CO2-Catalysed aldol condensation of 5-hydroxymethylfurfural and acetone to a jet fuel precursor

Green Chemistry International

CO2-Catalysed aldol condensation of 5-hydroxymethylfurfural and acetone to a jet fuel precursor

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC01697A, Communication

Roland Lee, Jesse R. Vanderveen, Pascale Champagne, Philip G. Jessop
CO₂ can act as a catalyst for the production of bio-jet fuel precursors through aldol condensation.

Roland Lee,^a  Jesse R. Vanderveen,^a  Pascale Champagne^b and  Philip G. Jessop*^a  

 *Corresponding authors

^aDepartment of Chemistry, Queen’s University, Kingston, Canada K7L 3N6
E-mail: Philip.jessop@queensu.ca

^bDepartment of Civil Engineering, Queen’s University, Kingston, Canada K7L 3N6

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC01697A, http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC01697A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

CO₂ can act as a catalyst for the production of bio-jet fuel precursors through aldol condensation. CO₂-Catalysed aldol condensation of HMF with acetone gives a >95% yield of [4-(5-hydroxymethyl-2-furyl)-3-butenone]…

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Visible-light induced oxidative Csp3-H activation of methyl aromatics to methyl esters

Green Chemistry International

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC01880G, Communication

Lingling Zhang, Hong Yi, Jue Wang, Aiwen Lei
A mild and catalytic oxidative Csp³-H activation of methyl aromatics using O₂via photocatalysis has been achieved. A lot of methyl aromatics can be tolerated, providing a route for aromatic methyl carboxylates. In addition, this protocol can be performed on a gram scale

Visible-light induced oxidative Csp3-H activation of methyl aromatics to methyl esters

Lingling Zhang,^a  Hong Yi,^a  Jue Wang^a and  Aiwen Lei*^ab  

*Corresponding authors

^aCollege of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Wuhan University, Wuhan, P. R. China
E-mail: aiwenlei@whu.edu.cn

^bNational Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, P. R. China

Green Chem., 2016, Advance…

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Multicomponent-Multicatalyst Reactions (MC)2R: Efficient Dibenzazepine Synthesis

Multicomponent-Multicatalyst Reactions (MC)2R: Efficient Dibenzazepine Synthesis
Jennifer Tsoung, Jane Panteleev, Matthias Tesch, and Mark Lautens

Org. Lett. 2014, 16, 110-113. DOI:10.1021/ol4030925 .

http://pubs.acs.org/doi/abs/10.1021/ol4030925

A Rh^I/Pd⁰ catalyst system was applied to the multicomponent synthesis of aza-dibenzazepines from vinylpyridines, arylboronic acids, and amines in a domino process with no intermediate isolation or purification.

5-(p-tolyl)-3-(trifluoromethyl)-10,11-dihydro-5H-benzo[b]pyrido[2,3-f]azepine (4a)

1H NMR
(400 MHz, CDCl3) δ 8.66 (d, J = 1.1 Hz, 1H), 7.97 (d, J = 1.8 Hz, 1H), 7.43 – 7.38 (m, 1H), 7.38 – 7.29
(m, 3H), 6.98 (d, J = 8.4 Hz, 2H), 6.57 – 6.51 (m, 2H), 3.33 – 3.21 (m, 2H), 3.09 – 2.99 (m, 2H), 2.26 (s,
3H);

13C NMR (101 MHz, CDCl3) δ 161.7 (q, J = 1.3 Hz), 145.8, 143.6, 143.4 (q, J = 4.0 Hz), 139.7,
139.5, 134.9 (q, J = 3.5 Hz), 130.3, 130.0, 129.9, 128.9, 128.2, 127.7, 125.3 (q, J = 33.1 Hz), 123.4 (q, J =
272.5 Hz), 114.0 (2), 35.9, 29.0, 20.4;

19F NMR (377 MHz, CDCl3) δ -62.0;

IR (NaCl, neat): 3063, 3028,
2926, 2862, 1616, 1506, 1489, 1456, 1435, 1429, 1410, 1339, 1319, 1296, 1267, 1240, 1207, 1165, 1128,
1086, 1036, 978, 947, 930, 910, 895, 808, 772, 756, 737, 721, 704, 687, 664, 646, 627 cm-1;

HRMS (ESI):
calcd for C21H18F3N2 (M+H)+: 355.1422; found. 355.1419.

Jennifer Tsoung

Jennifer Tsoung

PhD graduate, organic chemistry

Experience

PhD

University of Toronto

September 2010 – October 2015 (5 years 2 months)

Research Intern

Kyoto University

June 2014 – August 2014 (3 months)Kyoto, Japan

Methodology project in asymmetric phase-transfer catalyzed alkylations.

Co-op student

Angiotech

May 2009 – August 2009 (4 months)Vancouver, Canada Area

Formulation chemistry

Co-op student

Boehringer Ingelheim

January 2008 – August 2008 (8 months)Montreal, Canada Area

On two hit-to-lead teams working to synthesize analogues of hit compounds for HIV research.

Publications

Diastereoselective Friedel−Crafts Alkylation of Hydronaphthalenes(Link)

The Journal of Organic Chemistry

September 27, 2011

An efficient and versatile synthesis of chiral tetralins has been developed using both inter- and intramolecular Friedel-Crafts alkylation as a key step. The readily available hydronaphthalene substrates were prepared via a highly enantioselective metal-catalyzed ring opening of meso-oxabicyclic alkenes followed by hydrogenation. A wide variety of complex tetracyclic compounds have been isolated…more

One-Pot Synthesis of Chiral Dihydrobenzofuran Framework via Rh/Pd Catlaysis

Organic Letters

October 12, 2012

A one-pot synthesis of the chiral dihydrobenzofuran framework is described. The method utilizes Rh-catalyzed asymmetric ring opening (ARO) and Pd-catalyzed C-O coupling to furnish the product in excellent enantioselectivity without isolation of intermediates. Systematic metal-ligand studies were carried out to investigate the compatibility of each catalytic system using product enantiopurity as an…more

Rh/Pd Catalysis with Chiral and Achiral Ligands: Domino Synthesis of Aza-Dihydrodibenzoxepines(Link)

Angew. Chem. Int. Ed

July 19, 2013

A game of dominoes: A synthetic route to aza-dihydrodibenzoxepines is described, through the combination of a Rh-catalyzed arylation and a Pd-catalyzed C-O coupling in a single pot. For the first time, the ability to incorporate a chiral and an achiral ligand in a two-component, two-metal transformation is achieved, giving the products in moderate to good yields, with excellent enantioselectivities.

Multicomponent-multicatalyst reactions (MC)(2)R: efficient dibenzazepine synthesis.

Organic Letters

January 13, 2014

A Rh(I)/Pd(0) catalyst system was applied to the multicomponent synthesis of aza-dibenzazepines from vinylpyridines, arylboronic acids, and amines in a domino process with no intermediate isolation or purification.

Formation of substituted oxa- and azarhodacyclobutanes.

Chemistry – A European Journal

December 6, 2013

The preparation of substituted oxa- and azarhodacyclobutanes is reported. After exchange of ethylene with a variety of unsymmetrically and symmetrically substituted alkenes, the corresponding rhodium-olefin complexes were oxidized with H2O2 and PhINTs (Ts=p-toluenesulfonyl) to yield the substituted oxa- and azarhodacyclobutanes, respectively. Oxarhodacyclobutanes could be prepared with excellent…more

Education

University of Toronto

Doctor of Philosophy (PhD), Organic Chemistry

2010 – 2014

Activities and Societies: Pueblo Science executive member, Let’s Talk Science volunteer, International Chemistry Olympiad tutor

The University of British Columbia

Bachelor of Science (BSc), Chemistry

2005 – 2010

Activities and Societies: Undergraduate Chemistry Society (UCS) executive member, Science Undergraduate Society (SUS) executive member, Science Co-op Students Association (SCOOPS) president and founding member

port moody secondary

High school

Mark Nitz presents Jennifer Tsoung certificate for her CTFP award

Women in Chemistry group, 2015

Lautens Research Group :: Group Pictures

www.chem.utoronto.ca

July 2013

Mark Lautens , O.C.

University Professor
J. Bryan Jones Distinguished Professor
AstraZeneca Professor of Organic Chemistry
NSERC/Merck-Frosst Industrial Research Chair

Department of Chemistry
Davenport Chemical Laboratories
80 St. George St.
University of Toronto
Toronto, Ontario
M5S 3H6

Tel: (416) 978-6083
Fax: (416) 946-8185
E-Mail: mlautens@chem.utoronto.ca

Curriculum Vitae

Personal
Place and Date of Birth	Hamilton, Ontario, Canada	July 9, 1959
Education
Harvard University	NSERC PDF with D. A. Evans	1985 – 1987
University of Wisconsin-Madison	Ph.D. with B. M. Trost	1985
University of Guelph	B.Sc. – Distinction	1981
Academic Positions
J. Bryan Jones Distinguished Professor	University of Toronto	2013 – 2018
University Professor	University of Toronto	2012 – present
NSERC/Merck Frosst Industrial Research Chair	NSERC/Merck Frosst	2003 – 2013
AstraZeneca Professor of Organic Synthesis	University of Toronto	1998 – present
Professor	University of Toronto	1995 – 1998
Associate Professor	University of Toronto	1992 – 1995
Assistant Professor	University of Toronto	1987 – 1992
Awards & Honors
University of Toronto Alumni Faculty Award	University of Toronto	2016
CIC Catalysis Award	CSC	2016
Officer of the Order of Canada	Governor General	2014
Killam Research Fellowship	Canada Council for the Arts	2013-2015
CIC Medal	Chemical Institute of Canada	2013
Fellow of the Royal Society of UK	Royal Society of Chemistry	2011
Pedler Award	Royal Society of Chemistry	2011
Senior Scientist Award	Alexander von Humboldt Foundation Berlin, Aachen and Gottingen	2009-2014
Visiting Professor	University of Berlin	2009
Visiting Professor	Université de Marseilles	2008
ICIQ Summer School	ICIQ Tarragona, Spain	2008
Attilio Corbella Summer School Professor	Italian Chemical Society	2007
Arthur C. Cope Scholar Award	American Chemical Society	2006
Alfred Bader Award	Canadian Society for Chemistry	2006
R. U. Lemieux Award	Canadian Society for Chemistry	2004
Solvias Prize	Solvias AG	2002
Fellow of the Royal Society of Canada	Royal Society of Canada	2001
Areas of Research Interest and Expertise
new synthetic methods metal catalyzed cycloaddition and annulation reactions asymmetric catalysis with focus on rhodium, nickel and palladium catalysts cyclopropane synthesis and reactions hydrometallation reactions reactions of organosilicon and organotin compounds fragmentation reactions new routes to medicinally/biologically interesting compounds heterocycle synthesis using metal catalysts

///////Multicomponent, Multicatalyst Reactions,  (MC)2R,  Dibenzazepine Synthesis, Mark Lautens, University of Toronto , Toronto, Ontario, Jennifer Tsoung

Flow Grignard and Lithiation: Screening Tools and Development of Continuous Processes for a Benzyl Alcohol Starting Material

Efficient continuous Grignard and lithiation processes were developed to produce one of the key regulatory starting materials for the production of edivoxetine hydrochoride. For the Grignard process, organometallic reagent formation, Bouveault formylation, reduction, and workup steps were run in continuous stirred tank reactors (CSTRs). The lithiation utilized a hybrid approach where plug flow reactors (PFRs) were used for the metal halogen exchange and Bouveault formylation steps, while the reduction and workup steps were performed in CSTRs. Relative to traditional batch processing, both approaches offer significant advantages. Both processes were high-yielding and produced the product in high purity. The two main processes were directly compared from a number of perspectives including reagent and operational safety, fouling potential, process footprint, need for manual operation, and product yield and purity.

Michael E. Kopach^*†, Kevin P. Cole^†, Patrick M. Pollock^†, Martin D. Johnson^†, Timothy M. Braden^†, Luke P. Webster^†, Jennifer McClary Groh^†, Adam D. McFarland^†, John P. Schafer^‡, Jonathan J. Adler^‡, and Morgan Rosemeyer^‡

^† Small Molecule Design and Development, Eli Lilly and Company, Indianapolis, Indiana 46285, United States

^‡ D&M Continuous Solutions, LLC, Greenwood, Indiana 46143, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00131, http://pubs.acs.org/doi/suppl/10.1021/acs.oprd.6b00131

*E-mail: kopach_michael@lilly.com.

//////////Flow Grignard,  Lithiation, Screening Tools,  Development, Continuous Processes,  Benzyl Alcohol, Starting Material

• Supporting Info

MICONAZOLE NITRATE , Миконазол , ミコナゾール硝酸塩

New Drug Approvals

Miconazole            C₁₈H₁₄Cl₄N₂O    416.13             [22916–47–8]

Miconazole Nitrate            C₁₈H₁₄Cl₄N₂O.HNO₃              479.14             [22832–87–7]

ミコナゾール硝酸塩 JP16 Miconazole Nitrate C18H14Cl4N2O▪HNO3 : 479.14 [22832-87-7]

click on above image for clear view

MORE GRAPHS

13C

2D [1H,1H]-TOCSY  BELOW

1D DEPT90

1D DEPT135

2D [1H,13C]-HSQC

2D [1H,13C]-HMBC

2D [1H,1H]-COSY

2D [1H,13C]-HMQC

Miconazole is an imidazole antifungal agent, developed by Janssen Pharmaceutica, commonly applied topically to the skin or tomucous membranes to cure fungal infections. It works by inhibiting the synthesis of ergosterol, a critical component of fungal cell membranes. It can also be used against certain species of Leishmania protozoa which are a type of unicellular parasites that…

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Directed alkynylation of unactivated C(sp3)-H bonds with ethynylbenziodoxolones mediated by DTBP

Green Chemistry International

Directed alkynylation of unactivated C(sp3)-H bonds with ethynylbenziodoxolones mediated by DTBP

Green Chem., 2016, 18,4185-4188

DOI: 10.1039/C6GC01336H, Communication

Zhi-Fei Cheng, Yi-Si Feng, Chun Rong, Tao Xu, Peng-Fei Wang, Jun Xu, Jian-Jun Dai, Hua-Jian Xu
A general and efficient alkynylation of unactivated C(sp³)-H bonds under metal-free conditions was developed herein.

Zhi-Fei Cheng,^a  Yi-Si Feng,*^abc  Chun Rong,^a  Tao Xu,^a  Peng-Fei Wang,^a  Jun Xu,^a  Jian-Jun Dai^a and  Hua-Jian Xu*^abc  

*Corresponding authors

^aSchool of Chemistry and Chemical Engineering, School of Biological and Medical Engineering, Hefei University of Technology, Hefei 230009, P. R. China

^bAnhui Key Laboratory of Controllable Chemical Reaction and Material Chemical Engineering, Hefei 230009, P. R…

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Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis

Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC01600F, Paper

Li Chen, Jinmo Zhao, Sivaram Pradhan, Bruce E. Brinson, Gustavo E. Scuseria, Z. Conrad Zhang, Michael S. Wong
The nonselective nature of glucose pyrolysis chemistry can be controlled by preventing the sugar ring from opening and fragmenting.

Li Chen,^a   Jinmo Zhao,^b   Sivaram Pradhan,^a   Bruce E. Brinson,^b  Gustavo E. Scuseria,^b   Z. Conrad Zhang*^c and  Michael S. Wong*^abde  

*Corresponding authors

^aDepartment of Chemical and Biomolecular Engineering, Rice University, Houston, USA
E-mail: mswong@rice.edu

^bDepartment of Chemistry, Rice University, Houston, USA

^cDalian National Laboratory of Clean Energy, Dalian Institute of Chemical Physics, Dalian, China
E-mail: zczhang@dicp.ac.cn

^dDepartment of Civil and Environmental Engineering, Rice University, Houston, USA

^eDepartment of Materials Science and NanoEngineering, Rice University, Houston, USA

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC01600F

see ………………..http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC01600F?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

The selective production of platform chemicals from thermal conversion of biomass-derived carbohydrates is challenging. As precursors to natural products and drug molecules, anhydrosugars are difficult to synthesize from simple carbohydrates in large quantities without side products, due to various competing pathways during pyrolysis. Here we demonstrate that the nonselective chemistry of carbohydrate pyrolysis is substantially improved by alkoxy or phenoxy substitution at the anomeric carbon of glucose prior to thermal treatment. Through this ring-locking step, we found that the selectivity to 1,6-anhydro-β-D-glucopyranose (levoglucosan, LGA) increased from 2% to greater than 90% after fast pyrolysis of the resulting sugar at 600 °C. DFT analysis indicated that LGA formation becomes the dominant reaction pathway when the substituent group inhibits the pyranose ring from opening and fragmenting into non-anhydrosugar products. LGA forms selectively when the activation barrier for ring-opening is significantly increased over that for 1,6-elimination, with both barriers affected by the substituent type and anomeric position. These findings introduce the ring-locking concept to sugar pyrolysis chemistry and suggest a chemical-thermal treatment approach for upgrading simple and complex carbohydrates.

////////Ring-locking ,  selective anhydrosugar, carbohydrate pyrolysis, synthesis