regular Büchner filter can be used). Step 3. Sample loading to chromatographic system. • The loading cartridge can be directly attached to the commercial flash chromatographic system (e.g., CombiFlash Rf series). • For manual chromatographic separation, the polymer powder is loaded directly onto a manual flash silica gel column (dry loading).

Because the polymer pad may contain some trapped air, it is recommended to start with the least polar solvent (e.g., hexane) during chromatographic separation to remove the trapped air.

1-(biphenyl-4-yl)ethanone

1-(biphenyl-4-yl)ethanone

Han, W.; Liu, C.; Jin, Z.-L. Organic Letters 2007, 9, 4005-4007

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