A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SO2F2). The proposed method employs 1,1′-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SO2F2 gas using a two-chamber reactor. With NMR studies, it was shown that this ex situ gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.

Ex Situ Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates

Cedrick Veryser‡ , Joachim Demaerel‡, Vidmantas Bieliu̅nas, Philippe Gilles, and Wim M. De Borggraeve* 

Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.7b02522

*E-mail: wim.deborggraeve@kuleuven.be.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.7b02522?utm_content=bufferd3ad9&utm_medium=social&utm_source=twitter.com&utm_campaign=buffer

4-fluoro-[1,1'-biphenyl]-4-yl sulfurofluoridate (compound 1) 

General procedure A was followed using 192 mg of 4-fluoro-4’-hydroxybiphenyl (98 wt%, 1.0 mmol, 1.0 eq.). The crude reaction mixture was purified by solid-phase flash column chromatography on silicagel (heptane, 100%). The title compound was obtained as a white solid (258 mg, 96%). Rf = 0.39 (heptane/ethyl acetate, 9/1). Melting point = 47 – 49 °C.

1 H NMR (400 MHz, CDCl3): 7.62 (d, J = 8.5 Hz, 1H), 7.52 (dd, J = 8.1, 5.5 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 7.16 (t, J = 8.5 Hz, 1H). 

13C NMR (101 MHz, CDCl3): δ 163.05 (d, J = 247.9 Hz), 149.51, 141.17, 135.55 (d, J = 3.3 Hz), 129.06, 128.98, 121.42, 116.13 (d, J = 21.6 Hz).

19F NMR (376 MHz, CDCl3): δ 37.18, -114.68 (m).

 IR (neat) cm-1 : 1437, 1232, 921, 815. 

CHN: calculated for C12H8F2O3S: C 53.33%, H 2.98%, N 0.00%; found: C 53.43%, H 3.26%, N 0.00%.

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2,5-Bis(morpholinomethyl)furan

2,5-Bis(morpholinomethyl)furan, 11

Yield 98%, 1H NMR (CDCl3) = 6.13 (s, 2H), 3.70 (m, 8H), 3.51 (s, 4H), 2.45 (m, 8H);

13C NMR (CDCl3) = 150.9, 109.7, 66.8, 55.3, 53.2 ppm.

 m/z HRMS (ESI) Calcd. for C14H22N2O3 [M+H]: 267.1703. Found 267.1703.

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis

Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis

Catal. Sci. Technol., 2017, Advance Article
DOI: 10.1039/C7CY00879A, Minireview

Ekambaram Balaraman, Avanashiappan Nandakumar, Garima Jaiswal, Manoj K. Sahoo
This review article describes recent developments of iron-based acceptorless dehydrogenation (AD) reactions of fundamentally important feedstock, as a route to sustainable chemical synthesis and energy storage applications

From the journal:

Catalysis Science & Technology

Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis

 

Ekambaram Balaraman,*ab  Avanashiappan Nandakumar,*a  Garima Jaiswalab  and  Manoj K. Sahooab 

*Corresponding authors

aCatalysis Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune 411008, India
E-mail: eb.raman@ncl.res.in

bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110 025, India

Abstract

Inspired by nature, chemists have designed new catalysts in the pursuit of selective bond activation and chemical transformations. Emergent biological systems often use earth-abundant first-row transition elements as catalytically active sites to facilitate specific and highly selective chemical processes. The design of a new catalytic system based on abundant and inexpensive catalysts, particularly the iron-based catalysts, for fundamentally significant synthetic transformations under environmentally benign conditions is an important paradigm in chemical synthesis. In recent times, iron-based catalytic systems have shown unprecedented reactivity in the acceptorless dehydrogenation reactions of feedstock chemicals, with the liberation of molecular hydrogen as the by-product, and have enabled greener chemical synthetic methods and alternative energy storage systems. Indeed, it has been demonstrated that the proper design of iron catalysts by judiciously choosing ligands, can aid in the development of new sustainable energy storage systems and catalysis. This tutorial review focuses on the recent development of iron-based dehydrogenation reactions of fundamentally important feedstock, as a route to sustainable chemical synthesis and energy storage applications. The emerging area of the iron-based dehydrogenation strategy provides an opportunity to make industrially applicable, cost-effective and environmentally benign catalytic systems

http://pubs.rsc.org/en/Content/ArticleLanding/2017/CY/C7CY00879A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2Fcy+%28RSC+-+Catalysis+Science+%26+Technology+latest+articles%29#!divAbstract

Dr.Ekambaram Balaraman
Catalysis Division
CSIR-National Chemical Laboratory

 eb.raman@ncl.res.in; balaramanekambaram@gmail.com

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Synthesis of 2-substituted quinazolines by CsOH-mediated direct aerobic oxidative cyclocondensation of 2-aminoarylmethanols with nitriles in air

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00977A, Communication

Song Yao, Kaijing Zhou, Jiabing Wang, Hongen Cao, Lei Yu, Jianzhang Wu, Peihong Qiu, Qing Xu
An atom-efficient synthesis of 2-substituted quinazolines is developed by a CsOH-mediated aerobic oxidative reaction of 2-aminoarylmethanols and nitriles in air.

Synthesis of 2-substituted quinazolines by CsOH-mediated direct aerobic oxidative cyclocondensation of 2-aminoarylmethanols with nitriles in air

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC00977A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

• From the journal:

  Green Chemistry

Synthesis of 2-substituted quinazolines by CsOH-mediated direct aerobic oxidative cyclocondensation of 2-aminoarylmethanols with nitriles in air

Song Yao,ab  Kaijing Zhou,b  Jiabing Wang,a  Hongen Cao,c  Lei Yu,c  Jianzhang Wu,*a  Peihong Qiu*a  and  Qing Xu*abc 

 Author affiliations

*Corresponding authors

aChemical Biology Research Center, College of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou, China
E-mail: wjzwzmu@163.com, wzqph@163.com
Tel: +86-158-25672558

bCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, P. R. China
E-mail: qing-xu@wzu.edu.cn
Fax: +86-577-86689302
Tel: +86-138-57745327

cInstitute of Pesticide, School of Horticulture and Plant Protection and School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, China

Abstract

By using air as the superior oxidant, a highly atom-efficient synthesis of 2-substituted quinazolines is developed by a CsOH-mediated direct aerobic oxidative reaction of the readily available and stable 2-aminoarylmethanols and nitriles. Effectively working as the promoter in the alcohol oxidation, nitrile hydration, and cyclocondensation steps, CsOH is the best base for the reaction. A similar method can also be extended to the synthesis of substituted quinolines starting from methyl ketones instead of nitriles.

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USA Viewership touched 3 lakhs on New Drug Approvals

USA Viewership touched 3 lakhs on New Drug Approvals

https://newdrugapprovals.org/

Total 16.9 lakhs in 213 countries

DR PRAVIN PATIL (Guest blogger) m-Chloroperbenzoic acid-oxchromium (VI)-mediated cleavage of 2,4,5-trisubstituted oxazoles

Here is the another publication details 

The paper is about m-CPBA/Chromium-VI mediated oxidation of oxazoles and published in Tetrahedron Letters recently.

m-Chloroperbenzoic acid-oxchromium (VI)-mediated cleavage of  2,4,5-trisubstituted oxazoles 

Pravin C. Patil and Frederick A. Luzzio*

Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292 USA

[Invited article: Tetrahedron Letters 2017, 58 (13), 1280-1282]

http://www.sciencedirect.com/science/article/pii/S004040391730196X

DOI: https://doi.org/10.1016/j.tetlet.2017.02.027]

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Graphical Abstract:

Abstract:

An array of 2-substituted-4,5-diphenyloxazoles were found to be cleaved to triacylamines and diacylamines (imides) using a reagent system composed of 3-chloroperbenzoic acid (MCPBA) and 2,2'-bipyridinium chlorochromate (BPCC). The 2-alkyl-4,5-diphenyloxazoles give imides (38-60%) as the predominant cleavage product while the 2-aryl-4,5-diphenyloxazoles give triacylamines (62-71%). Two mechanisms involving intermediates such as cyclic endoperoxides or oxachromacycles were proposed. An application of the oxidative cleavage to the multi-step synthesis of phoracantholide I seco acid is detailed.

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Application of methodology toward synthesis of Phoracantholide-I seco acid

                                                                                          

 Highlights

A new method for the cleavage of 2,4,5-trisubstituted oxazoles to imides and triacylamines is detailed.

The oxidation system utilizes two reagents composed of a peroxide and oxochromium (VI).

Mechanisms are proposed for the oxidative cleavage reaction.

A synthesis of (±)-phoracantholide seco-acid is detailed.

ABOUT GUEST BLOGGER

Dr. Pravin C. Patil

Postdoctoral Research Associate at University of Louisville

Email, pravinchem@gmail.com

see…….http://oneorganichemistoneday.blogspot.in/2017/04/dr-pravin-patil.html

Dr. Pravin C Patil completed his B.Sc. (Chemistry) at ASC College Chopda (Jalgaon, Maharashtra, India) in 2001 and M.Sc. (Organic Chemistry) at SSVPS’S Science College Dhule in North Maharashtra University (Jalgaon, Maharashtra, India) in year 2003. After M.Sc. degree he was accepted for summer internship training program at Bhabha Atomic Research Center (BARC, Mumbai) in the laboratory of Prof. Subrata Chattopadhyay in Bio-organic Division. In 2003, Dr. Pravin joined to API Pharmaceutical bulk drug company, RPG Life Science (Navi Mumbai, Maharashtra, India) and worked there for two years. In 2005, he enrolled into Ph.D. (Chemistry) program at Institute of Chemical Technology (ICT), Matunga, Mumbai, aharashtra, under the supervision of Prof. K. G. Akamanchi in the department of Pharmaceutical Sciences and Technology.

After finishing Ph.D. in 2010, he joined to Pune (Maharashtra, India) based pharmaceutical industry, Lupin Research Park (LRP) in the department of process development. After spending two years at Lupin as a Research Scientist, he got an opportunity in June 2012 to pursue Postdoctoral studies at Hope College, Holland, MI, USA under the supervision of Prof. Moses Lee. During year 2012-13 he worked on total synthesis of achiral anticancer molecules Duocarmycin and its analogs. In 2014, he joined to Prof. Frederick Luzzio at the Department for Chemistry, University of Louisville, Louisville, KY, USA to pursue postdoctoral studies on NIH sponsored project “ Structure based design and synthesis of Peptidomimetics targeting P. gingivalis.

During his research experience, he has authored 23 international publications in peer reviewed journals and inventor for 4 patents.

//////////////guest blogger, pravin patil

Visible-light-induced and iron-catalyzed methylation of N-arylacrylamides with dimethyl sulphoxide: a convenient access to 3-ethyl-3-methyl oxindoles

Visible-light-induced and iron-catalyzed methylation of N-arylacrylamides with dimethyl sulphoxide: a convenient access to 3-ethyl-3-methyl oxindoles

Org. Biomol. Chem., 2017, Advance Article
DOI: 10.1039/C7OB00779E, Paper

Zuguang Xie, Pinhua Li, Yu Hu, Ning Xu, Lei Wang
An efficient synthesis of 3-ethyl-3-methyl oxindoles by visible-light promoted and iron-catalyzed difunctionalization of N-arylacrylamides with dimethyl sulphoxide was developed

Visible-light-induced and iron-catalyzed methylation of N-arylacrylamides with dimethyl sulphoxide: a convenient access to 3-ethyl-3-methyl oxindoles

Zuguang Xie,a  Pinhua Li,*a  Yu Hu,a  Ning Xua  and  Lei Wang*ab 

Author affiliations

*Corresponding authors

aDepartment of Chemistry, Huaibei Normal University, Huaibei, P. R. China
E-mail: pphuali@126.com, leiwang@chnu.edu.cn
Fax: +86-561-3090-518
Tel: +86-561-3802-069

bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China

Abstract

A visible-light-induced and iron-catalyzed methylation of arylacrylamides by dimethyl sulphoxide (DMSO) is achieved, leading to 3-ethyl-3-methyl indolin-2-ones in high yields. This reaction tolerates a series of functional groups, such as methoxy, trifluoromethyl, cyano, nitro, acetyl and ethyloxy carbonyl groups. The visible-light promoted radical methylation and arylation of the alkenyl group are involved in this reaction.

 

 

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N-Methyl-3-Bromo-5-Methyl Pyrazole

N-Methyl-3-Bromo-5-Methyl Pyrazole

3·HCl as a white solid in 27% yield; sublimes at 40 °C; 1H NMR (500 MHz, DMSO-d6) δ 11.88 (s, 1 H), 6.07 (s, 1 H), 3.62 (s, 3 H), 2.16 (s, 3 H); 13C NMR (125 MHz, DMSO-d6) δ 141.7, 123.0, 107.5, 36.5, 10.9; HRMS-ESI (m/z) calcd for C5H8N2Br [M + H]+ 174.9864, found 174.9864.

3·TfOH as an off-white solid; mp = 145 °C; 1H NMR (400 MHz, DMSO-d6) δ 11.73 (s, 1 H), 6.06 (s, 1 H), 3.62 (s, 3 H), 2.16 (s, 3 H); 13C NMR (100 MHz, DMSO-d6) δ 141.9, 123.2, 121.2 (q, J = 320 Hz), 107.6, 36.5, 10.9; HRMS-ESI (m/z) calcd for C5H8N2Br [M + H]+ 174.9864, found 174.9865.

Development of Scalable Processes for the Preparation of N-Methyl-3-Bromo-5-Methyl Pyrazole

Richard J. Fox* , Chester E. Markwalter, Michael Lawler, Keming Zhu, Jacob Albrecht, Joseph Payack, and Martin D. Eastgate

Chemical & Synthetic Development, Bristol-Myers Squibb Company, P.O. Box 191 New Brunswick, New Jersey 08903-0191, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00091

 

*E-mail: richard.fox@bms.com.

The development and optimization of two scalable routes to N-methyl-3-bromo-5-methyl pyrazole is described. The initial Sandmeyer route entailed a three-step sequence from crotonitrile and methyl hydrazine, proceeding through the 3-amino pyrazole intermediate. Due to the GTI liability of the 3-amino pyrazole intermediate, a tedious steam-distillation, and <30% overall yield, we developed a second-generation Sandmeyer-free approach from methyl crotonate and methyl hydrazine which leveraged a condensation, bromination, and oxidation sequence. Process development led to the improved preparation of N-methyl-3-bromo-5-methyl pyrazole with increased efficiency and overall yield. The isolation, handling, and storage of the final product was greatly improved through the generation of the triflic acid salt, and salt form studies are also discussed.

   

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00091

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