Heck–Matsuda Reaction in Flow

Product 3 was obtained as a mixture of diastereomers (58:42). The NMR data are consistent with literature precedent.20a

Major diastereomer: 1H NMR (300 MHz, CDCl3) δ (ppm) 7.25-7.28 (m, 2H), 7.14-7.17 (m, 2H), 5.14 (dd, 1H, J = 2.5, 5.8 Hz), 4.29 (t, 1H, J = 8.3 Hz), 3.79 (dd, 1H, J = 6.9, 8.4 Hz), 3.54-3.62 (m, 1H), 3.38 (s, 3H), 2.32 (dd, 1H, J = 7.7, 12.9 Hz), 2.04 (ddd, 1H, J = 5.1, 9.3, 13.1 Hz);
Minor diastereomer: 1H NMR (300 MHz, CDCl3) δ 7.25-7.28 (m, 4H), 5.16 (d, 1H, J = 4.4 Hz), 4.17 (t, 1H, J = 8.1 Hz), 3.72 (dd, 1H, J = 8.5, 9.7 Hz), 3.42 (s, 3H), 3.32-3.36 (m, 1H), 2.59 (ddd, 1H, J = 5.5, 10.3, 13.7 Hz), 1.91 (ddd, 1H, J = 2.4, 7.7, 10.2 Hz);

13C NMR (75 MHz, CDCl3) δ (ppm) 141.4, 140.0, 132.4, 132.3, 129.1, 128.7, 128.7, 128.5, 105.7, 105.4, 73.7, 73.0, 54.9, 54.7, 43.6, 42.1, 41.4, 41.1.
(20) (a) Oliveira, C. C.; Angnes, R. A.; Correia, C. R. D. J. Org. Chem. 2013, 78, 4373. (b) Oliveira, C. C.; Pfaltz, A.; Correia, C. R. D. Angew. Chem. Int. Ed. 2015, 54, 14036.

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00310

The optimization of a palladium-catalyzed Heck–Matsuda reaction using an optimization algorithm is presented. We modified and implemented the Nelder–Mead method in order to perform constrained optimizations in a multidimensional space. We illustrated the power of our modified algorithm through the optimization of a multivariable reaction involving the arylation of a deactivated olefin with an arenediazonium salt. The great flexibility of our optimization method allows to fine-tune experimental conditions according to three different objective functions: maximum yield, highest throughput, and lowest production cost. The beneficial properties of flow reactors associated with the power of intelligent algorithms for the fine-tuning of experimental parameters allowed the reaction to proceed in astonishingly simple conditions unable to promote the coupling through traditional batch chemistry.

NMR PREDICT

13C NMR PREDICT

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Nanopalladium-catalyzed conjugate reduction of Michael acceptors - application in flow

Green Chem., 2016, 18,2632-2637
DOI: 10.1039/C5GC02920A, Communication

Anuja Nagendiran, Henrik Sorensen, Magnus J. Johansson, Cheuk-Wai Tai, Jan-E. Backvall
A continuous-flow approach towards the selective nanopalladium-catalyzed hydrogenation of the olefinic bond in various Michael acceptors, which could lead to a greener and more sustainable process, has been developed.

Nanopalladium-catalyzed conjugate reduction of Michael acceptors - application in flow

Communication

Nanopalladium-catalyzed conjugate reduction of Michael acceptors – application in flow

Anuja Nagendiran,^ab   Henrik Sörensen,^bc  Magnus J. Johansson,^bc   Cheuk-Wai Tai^d and   Jan-E. Bäckvall*^ab  

 

*Corresponding authors

^aDepartment of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden
E-mail: jeb@organ.su.se

^b

Berzelii Centre EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden

^c

AstraZeneca R&D, Innovative Medicines, Cardiovascular and Metabolic Disorders, Medicinal Chemistry, Pepparedsleden 1, SE-431 83 Mölndal, Sweden

^d

Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden

Green Chem., 2016,18, 2632-2637

DOI: 10.1039/C5GC02920A

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C5GC02920A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract
A continuous-flow approach towards the selective nanopalladium-catalyzed hydrogenation of the olefinic bond in various Michael acceptors, which could lead to a greener and more sustainable process, has been developed. The nanopalladium is supported on aminofunctionalized mesocellular foam. Both aromatic and aliphatic substrates, covering a variation of functional groups such as acids, aldehydes, esters, ketones, and nitriles were selectively hydrogenated in high to excellent yields using two different flow-devices (H-Cube® and Vapourtec). The catalyst was able to hydrogenate cinnamaldehyde continuously for 24 h (in total hydrogenating 19 g cinnanmaldehyde using 70 mg of catalyst in the H-cube®) without showing any significant decrease in activity or selectivity. Furthermore, the metal leaching of the catalyst was found to be very low (ppb amounts) in the two flow devices.






////////Nanopalladium-catalyzed,  conjugate reduction,  Michael acceptors, application,  flow  chemistry


Hvar Islands (Pakleni, Hvar Island)




























 


 

Kamp Nudist in Vrboska

Hvar has a strong naturist tradition, and Jerolim was named as CNN's top FKK beach for 2011. For the best comnbination of naturist camping and beaches, head through the pine trees to Kamp Nudist near Vrboska.

The history of naturism dates back to another British royal jumping in the water, this time Edward and Mrs. Simpson in the 1930s, when they received permission to bathe nude on the island of Rab. Naturism became very attractive in the 1960s with the emergence of mass tourism, and remains an important part of Croatia's tourism makeup, with more than a million naturist tourists last year, according to official figures.
Hidden from the rest of the tourists through the pine trees just outside Vrboska is the best option for a naturist holiday - the wonderful Kamp Nudist with adjoining beach. A new website for the camp will be launched soon (and we will bring it to you), but for now, enjoy the relaxed atmosphere of Hvar's premier naturist camp through the pictures below, and come on in - the water's lovely!

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Hydrogenation in flow: homogenous and heterogeneous catalysts using Teflon AF-2400 to effect gas-liquid contact at elevated pressure

Hydrogenation in flow: homogenous and heterogeneous catalysts using Teflon AF-2400 to effect gas-liquid contact at elevated pressure

http://pubs.rsc.org/en/Content/ArticleLanding/2011/SC/c1sc00055a#!divAbstract

M. O’Brien, N. Taylor, A. Polyzos, I.R. Baxendale, S.V. Ley, Chem. Sci. 2011, 2, 1250-1257.

A Tube-in-Tube reactor/injector has been developed, based on a gas-permeable Teflon AF-2400 membrane, which allows both heterogeneous and homogeneous catalytic hydrogenation reactions to be efficiently carried out at elevated pressure in flow, thereby increasing the safety profile of these reactions. Measurements of the gas permeation through the tubing and uptake into solution, using both a burette method and a novel computer-assisted ‘bubble counting’ technique, indicate that permeation/dissolution follows Henry's law and that saturation is achieved extremely rapidly. The same gas-permeable membrane has also been shown to efficiently effect removal of excess unreacted hydrogen, thus enabling further downstream reaction/processing.

Homogenous hydn...ABOVE

Heterogenous hydrogenation

M. Amatore, C. Gosmini and J. Périchon, J. Org. Chem., 2006, 71, 6130-6134. \