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Novel Reactions

Schaubild: Development of Homogeneously Catalysed Reactions: Feedstock(organic, oil etc.) -> steering wheel (Rh, Fe, Pd, Co, Ru, Ir, Ni, Pt) -> Himmlsrichtungen beschriftet (starting north,clockwise; carbonylation, hydrogenation, hydroformylation, telomerisation, aminations, metathesis, tandem reactions, oxidations) -> Endprodukte

Direct Synthesis of an a,w-Diester from 2,7-Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Ostrowski, K. A., Vogelsang, D., Seidensticker, T., Vorholt A. J.

Abstract: A new tandem catalytic process was designed and developed as at tool for the direct conversion of the widely available feedstock 2,7-octadienol into an a,w-diester. This innovative auto-tandem catalysis is atom efficient and consists of three consecutive palladium-catalysed reactions: ether formation, ether carbonylation and alkoxycarbonylation. By using the design of experiments (DoE) approach, significant parameters were determined and the yield of the desired a,w-diester was optimised. Model substrates allowed deeper insight into the progress of the reaction to be gained and, as a result, the reaction sequence was uncovered. Furthermore, by simply applying other ligands, a different reaction path was followed, allowing other, new tandem catalytic sequences to be explored and enabling new compounds to be obtained.

Chem. Eur. J. 2016, 22 (5), 1840-1846; DOI: 10.1002/chem.201503785

Bausteine aufeinander gestapelt mit Strukturformeln, von unten nach oben: 2,7-octadienol, 2-Methoxy-3,8-nonen und 2-Methoxy-2-Ethylen-6-Hepten, 3,8-nonenethylester, a,w-diester

Rhodium-Catalyzed Bis-Hydroaminomethylation of Linear Aliphatic Alkenes with Piperazine

Seidensticker, T. , Vosberg, J. M., Ostrowksi, K. A., Vorholt, A. J.

Abstract: An efficient protocol was developed to prepare a series of dialkylpiperazines via Rh-catalyzed bis-hydroaminomethylation of linear aliphatic alkenes with piperazine. The well-known Rh/Biphephos catalytic system was applied, yielding the desired dialkylpiperazines within six tandem catalytic steps, already at low catalyst loadings of 0.1mol%. For the model alkene 1-octene, good yields and linearities of 80% and 77:23, respectively, were achieved under optimized conditions. Influences on the catalytic system regarding n/isoratio, possible side reactions and the reaction path are discussed on the basis of yield vs.time plots and parameter optimization. With the developed general protocol, other linear, functionalized and branched substrates were effectively transformed to the corresponding linear N,N-disubstituted piperazines.

Adv. Synth. Catal. 2016, 358, 610-621; DOI: 10.1002/adsc.201500896

Schaubild: linear aliphatic olefins

Linear selective isomerization / hydroformylation of unsaturated fatty acid methyl esters –A bimetallic approach

Gaide, T., Bianga, J., Schlipköter, K. E., Behr , A., Vorholt, A. J.

Abstract: A key challenge in synthesis of non-ionic surfactants is opposite polarity of the substrates and the connected challenge to use homogeneous catalysis. We present the telomerisation ofβ-myrcene with N-methylglucamine to C20-N-alkylated polyols, which show surface activity. The use of aqueous solvent systems along with amphiphilic ligands bridges the polaritiy gap and shows high reactivities.

ACS Catal. 2017, 7, 6, 4163-4171; DOI: 10.1021/acscatal.7b00249

Mensch mit Cap mit der Aufschrift [Pd] hilft Mensch mit Cap mit der Aufschrift [Rh] über eine Mauer die mit "Isomerization" und "Hydroformylation" und der Strukturformel von einer ungesättigten Fettsäuremethylester beschriftet ist

From Carboxytelomerisation of 1,3-Butadiene to Linear a,w-C10-Diester Combinatoric Approaches for an Efficient Synthetic Route

Vogelsang, D., Raumann, B. A., Hares, K., Vorholt, A. J.

Abstract: Two novel reaction pathways were tested to synthesize the linear a,w-C10-diester exclusively from three basic reagents: 1,3-butadiene, carbon monoxide and methanol. Therefor, carboxytelomerization of 1,3-butadiene with methanol was merged with methoxycarbonylation in two different ways to obtain highly linear C10-diester. Through a palladium-based and –assisted tandem catalytic system, 22% yield of the desired C10-diester was obtained without isolating the intermediates. Subsequently, the limitations of the novel assisted tandem catalytic concept were uncovered and based on that, a two-step reaction regime was established. By optimization of the carboxytelomerization, the C9-monoester as intermediate could be formed in nearly quantitative yields and excellent linearity. In a second reaction step, the isolated monoester was successfully converted by methoxycarbonylation into the desired linear C10-diester in overall yields up to 84%.

Chem. Eur. J. 2018, 24, 9, 2264-2269; DOI: 10.1002/chem.201705381

Schaubild: Tornado mit Beschriftung Pd in den MeOH, CO, Diethen gesaugt wird und unten kommt a,w-C10-Diester raus, Seitenbeschriftung neben tornado: carboxy telomerization, methoxy carbonylation

Location & approach

The campus of TU Dort­mund University is located close to interstate junction Dort­mund West, where the Sauerlandlinie A 45 (Frankfurt-Dort­mund) crosses the Ruhrschnellweg B 1 / A 40. The best interstate exit to take from A 45 is “Dort­mund-Eichlinghofen” (closer to South Campus), and from B 1 / A 40 “Dort­mund-Dorstfeld” (closer to North Campus). Signs for the uni­ver­si­ty are located at both exits. Also, there is a new exit before you pass over the B 1-bridge leading into Dort­mund.

To get from North Campus to South Campus by car, there is the connection via Vogelpothsweg/Baroper Straße. We recommend you leave your car on one of the parking lots at North Campus and use the H-Bahn (suspended monorail system), which conveniently connects the two campuses.

TU Dort­mund University has its own train station (“Dort­mund Uni­ver­si­tät”). From there, suburban trains (S-Bahn) leave for Dort­mund main station (“Dort­mund Hauptbahnhof”) and Düsseldorf main station via the “Düsseldorf Airport Train Station” (take S-Bahn number 1, which leaves every 20 or 30 minutes). The uni­ver­si­ty is easily reached from Bochum, Essen, Mülheim an der Ruhr and Duisburg.

You can also take the bus or subway train from Dort­mund city to the uni­ver­si­ty: From Dort­mund main station, you can take any train bound for the Station “Stadtgarten”, usually lines U41, U45, U 47 and U49. At “Stadtgarten” you switch trains and get on line U42 towards “Hombruch”. Look out for the Station “An der Palmweide”. From the bus stop just across the road, busses bound for TU Dort­mund University leave every ten minutes (445, 447 and 462). Another option is to take the subway routes U41, U45, U47 and U49 from Dort­mund main station to the stop “Dort­mund Kampstraße”. From there, take U43 or U44 to the stop “Dort­mund Wittener Straße”. Switch to bus line 447 and get off at “Dort­mund Uni­ver­si­tät S”.

The AirportExpress is a fast and convenient means of transport from Dortmund Airport (DTM) to Dortmund Central Station, taking you there in little more than 20 minutes. From Dortmund Central Station, you can continue to the university campus by interurban railway (S-Bahn). A larger range of international flight connections is offered at Düsseldorf Airport (DUS), which is about 60 kilometres away and can be directly reached by S-Bahn from the university station.

The H-Bahn is one of the hallmarks of TU Dort­mund University. There are two stations on North Campus. One (“Dort­mund Uni­ver­si­tät S”) is directly located at the suburban train stop, which connects the uni­ver­si­ty directly with the city of Dort­mund and the rest of the Ruhr Area. Also from this station, there are connections to the “Technologiepark” and (via South Campus) Eichlinghofen. The other station is located at the dining hall at North Campus and offers a direct connection to South Campus every five minutes.

The facilities of TU Dortmund University are spread over two campuses, the larger Campus North and the smaller Campus South. Additionally, some areas of the university are located in the adjacent “Technologiepark”.

Site Map of TU Dortmund University (Second Page in English).