Eco-Friendly, Catalyst and Solvent-Free, Synthesis of Acetanilides and N-Benzothiazole-2-yl-acetamides

N-(o-Tolyl)acetamide (3b) White solid, 51.5 mg, 71% yield; m.p. 108.4-109.0 °C (Lit.27 108-109 °C); IR (KBr) n / cm-1 3291, 1647, 1587, 1527, 1458, 1369, 1271, 1116, 1039, 933, 854, 756, 698, 651, 607; 1H NMR (500 MHz, CDCl3) d 2.19 (s, 3H, CH3), 2.30 (s, 3H, CH3), 7.10 (t, 1H, J 7.5 Hz, CH), 7.21 (t, 1H, J 8.0 Hz, CH), 7.71 (d, 1H, J 8.0 Hz, CH); 13C NMR (125 MHz, CDCl3) d 17.8, 24.2, 123.7, 125.4, 126.7, 129.7, 130.5, 135.6, 168.6.

Short ReportJ. Braz. Chem. Soc. 2016

Eco-Friendly, Catalyst and Solvent-Free, Synthesis of Acetanilides and N-Benzothiazole-2-yl-acetamides

Silvio Cunha; Lourenço L. B. de Santana

An expeditious and green synthesis of acetamides is described in good yield without external heating, and with simple purification. 

This paper is part of the PubliSBQ Special Issue in honor of the late Prof Angelo da Cunha Pinto.

http://dx.doi.org/10.21577/0103-5053.20160265

Published online: September 27, 2016.

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Synthesis of symmetrical pyridines by iron-catalyzed cyclization of ketoxime acetates and aldehydes

Synthesis of symmetrical pyridines by iron-catalyzed cyclization of ketoxime acetates and aldehydes

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03137D, Paper

YuKun Yi, Mi-Na Zhao, Zhi-Hui Ren, Yao-Yu Wang, Zheng-Hui Guan
A facile iron-catalyzed cyclization of aldehydes with ketoxime acetates for the synthesis of multisubstituted symmetrical pyridines has been developed.

Synthesis of symmetrical pyridines by iron-catalyzed cyclization of ketoxime acetates and aldehydes

YuKun Yi,^a   Mi-Na Zhao,^a   Zhi-Hui Ren,^a  Yao-Yu Wang^a and   Zheng-Hui Guan*^a  

*

Corresponding authors

^a

Key Laboratory of Synthetic and Nature Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi'an 710127, P.R. China
 E-mail: guanzhh@nwu.edu.cn

Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03137D

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C6GC03137D?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

A novel and facile iron-catalyzed cyclization of ketoxime acetates and aldehydes for the green synthesis of substituted pyridines has been developed. In the presence of a FeCl₃ catalyst, this reaction exhibited a good functional group tolerance to produce 2,4,6-triarylsubstituted symmetrical pyridines in high yields in the absence of any additive. A gram-scale reaction sequence was performed to demonstrate the scaled-up applicability of this synthetic method.

4-Phenyl-2,6-di-p-tolylpyridine (3bb). Yield 70% (47.0 mg); Yellow solid; mp 148-150 o C; S-3

1 H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.0 Hz, 4H), 7.82 (s, 2H), 7.72 (d, J = 7.2 Hz, 2H), 7.52-7.45 (m, 3H), 7.31 (d, J = 8.0 Hz, 4H), 2.42 (s, 6H).

13C NMR (100 MHz, CDCl3): δ 157.3, 149.9, 139.2, 138.9, 136.8, 129.4, 129.0, 128.8, 127.1, 126.9, 116.5, 21.3.

HRMS Calcd (ESI) m/z for C25H22N: [M+H] + 336.1747. Found: 336.1731.





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Product Control Using Substrate Design

Product Control Using Substrate Design

New class of cyclic Weinreb amides for oxidative C-H olefination or Heck reaction

Read more

Silver-initiated radical ring expansion/fluorination of ethynyl cyclobutanols: efficient synthesis of monofluoroethenyl cyclopentanones

Silver-initiated radical ring expansion/fluorination of ethynyl cyclobutanols: efficient synthesis of monofluoroethenyl cyclopentanones

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02656G, Communication

Qingshan Tian, Bin Chen, Guozhu Zhang
A stereoselective synthesis of [small beta]-halogenated 2-methylenecyclopentanones via silver-catalyzed formal ring expansion using water as the cosolvent is described.

Silver-initiated radical ring expansion/fluorination of ethynyl cyclobutanols: efficient synthesis of monofluoroethenyl cyclopentanones

Qingshan Tian,^a   Bin Chen^a and   Guozhu Zhang*^a  

*

Corresponding authors

^a

State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China
E-mail: guozhuzhang@sioc.ac.cn

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02656G

A stereoselective synthesis of β-halogenated 2-methylenecyclopentanones via silver-catalyzed formal ring expansion using water as the cosolvent is described. A variety of 2-methylenecyclopentanones with fluoro, chloro and bromo functionalities are efficiently prepared from 1-alkynyl cyclobutanols. This method offers facile access to halogenated complex molecules which are not only useful chemicals but also valuable building blocks for further derivatizations.

1-(m-tolylethynyl)cyclobutan-1-ol (1b) Yield: 89%; Yellow oil;

1H NMR (400 MHz, CDCl3)

δ 7.25 (s, 1H), 7.23 (d, J = 8.1 Hz, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H), 2.51 (dt, J = 15.8, 6.3 Hz, 2H), 2.34 (t, J = 9.3 Hz, 2H), 2.30 (s, 3H), 1.85 (m, 2H);

13C NMR (100 MHz, CDCl3)

δ 137.94, 132.27, 129.19, 128.72, 128.17, 122.49, 92.16, 83.58, 68.31, 38.64, 21.20, 12.98; HRMS (EI+ , 70 eV): C13H14O [M]+ : calcd. 186.1045, found 186.1047

(E)-2-(fluoro(phenyl)methylene)cyclopentan-1-one (2a) Yield: 85%; Colorless oil;

1H NMR (400 MHz, CDCl3) δ 7.79 (dd, J = 8.0, 1.5 Hz, 2H), 7.46-7.40 (m, 3H), 2.94 (td, J = 7.3, 3.3 Hz, 2H), 2.43 (td, J = 7.9, 1.2 Hz, 2H),1.99 (m, 2H);

13C NMR (100 MHz, CDCl3) δ 204.7 (d, J = 14.4 Hz), 162.4 (d, J = 270.7 Hz), 131.1, 130.0, 129.7, 128.7 (d, J = 7.0 Hz), 127.8, 117.3 (d, J = 19.4 Hz), 40.7 (d, J = 4.3 Hz), 27.6 (d, J = 3.9 Hz), 19.4;

19F (376 MHz, CDCl3) δ -76.9;

HRMS (EI+ , 70 eV): C12H11FO [M]+ : calcd. 190.0794, found 190.0795.

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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  

Hide Affiliations

*

Corresponding authors

^a

Department of Chemistry, University of Louisville, Louisville, USA
E-mail: gb.hammond@louisville.edu

^b

College 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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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 Zhang^a and   Rui Wang*^ab  

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02517J?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

*

Corresponding authors

^a

School of Life Sciences, Institute of Biochemistry and Molecular Biology, Lanzhou University, Lanzhou 730000, P. R. China
E-mail: wangrui@lzu.edu.cn

^b

State Key Laboratory of Chiroscience, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Kowloon, P. R. China
E-mail: bcrwang@polyu.edu.hk

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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Register Today for the ACS Symposium in India on Recent Advances in Drug Development, 11-12 November 2016 in Hyderabad, India

Inaugural ACS Industry Symposium, 11-12 November 2016 in Hyderabad, India

Recent Advances in Drug Development

Register Today for the ACS Symposium in India on Recent Advances in Drug Development

To view this email as a web page, go here.

Register now for the inaugural ACS Industry Symposium, 11-12 November 2016 in Hyderabad, India. Be sure to secure your seat today as rates will increase on 27 October!
The theme of the Symposium is Recent Advances in Drug Development. The event will feature lectures by the world's leading researchers and experts in the pharma industry, including:

• Dr. Peter Senter of Seattle Genetics
• Dr. Jagath Reddy Junutula of Cellerant Therapeutics, Inc.
• Dr. Ming-Wei Wang of the Shanghai Institute of Materia Medica, Chinese Academy of Sciences

This is an exclusive event being organized in partnership with Dr. Reddy's Laboratories for pharma professionals throughout India. Space is limited so register today!

Please visit our website to learn more about the speakers and the program.

Register today to ensure your access to the ACS Industry Symposium. We look forward to seeing you in Hyderabad in November.

CAS
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A Brønsted Acid–Primary Amine as a Synergistic Catalyst for Stereoselective Asymmetric Diels–Alder Reactions

Ramachary Dhevalapally

September 14 · 

 on facebook wrote, quote

I am happy to share with you our laboratory recent publication on asymmetric catalysis.

This communication deals with the understanding and development of Brønsted Acid-Primary Amine as a Synergistic-catalyst for Stereoselective Asymmetric Barbas [4+2]-cycloaddition reaction by using 2-aminobuta-1,3-diene-catalysis under ambient conditions.

I believe this reaction can become good tool for chemists.

I congratulate my co-workers for their hard work to make this work more successful.

For more information, please click below link:
http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201601011/full          ..........unquote

http://onlinelibrary.wiley.com/store/10.1002/ejoc.201601011/asset/supinfo/ejoc201601011-sup-0001-SupMat.pdf?v=1&s=df97504ed59dfa57793737f8f4186106bcbac24c

(1R,3S,5S)-5-hydroxy-3-methyl-2'-oxospiro[cyclohexane-1,3'-indoline]-2,2-dicarbonitrile (7ag): Prepared by following the procedure E and purified by column chromatography using EtOAc/hexane and isolated as solid.

[]D 25 = –119.2 (c = 0.1 g/100 mL, CHCl3, 99% ee);

IR (Neat): max 3313, 2977, 2930, 1701, 1618, 1479, 1350, 1272, 1246, 1200, 1148, 1066, 1014 and 750 cm-1 ; 

1H NMR (CDCl3)  8.58 (1H, br s, NH), 7.64 (1H, d, J = 8.0 Hz), 7.41 (1H, t, J = 7.5 Hz), 7.23 (1H, t, J = 7.5 Hz), 6.99 (1H, d, J = 7.5 Hz), 5.32 (1H, dd, J = 11.0, 4.0 Hz), 4.22-4.18 (1H, m), 3.44-3.89 (1H, m), 2.33 (1H, dd, J = 16.0, 4.0 Hz), 2.20-2.13 (2H, m), 1.89 (1H, dt, J = 13.0, 3.5 Hz), 1.40 (3H, d, J = 6.5 Hz); 

13C NMR S-15 (CDCl3, DEPT-135)  178.2 (C, N_C=O), 139.8 (C), 130.9 (CH), 127.6 (C), 124.9 (CH), 124.2 (CH), 112.9 (C, CN), 111.8 (C, CN), 110.8 (CH), 64.7 (CH), 52.3 (C), 47.2 (C), 36.9 (CH2), 34.0 (CH2), 28.8 (CH), 18.4 (CH3); 

HRMS m/z 304.1060 (M + Na), calcd for C16H15N3O2Na 304.1062.

Ramachary D B

Details

• 

   

Dr. D. B. Ramchary, Ph.D. Associate Professor 
   School of Chemistry
   University of Hyderabad
   Prof. C. R. Rao Road, Gachibowli
   Hyderabad, 500046, India
   Tel: 0091-40-23134816
   Email: ramsc@uohyd.ernet.in

Ramachary obtained his Masters degree (General Chemistry) at the University of Hyderabad in 1996. There as part of curricula he studied and actively involved in the project, entitled Synthesis and Utilization of Aromatic Radical Anions for Reduction of Carbon Monoxide (with Prof. M. Periasamy).

Ramachary obtained his Doctoral degree (Organic Synthesis) at the Indian Institute of Science, Bangalore for his research work on Total Synthesis of Sesquiterpenes Containing Three Contiguous Quaternary Carbon Atoms (with Prof. A. Srikrishna).

In January 2002, he moved to Prof. Carlos F. Barabas III research group as Skaggs Post Doctoral fellow at The Scripps Research Institute, San Diego. After three year post doctoral studies at TSRI, he then joined as Faculty member in School of Chemistry, University of Hyderabad in Jan 2005, where at present he is a Reader.

Dr Ramachary has been awarded the INSA Medal for Young Scientists in Chemical Sciences for the year 2006 for his outstanding contributions to the emerging area of asymmetric organocatalysis.

The main focus of his research group is to engineer the novel and green asymmetric cascade and multi-component reactions (MCRs) to generate the biologically important molecules and natural products in a single step via emerging chiral amines or amino acid-catalysis.

His research group is actively engaged in the design and synthesis of novel enzyme mimetic small organic amines and amino acids to catalyze the fundamental organic reactions in enantioselective manner.

His interest about inquisitive questions like how small can be highly active and stereo-selective catalysts and what are the minimal functional and structural features required in a chiral catalyst had made him to venture in the most advanced versions of synthetic chemistry. 

For the more information about his research group please Click here for Home Page

Significant Publications:
D. B. Ramachary, M. Kishor and Y. Vijayendar Reddy, Development of Pharmaceutical Drugs, Drug Intermediates and Ingredients by Using Direct Organo-Click Reactions, Eur. J. Org. Chem., 2007, xxxx-xxxx (DOI: 10.1002/ejoc.200701014).

D. B. Ramachary, G. Babul Reddy and Rumpa Mondal, New Organocatalyst for Friedel-Crafts Alkylation of 2-Naphthols with Isatins: Application of an Organo-Click Strategy for the Cascade Synthesis of Highly Functionalized Molecules, Tetrahedron Lett., 2007, 48, 7618-7623.

D. B. Ramachary and M. Kishor, Organocatalytic Sequential One-Pot Double Cascade Asymmetric Synthesis of Wieland-Miescher Ketone Analogs from a Knoevenagel/Hydrogenation/Robinson Annulation Sequence: Scope and Applications of Organocatalytic Bio-Mimetic Reductions, J. Org. Chem., 2007, 72, 5056-5068.

D. B. Ramachary, K. Ramakumar and V. V. Narayana, Organocatalytic Cascade Reactions Based on Push-Pull Dienamine Platform: Synthesis of Highly Substituted Anilines, J. Org. Chem., 2007, 72, 1458-1463.

D. B. Ramachary and G. Babul Reddy, Towards Organo-Click Reactions: Development of Pharmaceutical Ingredients by Using Direct Organocatalytic Bio-Mimetic Reductions, Org. Biomol. Chem., 2006, 4, 4463-4468.

D. B. Ramachary and Rumpa Mondal, Direct Organocatalytic Hydroalkoxylation of a,b-Unsaturated Ketones, Tetrahedron Lett., 2006, 47, 7689-7693.

Jorly Joseph, D. B. Ramachary, Eluvathingal D. Jemmis, Electrostatic Repulsion as an additional Selectivity Factor in Asymmetric Proline Catalysis, Org. Biomol. Chem., 2006, 4, 2685-2689.

D. B. Ramachary, M. Kishor and G. Babul Reddy, Development of Drug Intermediates by Using Direct Organocatalytic Multi-Component Reactions, Org. Biomol. Chem., 2006, 4, 1641-1646.

D. B. Ramachary, M. Kishor and K. Ramakumar, A Novel and Green Protocol for Two-Carbon Homologation: A Direct Amino Acid/K2CO3-Catalyzed Four-Component Reaction of Aldehydes, Active Methylenes, Hantzsch Esters and Alkyl Halides, Tetrahedron Lett., 2006, 47, 651-656.

D. B. Ramachary, K. Ramakumar and M. Kishor, Direct Organocatalytic in situ Generation of Novel Push-Pull Dienamines: Application in Tandem Claisen-Schmidt/Iso-Aromatization Reactions, Tetrahedron Lett., 2005, 46, 7037-7042.

D. B. Ramachary and Carlos F. Barbas III, Direct Amino Acid-Catalyzed Asymmetric Desymmetrization of meso-Compounds: Tandem Aminoxylation/O-N Bond Heterolysis Reactions, Org. Lett., 2005, 7, 1577-1580.

D. B. Ramachary, Naidu S. Chowdari and Carlos F. Barbas III, Organocatalytic Asymmetric Domino Knoevenagel/Diels-Alder Reactions: A Bioorganic Approach to the Diastereospecific and Enantioselective Construction of Highly Substituted Spiro[5,5]undecane-1,5,9-triones, Angew. Chem. Int. Ed., 2003, 42, 4233-4237. 

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