trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

yellowish solid (53 mg, 66%);

m.p. = 72 °C;

1 H-NMR (600 MHz, CDCl3): δ = 6.77 – 6.71 (m, 3H), 5.94 (s, 2H), 1.63 – 1.59 (m, 4H), 1.50 (dd, J = 9.1, 5.0 Hz, 1H), 1.26 (t, J = 5.3 Hz, 1H);

13CNMR (151 MHz, CDCl3): δ = 147.80, 146.73, 136.69, 120.64, 120.23, 108.28, 108.17, 101.19, 28.75, 23.86, 21.40, 11.30;

HRMS (ESI): m/z calc. for [C12H11O2NK]: 240.0414, found 240.04204;

IR (KBr): νmax/cm-1 = 2972, 2897, 2231, 1490, 1457, 1434, 1349, 1226, 1080, 1033, 924, 869, 808, 728.

1H NMR PREDICT

13C NMR PREDICT

 Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00602K, Communication

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C[C@@]1([C@H](C#N)C1)C2=CC(OCO3)=C3C=C2

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile (4)

white solid . Mp: 193–195 °C.
1H NMR (400 MHz, CDCl3) δ (ppm): 7.74–7.76(m, 1H), 7.14–7.17 (m, 1H), 6.95–6.97 (m, 1H), 6.05 (s, 1H), 5.51 (s, 2H), 3.40 (s, 3H).

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00267J, Paper
Kun Hu, Linjun Qi, Shuling Yu, Tianxing Cheng, Xiaodong Wang, Zhaojun Li, Yuanzhi Xia, Jiuxi Chen, Huayue Wu
Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids for the synthesis of diverse isoquinolines in water.

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Kun Hu,a   Linjun Qi,a   Shuling Yu,a   Tianxing Cheng,a  Xiaodong Wang,a   Zhaojun Li,b   Yuanzhi Xia,a  Jiuxi Chen*a and   Huayue Wua  
*Corresponding authors
aCollege of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China
E-mail: jiuxichen@wzu.edu.cn
bInstitute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing, China
Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00267J, 

A palladium-catalyzed tandem reaction of 2-(cyanomethyl)benzonitriles or 2-(2-carbonylphenyl)acetonitriles with arylboronic acids in water has been developed for the first time. This reaction features good functional group tolerance and provides a new strategy for the synthesis of diverse isoquinolines under mild conditions. The use of water as the reaction medium makes the synthesis process environmentally benign. Preliminary mechanistic experiments indicate that the major reaction pathway involves carbopalladation of the C(sp3)–cyano group and subsequent intramolecular cyclization findings that were further supported by density functional theory (DFT) calculations.
Capture
STR1

1,3-Diphenylisoquinoline (3a). Pale-yellow solid (103.5 mg, 92%),

mp 78-79 oC (lit.24,  73-74.5 oC). 24 J. D. Tovar and T. M. Swager, J. Org. Chem., 1999, 64, 6499

1H NMR (500 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15-8.14 (m, 1H), 8.09 (s, 1H), 7.95-7.93 (m, 1H), 7.84-7.83 (m, 2H), 7.70-7.67 (m, 1H), 7.59-7.50 (m, 6H), 7.44-7.40 (m, 1H);

13C NMR (125 MHz, CDCl3) δ 160.5, 150.3, 140.1, 139.8, 138.0, 130.4, 130.2, 128.8, 128.7, 128.6, 128.4, 127.7, 127.6, 127.2, 127.0, 126.0, 115.8.

//////// isoquinoline, pd-catalyzed, arylboronic acids

Resolution of Thiele’s acid

Resolution of Thiele’s acid

Jun Chen,a XuXin Sun,a Allen G. Oliver,b Jeremy E. Wulffa

aDepartment of Chemistry, University of Victoria, P.O. Box 3065 STN CSC, Victoria, BC V8W 3V6, Canada.

bMolecular Structure Facility, Department of Chemistry and Biochemistry, University of Notre Dame, 251 Nieuwland Science Hall, Notre Dame, IN 46556, USA.

Corresponding author: Jeremy E. Wulff (e-mail: ).

ABSTRACT

Thiele’s acid has been resolved for the first time by diastereomeric salt formation with brucine. Determination of absolute stereochemistry was accomplished by X-ray crystallography of the corresponding diester. We anticipate that access to optically resolved Thiele’s acid will stimulate its use in a diverse range of applications requiring chiral molecular clefts.

Canadian Journal of Chemistry, 2017, 95(3): 234-238, 10.1139/cjc-2016-0125

STR0.JPG

 

str1

(–)-Thiele’s ester 2a as a white solid (200 mg, 81%). Spectral data were consistent with the racemic compound that has been described previously in the literature.5 [α]D 25 = –216 deg mL dm-1 g-1 (c = 0.25, ethanol solution). MP = 87–89 °C.

CCDC 1469300 contains the supplementary crystallographic data for compound (–)-2a. These data are available from the Cambridge Crystallographic Data Centre.

 

Synthesis of tetrazines from gem-difluoroalkenes under aerobic conditions at room temperature

Synthesis of tetrazines from gem-difluoroalkenes under aerobic conditions at room temperature

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03494B, Paper
Zheng Fang, Wen-Li Hu, De-Yong Liu, Chu-Yi Yu, Xiang-Guo Hu
A procedure for the synthesis of tetrazines from gem-difluoroalkenes under aerobic conditions has been developed.

Synthesis of tetrazines from gem-difluoroalkenes under aerobic conditions at room temperature

Zheng Fang,a   Wen-Li Hu,a   De-Yong Liu,a  Chu-Yi Yuab and   Xiang-Guo Hu*a  
*Corresponding authors
aNational Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, P. R. China
E-mail: huxiangg@iccas.ac.cn
bBeijing National Laboratory for Molecular Science (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03494B, http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C6GC03494B?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

An efficient and green procedure for the synthesis of tetrazines has been developed based on an old chemistry reported by Carboni in 1958. Both symmetric and asymmetric 3,6-disubstituted 1,2,4,5-tetrazines can be obtained in moderate to high yields from the corresponding gem-difluoroalkenes under aerobic conditions at room temperature. This work represents a rare example that ambient air is utilized as an oxidant for the synthesis of tetrazines.
Synthesis of symmetric 3,6-dialkyl-1,2,4,5−tetrazine(3a−3h)
To a solution of 1,1−difluoroalkenes (1a, 50 mg, 0.27 mmol) in N,N-dimethylformide (DMF,5 mL) was added hydrazine (80%, 35 mg, 1.35 mmol). After stirring at room temperature for 4−6 hours, saturated ammonium chloride (20 mL) was added and the reaction mixture was extracted with dichloromethane (10 mL×3). The organic layer was combined, dried with anhydrous sodium sulfate. The solvent was concentrated and the crude product was dissolved in a suspension of Ethyl Acetate(5 mL) and 10% potassium carbonate solution(wt%, 5 mL) and stirred at room temperature for 24h under air atomerspere until the organic layer turned into amaranth obviously. The organic layer was collected, dried with anhydrous sodium sulfate. The crude product was purified by flash column chromatography[silica gel(#100–200), toluene] to afford the pure 1,2,4,5−tetrazines(3a−3h).
3,6−bis([1,1’−biphenyl]−4−ylmethyl)−1,2,4,5−tetra zine (3a).
str1
(41 mg, 83%).
purple solid; m.p. 200−202°C;
IR(KBr) nmax/cm−1 2924, 2850, 1488, 1451, 1432, 1388, 851, 750;
1 H NMR (400 MHz, CDCl3) 7.55−7.33 (m, 18H), 4.65 (s, 4H).
13C NMR (100 MHz, CDCl3) δ 169.2, 140.6, 140.4, 134.8, 129.7, 128.8, 127.6, 127.4, 127.1, 40.9;
HRMS (ESI): calcd. for C28H22N4 [M+H]+ 415.19172, found 415.19124.

///////tetrazines,  gem-difluoroalkenes, aerobic conditions, room temperature

Pd/Cu-free Heck and Sonogashira cross-coupling reaction by Co nanoparticles immobilized on magnetic chitosan as reusable catalyst

 

Pd/Cu-free Heck and Sonogashira cross-coupling reaction by Co nanoparticles immobilized on magnetic chitosan as reusable catalyst

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03377F, Paper
Abdol R. Hajipour, Fatemeh Rezaei, Zahra Khorsandi
Chitosan (CS) is a porous, self-standing, nanofibrillar microsphere that can be used as a metal carrier. Amino groups on CS enable to modulate cobalt coordination using a safe organic ligand (methyl salicylate).

Pd/Cu-free Heck and Sonogashira cross-coupling reaction by Co nanoparticles immobilized on magnetic chitosan as reusable catalyst

aDepartment of Chemistry, Isfahan University of Technology, Isfahan 84156, Iran
E-mail: haji@cc.iut.ac.ir
Fax: +98 311 391 2350
Tel: +98 311 391 3262
bDepartment of Neuroscience, University of Wisconsin, Medical School, Madison, USA
Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03377F

Department of Chemistry
Office : College of Chemistry, Isfahan University of Technology, Isfahan 84156, IR IranPhone : +98 311 391xxxxFax : +98 311 391xxxxWeb Site : Prof. Abdolreza Hajipour
EDUCATION:
1970-1974               High School, Shahpour high school, Kazerun, IR, Iran
1975-1979               B.S., Chemistry, Department of Chemistry, Isfahan University, Isfahan, I.R. Iran
1981-1983               M.S., Organic Chemistry, Synthesis, Shiraz University, Shiraz, I.R. Iran
Thesis Title: “Synthesis of 2,6,7,11-Tetraphenyl Isobenzofuran B Cyclobutadiene”
Advisor: Professor Habib Firouzabadi
1990-1994               Ph.D., Organic Chemistry, Wollongong University, Australia
Dissertation Title: “Asymmetric Synthesis of Chiral Amines and Benzazepine Alkaloids from Chiral Sulfoxides”
Advisor: Professor Stephen G. Pyne

POSITIONS:
09/94-11/98            Assistant Professor, Isfahan University of Technology
12/98-02/03            Associate Professor, Isfahan University of Technology
03/03-present        Professor, Isfahan University of Technology
02/01-03/02            Visiting Scientist, University of Wisconsin Medical School, Madison, WI
04/02-09/02            Associate Researcher, University of Wisconsin Medical School, Madison, WI
10/02-1/05              Associate Scientist, University of Wisconsin Medical School, Madison, WI
1/04 to present      Senior Scientist, University of Wisconsin Medical School, Madison, WI
 str1
Chitosan (CS) is a porous, self-standing, nanofibrillar microsphere that can be used as a metal carrier. Amino groups on CS enable to modulate cobalt coordination using a safe organic ligand (methyl salicylate). This catalyst efficiently promotes Heck cross-coupling of a large library of functional substrates under mild and sustainable conditions (polyethylene glycol as solvent at 80 °C in a short time (1 h)). The cobalt complex was also used as a heterogeneous, efficient, inexpensive, and green catalyst for Sonogashira cross-coupling reactions. The reactions of various aryl halides and phenylacetylene provided the corresponding products in moderate to good yields. More importantly, this phosphine, copper, and palladium-free catalyst was stable under the reaction conditions and could be easily reused using an external magnet for at least five successive runs without a discernible decrease in its catalytic activity.
Reaction yields were analyzed by gas chromatography (GC, BEIFEN-3420, detector type: FID, TCD equipped with Nukol™ capillary GC column, size × I.D. 30 m × 0.25 mm, df 0.25 μm). 2,3-Dimethylnaphthalene as was used as internal standard. The gas flow rate of 2 mL min-1; and oven temperature at 80 oC for 15 min and then increased to 170 oC.
str1
str2
General procedure for catalyst preparation The magnetic nanoparticles (MNPs) were prepared according to the method reported in literature64 based on the precipitation of magnetite nanoparticles from a mixture of iron(III) chloride and iron(II) sulfate by ammonia (25% solution in water). Subsequently, in a round-bottom flask equipped with a mechanical stirrer and condenser, a mixture of magnetic nanoparticles and sodium sulfate (20%, w/v) was added to a solution of chitosan (1%, w/v) in acetic acid (2%, w/v) under stirring. Stirring was continued for 1 h to obtain the aqueous suspension of MNPs/CS. Then, the magnetic nanoparticles were separated from the reaction mixture by an external permanent magnet, washed with ethanol and methanol several times, and dried under vacuum at 70 °C. For the preparation of supported methyl salicylate ligands, a solution of ethanol suspension of MNPs/CS (1.5 g per 10 mL) was added to methyl salicylate (6.5 mmol), and the mixture was stirred at 60 °C for 24 h. The final Co-MS@MNPs/CS was obtained as a brown solid by the addition of CoCl2·6H2O (4.2 mmol) dissolved in 10 mL of ethanol to disperse the mixture of MNPs/CS-MS (1.01 g) in ethanol (5 mL) and stirred at 60 °C for 18 h. The resulting complex was collected by an external permanent magnet, washed with ethanol (3 × 10 mL) to remove the unreacted materials, and finally dried in air (89% yield based on the amount of Co in the catalyst determined by ICP).
General procedure for the Heck reaction In a round-bottom flask equipped with a mechanical stirrer, a mixture of K3PO4 (4 eq.), olefin (1.1 mmol), and aryl halide (1 mmol) in PEG (3 mL) was added to 5 mg of catalyst (1.1 mol% of Co) and the flask was equipped with a condenser for refluxing. The abovementioned mixture was heated at 80 °C in an oil bath. The progress of the reaction was monitored by TLC (hexane/EtOAc, 80 : 20) and gas chromatography (GC). After the completion of the reaction, the mixture was diluted with dichloromethane and water. The organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The residue was purified by column chromatography. The products were characterized by comparing their physical properties, such as m.p., IR, 1 H, and 13C NMR spectra, with those reported in literature
General procedure for Sonogashira reaction In a round-bottom flask equipped with a mechanical stirrer, phenyl acetylene (1.2 mmol), aryl halide (1.0 mmol), catalyst (10 mg), and KOH (2 eq.) in DMSO (3 mL) were stirred under an air atmosphere at 140 °C. The progress of the reaction was monitored using TLC and GC. After the completion of the reaction, the mixture was diluted with dichloromethane and water. The organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The product was isolated by column chromatography to afford the corresponding products in 55–80% yields. The products were characterized by comparing their physical properties, such as m.p, IR, 1 H, and 13C NMR spectra with those reported in literature.
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Endogenous water-triggered and ultrasound accelerated synthesis of 1,5-disubstituted tetrazoles via a solvent and catalyst-free Ugi-azide reaction

 

Endogenous water-triggered and ultrasound accelerated synthesis of 1,5-disubstituted tetrazoles via a solvent and catalyst-free Ugi-azide reaction

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03324E, Communication
Shrikant G. Pharande, Alma Rosa Corrales Escobosa, Rocio Gamez-Montano
An ultrasound accelerated, environmentally benign Ugi-azide based method was developed for the synthesis of 1,5-disubstituted tetrazoles under solvent and catalyst-free conditions.

Endogenous water-triggered and ultrasound accelerated synthesis of 1,5-disubstituted tetrazoles via a solvent and catalyst-free Ugi-azide reaction

 *Corresponding authors
aDepartamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Noria Alta S/N, Col. Noria Alta, Guanajuato, México
E-mail: rociogm@ugto.mx
Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03324E,  http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C6GC03324E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

A novel, sustainable, endogenous water-triggered, environmentally friendly, high substrate scope, efficient, solvent-free and catalyst-free Ugi-azide based method for the synthesis of 1,5-disubstituted tetrazoles is described.
Shrikant Pharande

Shrikant Pharande

Doctoral student

Research experience

  • Apr 2014–Jun 2014, Research chemist
    TCG Lifesciences · pune
  • Mar 2012–Dec 2013, project assistant
    CSIR – National Chemical Laboratory, Pune · Organic Chemistry Division (NCL)
N-((1-(tert-butyl)-1H-tetrazol-5-yl)(4-chlorophenyl)methyl)aniline (4a)
Based on GP, 100 mg 4-Chlorobenzaldehyde (0.71 mmol), 0.065 cm3 aniline (0.71 mmol), 0.080 cm3 ter. Butyl isocyanide (0.71 mmol), and 0.093 cm3 TMS-azide (0.71 mmol) were reacted together to afford 237 mg (97%) as a white solid.
Melting range 144-145oC,
Rf = 0.45 (Hexane-AcOEt = 7/3 V/V),
1H NMR (500 MHz, CDCl3) δ 7.34 – 7.29 (m, 4H), 7.18 – 7.13 (m, 2H), 6.79 – 6.75 (m, 1H), 6.65 (d, J = 7.6 Hz, 2H), 6.11 (d, J = 6.2 Hz, 1H), 4.78 (d, J = 5.6 Hz, 1H), 1.71 (s, 9H);
13C NMR (126 MHz, CDCl3) δ 155.03, 145.54, 136.81, 134.71, 129.62, 129.43, 129.19, 119.64, 114.42, 61.95, 53.93, 30.29;
FT-IR (ATR) νmax/cm-1 3330.5, 3052.5, 2940.9, 1603.6, 1284.1;
HRMS (ESI+): m/z calcd. for C18H20ClN5 + 342.1480, found 342.1474
str1
str2

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