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

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.

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

 *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] mono-aldol condensate, while direct conversion of glucose to the same mono-aldol condensate gave a yield of 11%
Method Single step dehydration, aldol condensation, and hydrogenation was carried out in a Parr 31 mL high pressure vessel (T316SS, Parr no. N4742, modified to 31 mL). Glucose/5-HMF, hydrogenation catalyst (Pt (nominally 50 %), Ru (nominally 25 %) on high surface area advanced carbon support supplied by Alfa Aesar (stock# 12100) and reaction solvents were added to the Parr vessel equipped with a stir bar. The vessel was then closed and heated in an oil bath to the required temperature and allowed to equilibrate for 30 min. Following equilibration, the reactor was pressurized with CO2 and H2 to operating conditions. Following reaction (both for conversion of 5-HMF to aldol condensation product or direct conversion from glucose) and dilution, the samples were analyzed with the use of GC-MS (Perkin Elmer Clarus 680 gas chromatograph (GC)), using an Elite-5MS column (30 m, 250 µm i.d., 0.25 µm film of 5% diphenyl 95% dimethyl polysiloxane). Initially the temperature was held at 30 °C for 0 min, followed by a ramp to 125 °C at a rate of 2.5 °C /min held for 1 min, ramp to 260 °C at a rate of 20 °C /min held for 1 min and, finally, ramp to 300 °C at a rate of 20 °C /min held for 3 min. The injector temperature was held at 250 °C and the detector at 200 °C for the duration of the analysis. Carrier gas (helium) flow rate was maintained at 1 mL/min. Aldol condensation products were independently prepared by a literature method17 and utilized for calibration and determination of retention time. Chromatograms and data were collected precisely with the use of Perkin Elmer TurboMass, version 5.4.2.1617 chromatography software.
Image result for bio-jet fuel precursors
Scheme 1 Proposed conversion of cellulose to biomass derived jet fuel.
Image result for bio-jet fuel precursors
Image result for bio-jet fuel precursors
///////////CO2-Catalysed,  aldol condensation, -hydroxymethylfurfural, jet fuel precursor

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

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

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

Lingling Zhang,a   Hong Yi,a   Jue Wanga 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 Article

DOI: 10.1039/C6GC01880G. http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC01880G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Direct functionalization of readily available hydrocarbons under mild conditions fulfills the requirements of green and sustainable chemistry. In this work, a mild and green catalytic oxidative Csp3–H activation of methyl aromatics using O2 via photocatalysis has been achieved. A lot of methyl aromatics can be tolerated, providing a green route for aromatic methyl carboxylates. In addition, this protocol can be performed on a gram scale.
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Methyl 4-methylbenzoate (2a): [1] 32.9 mg (yield: 73%, light yellow oil). 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.1 Hz, 2H), 7.06 (d, J = 8.0 Hz, 2H), 3.73 (s, 3H), 2.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 167.0, 143.5, 129.6, 129.0, 127.4, 51.8, 21.5.
Liu, H.; Chen, G.; Jiang, H.; Li, Y.; Luque, R., ChemSusChem. 2012, 5 , 1892-1896.
///////Visible-light,  induced oxidative,  Csp3-H activation,  methyl aromatics, methyl esters

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02012G, Paper
Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage
This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1) with very high turnover number.
This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki–Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.
(4-methoxyphenyl)(phenyl)methanone (3b) 59.3 mg, yield 56%
1H NMR (500 MHz, CDCl3): δ 7.86 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 7.6 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 3.92 (s, 3H).
13C{1H}NMR (125 MHz, CDCl3): δ 195.4, 163.1, 138.2, 132.4, 131.8, 130.0, 129.6, 128.1, 113.4, 55.4.
GCMS (EI, 70 eV): m/z (%): 212 (40), 135 (100), 105 (14), 77 (36).

 

 

 

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki–Miyaura cross-coupling

*Corresponding authors
aDepartment of Chemistry, Institute of Chemical Technology, N.P. Marg, Matunga-400019, Mumbai, India
E-mail: bm.bhanage@ictmumbai.edu.in,bm.bhanage@gmail.com
bNanocatalysis Laboratories (NanoCat), Department of Chemical Sciences, Tata Institute of Fundamental Research (TIFR), Homi Bhabha Road, Colaba, Mumbai, India
E-mail: vivekpol@tifr.res.in
Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02012G

str1

Prashant Gautam

Image result for Bhalchandra M. Bhanage
\\\\\\\\\\KCC-1 supported,  palladium nanoparticles, sustainable nanocatalyst, carbonylative Suzuki-Miyaura cross-coupling, Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage

High Throughput Enzymatic Enantiomeric Excess: Quick-ee

.

High throughput screening techniques (HTS) are fast and efficient alternatives to evaluate enzymatic activities. Here, this technique is applied to obtain enantiomeric excess and conversions values with chiral fluorogenic probes and a non fluorogenic competitor, which was named Quick-ee. The fluorescent signal reveals of the enantioselectivity of the enzyme. Details are presented in the Article High Throughput Enzymatic Enantiomeric Excess: Quick-ee by Maria L. S. de O. Lima, Caroline C. da S. Gonçalves, Juliana C. Barreiro, Quezia Bezerra Cass and Anita Jocelyne Marsaioli on page 319.

http://dx.doi.org/10.5935/0103-5053.20140282

Cover Article

J. Braz. Chem. Soc. 2015, 26(2), 319-324

High Throughput Enzymatic Enantiomeric Excess: Quick-ee

Maria L. S. O. Lima; Caroline C. S. Gonçalves; Juliana C. Barreiro; Quezia B. Cass; Anita J. Marsaioli

Lima MLSO, Gonçalves CCS, Barreiro JC, Cass QB, Marsaioli AJ. High Throughput Enzymatic Enantiomeric Excess: Quick-ee.J. Braz. Chem. Soc. 2015;26(2):319-324

/////////////High Throughput,  Enzymatic,  Enantiomeric Excess,  Quick-ee

http://jbcs.sbq.org.br/imagebank/pdf/v26n2a14.pdf

http://jbcs.sbq.org.br/imagebank/pdf/v26n2a14-Sup01.pdf

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

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Abstract Image

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.

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

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

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

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The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?

A key pharmaceutical intermediate (1) for production of edivoxetine·HCl was prepared in >99% ee via a continuous Barbier reaction, which improves the greenness of the process relative to a traditional Grignard batch process. The Barbier flow process was run optimally by Eli Lilly and Company in a series of continuous stirred tank reactors (CSTR) where residence times, solventcomposition, stoichiometry, and operations temperature were optimized to produce 12 g h−1crude ketone 6 with 98% ee and 88% in situ yield for 47 hours total flow time. Continuous salt formation and isolation of intermediate 1 from the ketone solution was demonstrated at 89% yield, >99% purity, and 22 g h−1 production rates using MSMPRs in series for 18 hours total flow time. Key benefits to this continuous approach include greater than 30% reduced process mass intensity and magnesium usage relative to a traditional batch process. In addition, the flow process imparts significant process safety benefits for Barbier/Grignard processes including >100× less excess magnesium to quench, >100× less diisobutylaluminum hydride to initiate, and in this system, maximum long-term scale is expected to be 50 L which replaces 4000–6000 L batch reactors.

A continuous flow Barbier reaction was employed for the production of a key pharmaceutical intermediate (1) in the synthesis of edivoxetine·HCl (a highly selective norepinephrine re-uptake inhibitor).

US scientists from Eli Lilly and Company and D&M Continuous Solutions, led by Michael Kopach, report the development of a continuous Barbier reaction which preserves chirality and the product obtained in >99% ee.  The team ran the process in a series of continuous stirred tank reactors, where residence time, solvent composition, stoichiometry and operations temperature were optimised to produce 12 g per hour of the ketone precursor to 1 with 98% ee and 88% in situ yield for 47 hours total flow time.  Continuous salt formation and isolation of 1 could then be achieved from the ketone solution with >99% purity.

This process offers up several significant advantages over a traditional Grignard batch process.  This continuous flow method gave greater than 30% reduced process mass intensity and magnesium usage relative to the batch method.  Equally, the flow process resulted in >100 x less excess magnesium to quench and >100 x less diisobutylaluminum hydride to initiate giving significant safety benefits.  The authors expect that the maximum long-term scale of the process is 50 L which would replace 4000-6000 L batch reactors.

Continuous Flow Barbier Reaction

Figure 2. Continuous Barbier Laboratory Setup

For 100 years, Grignard reactions have been one of the most powerful and effi cient organic chemistry methodologies for C-C bond formation. However, Grignard reactions are also among the most challenging reactions from both operational and potential safety issues due to initiation diffi culties and runaway potential. A close variation to the Grignard reaction is the Barbier reaction wherein the Grignard reagent is prepared in the presence of an electrophile resulting in the immediate consumption of the Grignard. A Barbier reaction using a CSTR was developed for a key pharmaceutical intermediate in production of edivoxetine·HCl (Scheme 4) [9]. In the fl ow setup (Figure 2), solid magnesium is sequestered in the fi rst tank where the Grignard initiation event takes place. CSTR 2 was used as an aging tank and CSTR 3 was the quench tank. CSTRs were used for Grignard reaction rather than a PFDR because of the solid Mg reagent.

Scheme 4: Barbier Reaction to form Ketone 15

Continuous reaction improved process safety, product quality, and process greenness. The continuous reaction achieved >99% ee in situ versus 95% ee batch because of immediate conversion of unstable intermediate. Solvent volumes were reduced 30%. The safety hazards were reduced by decreasing the reactor size by 50X, which reduced chemical potential and also increased heat transfer surface area per unit volume by 4X. DIBAL-H initiating agent was reduced by more than 100X, and excess Mg that must be quenched at the end of reaction was almost eliminated. When run continuously, the commercial scale Grignard formation reactor was expected to be 50L, which replaces 4000-6000L batch reactor.

The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?

*Corresponding authors
aChemical Product Research and Development, Eli Lilly and Company, Indianapolis, USA
E-mail: kopach_michael@lilly.com
bD&M Continuous Solutions, Indianapolis, USA
Green Chem., 2012,14, 1524-1536

DOI: 10.1039/C2GC35050E

http://pubs.rsc.org/en/Content/ArticleLanding/2012/GC/C2GC35050E#!divAbstract

Three vessel Grignard CSTR process train.

Grignard synthesis of compound 1.

Retrosynthesis of edivoxetine·HCl.

Flow diagram for the whole continuous process from amide 3 to product 1.

Continuous crystallization of compound 1.

Distillation and continuous crystallization of compound 1.

Entry, Rxn temp. (°C), Vol. ratio THF–toluene (%), Conversion (%), ee (%)

//////////The continuous flow,  Barbier reaction,  improved environmental alternative,  Grignard reaction, FLOW SYNTHESIS

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Commercial Production of Semi-Synthetic Artemisinin

New Drug Approvals

STR1

Figure 1. Production of artemisinic acid or β-farnesene by engineered yeast. The sesquiterpene alkenes β-farnesene and amorphadiene are both derived from FPP (farnesyl diphosphate) by the action of specific enzymes introduced from plants: amorphadiene synthase (ADS) generates amorphadiene and β-farnesene synthase (FS) generates β-farnesene. Production strains express either ADS or FS, not both. Oxidation of amorphadiene to artemisinic acid is accomplished by the action of five plant enzymes expressed in the engineered yeast.17 Conversion of purified artemisinic acid to artemisinin is accomplished by in vitro organic chemistry. Isoprenoid production strains make little ethanol.

The antimalarial drug artemisinin and the specialty chemical β-farnesene are examples of natural product isoprenoids that can help solve global challenges, but whose usage has previously been limited by supply and cost impediments. This review describes the path to commercial production of these compounds utilizing fermentation of engineered yeast. Development of commercially viable yeast strains was a…

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