Revisiting the deoxydehydration of glycerol towards allyl alcohol under continuous-flow conditions

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00657H, Paper

Nelly Ntumba Tshibalonza, Jean-Christophe M. Monbaliu
Highly selective flash deoxydehydration of glycerol towards allyl alcohol under continuous-flow conditions.

Revisiting the deoxydehydration of glycerol towards allyl alcohol under continuous-flow conditions

Ms. Nelly Tshibalonza Ntumba

Nelly Tshibalonza was born in 1983 in Kinshasa, Congo. She received her diploma degree in Chemistry in 2006 from the University of Kinshasa. She is currently a fellow of the Belgian Technical Cooperation and is preparing a Ph.D. thesis on the development of catalytic methods to enhance the value of renewable raw materials.

E-mail: nel.tshibalonza@student.ulg.ac.be
Telephone: +32 (0)4 366-3493

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC00657H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Revisiting the deoxydehydration of glycerol towards allyl alcohol under continuous-flow conditions

Nelly Ntumba Tshibalonzaa  and  Jean-Christophe M. Monbaliu*a 

 Author affiliations

*Corresponding authors

aCenter for Integrated Technology and Organic Synthesis, Department of Chemistry, University of Liège, B-4000 Liège (Sart Tilman), Belgium
E-mail: jc.monbaliu@ulg.ac.be

Abstract

The deoxydehydration (DODH) of glycerol towards allyl alcohol was revisited under continuous-flow conditions combining a microfluidic reactor setup and a unique reactive dynamic feed solution approach. Short reaction times, high yield and excellent selectivity were achieved at high temperature and moderate pressure in the presence of formic acid, triethyl orthoformate, or a combination of both. Triethyl orthoformate appeared as a superior reagent for the DODH of glycerol, with shorter reaction times, lower reaction temperatures and more robust conditions. In-line IR spectroscopy and computations provided different perspectives on the unique reactivity of glycerol O,O,O-orthoesters.

JC M. Monbaliu, PhD.
Lecturer
Department of Chemistryjc.monbaliu@ulg.ac.be
t +32 (0) 4 366 35 10

Jean-Christophe M. Monbaliu

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A Flow Process for the Multi-Step Synthesis of the Alkaloid Natural Product Oxomaritidine: A New Paradigm for Molecular Assembly

 A Flow Process for the Multi-Step Synthesis of the Alkaloid Natural Product Oxomaritidine: A New Paradigm for Molecular Assembly 
I.R. Baxendale, J. Deeley, C.M. Griffiths-Jones, S.V. Ley, S. Saaby and G. Tranmer, J. Chem. Soc., Chem. Commun. 2006, 2566-2568.
http://pubs.rsc.org/en/Content/ArticleLanding/2006/CC/b600382f#!divAbstract 


 

A flow process for the multi-step synthesis of the alkaloid natural product (±)-oxomaritidine is described, mediated through the use of microfluidic pumping systems that progress material through various packed columns containing immobilized reagents, catalysts, scavengers or catch and release agents; our route involves the combination of seven separate synthetic steps linked into one continuous sequence utilizing flow chemistry.

Versatile, High Quality and Scalable Continuous Flow Production of Metal-Organic Frameworks

The precursor solutions are pumped continuously, mixed via a static-mixer (T-piece) and 

enter the coiled reactor tubes at temperature (T). A backpressure regulator (BPR) situated

after the reactor coil is used to maintain a constant liquid pressure. 

The residence time can be varied by changing the length of the reactor or pumping rates.

Figure 1: Schematic representation showing the general flow reactor

 setup for the production of MOFs.

http://www.nature.com/srep/2014/140625/srep05443/full/srep05443.html#f1

Further deployment of Metal-Organic Frameworks in applied settings 
requires their ready preparation at scale. Expansion of typical batch
 processes can lead to unsuccessful or low quality synthesis for some 
systems. Here we report how continuous flow chemistry can be
 adapted as a versatile route to a range of MOFs, by emulating 
conditions of lab-scale batch synthesis. This delivers ready 
synthesis of three different MOFs, with surface areas that 
closely match theoretical maxima, with production rates 
of 60 g/h at extremely high space-time yields.

Synthesis of Acetal Protected Building Blocks using Flow Chemistry and Flow I.R. Methods: Preparation of Butane 2, 3- Diacetal Tartrates

Synthesis of Acetal Protected Building Blocks using Flow Chemistry and Flow I.R. Methods: Preparation of Butane 2, 3- Diacetal Tartrates 

C.F. Carter, I.R. Baxendale, M. O’Brien, J.B.J. Pavey, S.V. Ley, Org. Biomol. Chem. 2009, 7, 4594.

http://pubs.rsc.org/en/Content/ArticleLanding/2009/OB/b917289k#!divAbstract
http://www.rsc.org/suppdata/ob/b9/b917289k/b917289k.pdf

Catherine F. Carter,^a   Ian R. Baxendale,^a   Matthew O'Brien,^a  John B. J. Pavey^b and   Steven V. Ley*^a  

*

Corresponding authors

^a

Department of Chemistry, Innovative Technology Centre, University of Cambridge, Lensfield Road, Cambridge, UK
E-mail: svl1000@cam.ac.uk

^b

AstraZeneca, Bakewell Road, Loughborough, Leics, UK

The syntheses of butane-2,3-diacetal protected tartrate derivatives are described using continuous flow processing techniques with in-line purification and I.R. analytical protocol
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Metal-free coupling of saturated heterocyclic sulfonylhydrazones with boronic acids

Metal-free coupling of saturated heterocyclic sulfonylhydrazones with boronic acids 

Daniel M. Allwood *†, David C. Blakemore ‡, Alan D. Brown ‡, and Steven V. Ley †

† Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K.

‡ Neusentis Chemistry, Pfizer Worldwide Research and Development, The Portway Building, Granta Park, Cambridge, CB21 6GS, U.K.

J. Org. Chem., 2014, 79 (1), pp 328–338

DOI: 10.1021/jo402526z

http://pubs.acs.org/doi/abs/10.1021/jo402526z

The coupling of aromatic moieties with saturated heterocyclic partners is currently an area of significant interest for the pharmaceutical industry. Herein, we present a procedure for the metal-free coupling of 4-, 5-, and 6-membered saturated heterocyclic p-methoxyphenyl (PMP) sulfonylhydrazones with aryl and heteroaromatic boronic acids. This procedure enables a simple, two-step synthesis of a range of functionalized sp2–sp3 linked bicyclic building blocks, including oxetanes, piperidines, and azetidines, from their parent ketones.

Flow chemistry syntheses of natural products

 Flow chemistry syntheses of natural products ..click here

J.C. Pastre, D.L. Browne, S.V. Ley, Chem. Soc. Rev. 2013, 42, 8801-9198.

The development and application of continuous flow chemistry methods for synthesis is a rapidly growing area of research. In particular, natural products provide demanding challenges to this developing technology. This review highlights successes in the area with an emphasis on new opportunities and technological advances.

read

http://pubs.rsc.org/en/Content/ArticleLanding/2013/CS/c3cs60246j#!divAbstract