@article{BehrendtSchlaad2018, author = {Behrendt, Felix Nicolas and Schlaad, Helmut}, title = {Entropy-Driven Ring-Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s}, series = {Macromolecular rapid communications}, volume = {39}, journal = {Macromolecular rapid communications}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201700735}, pages = {4}, year = {2018}, abstract = {Metal-free entropy-driven disulfide metathesis polymerization of unsaturated L-cystine based macrocycles produces high-molar-mass heterofunctional poly(disulfide)s, i.e., poly(ester-disulfide-alkene) and poly(amide-disulfide-alkene); M-w(app) = 44-60 kDa, (sic) > 1.7. The polymerization is fast and reaches equilibrium within 1-5 minutes (monomer conversion 70-90\%) in polar aprotic solvents such as N,N-dimethylacetamide, dimethylsulfoxide, or y-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.}, language = {en} } @article{KarrasDabrowskiPohletal.2018, author = {Karras, Manfred and Dabrowski, Michal and Pohl, Radek and Rybacek, Jiri and Vacek, Jaroslav and Bednarova, Lucie and Grela, Karol and Stary, Ivo and Stara, Irena G. and Schmidt, Bernd}, title = {Helicenes as Chirality-Inducing Groups in Transition-Metal Catalysis}, series = {Chemistry - a European journal}, volume = {24}, journal = {Chemistry - a European journal}, number = {43}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201802786}, pages = {10994 -- 10998}, year = {2018}, abstract = {Helical chirality is a novel enantioselectivity-inducing property in transition-metal-catalyzed transformations. The principle is illustrated herein for the example of asymmetric olefin metathesis. This work reports the synthesis of the first helically chiral Ru-NHC alkylidene complex from an aminohelicene-derived imidazolium salt, which was ligated to the first generation Hoveyda-Grubbs catalyst. Kinetic data were acquired for benchmark test reactions and compared to an achiral catalyst. The helically chiral Ru-catalyst was evaluated in asymmetric ring-closing metathesis (RCM) and ring-opening metathesis-cross-metathesis (ROM/CM) reactions, which proceeded with promising levels of enantioselectivity. Extensive NMR-spectroscopic investigations and a DFT geometry optimization were performed. These results led to a topographic steric map and calculation of percent-buried-volume values for each quadrant around the metal center.}, language = {en} } @article{DebsharmaBehrendtLaschewskyetal.2019, author = {Debsharma, Tapas and Behrendt, Felix Nicolas and Laschewsky, Andre and Schlaad, Helmut}, title = {Ring-opening metathesis polymerization of biomass-derived levoglucosenol}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker}, volume = {58}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker}, number = {20}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201814501}, pages = {6718 -- 6721}, year = {2019}, abstract = {The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100kgmol(-1) and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 degrees C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.}, language = {en} } @article{SchmidtStaude2006, author = {Schmidt, Bernd and Staude, Lucia}, title = {Unexpected transfer hydrogenation of C-C-double bonds during Tandem-RCM-isomerization reactions}, series = {Journal of organometallic chemistry}, volume = {691}, journal = {Journal of organometallic chemistry}, number = {24-25}, publisher = {Elsevier}, address = {Lausanne}, issn = {0022-328X}, doi = {10.1016/j.jorganchem.2006.07.011}, pages = {5218 -- 5221}, year = {2006}, abstract = {Unexpected hydrogen transfer from 2-propanol to C-C-double bonds has been observed in the course of a Tandem RCM-isomerization reaction leading to sterically congested spirocycles.}, language = {en} } @article{SchmidtHauke2014, author = {Schmidt, Bernd and Hauke, Sylvia}, title = {Olefin cross metathesis based de novo synthesis of a partially protected L-amicetose and a fully protected L-cinerulose derivative}, series = {Beilstein journal of organic chemistry}, volume = {10}, journal = {Beilstein journal of organic chemistry}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {1860-5397}, doi = {10.3762/bjoc.10.102}, pages = {1023 -- 1031}, year = {2014}, abstract = {Cross metathesis of a lactate derived allylic alcohol and acrolein is the entry point to a de novo synthesis of 4-benzoate protected L-amicetose and a cinerulose derivative protected at C5 and C1.}, language = {en} } @article{SchmidtHaukeMuehlenberg2014, author = {Schmidt, Bernd and Hauke, Sylvia and Muehlenberg, Nino}, title = {Imino glycals via Ruthenium-catalyzed RCM and isomerization}, series = {Synthesis}, volume = {46}, journal = {Synthesis}, number = {12}, publisher = {Thieme}, address = {Stuttgart}, issn = {0039-7881}, doi = {10.1055/s-0033-1338615}, pages = {1648 -- 1658}, year = {2014}, abstract = {N-Allyl-N-homoallylamines were converted in one step into cyclic enamides via a ruthenium-catalyzed assisted tandem catalytic ring-closing metathesis-isomerization sequence. The sequence relies on the in situ transformation of a metathesis active Ru-carbene into an isomerization active Ru-hydride by addition of hydroxide as a chemical trigger.}, language = {en} } @article{SchmidtKunz2012, author = {Schmidt, Bernd and Kunz, Oliver}, title = {alpha,beta-Unsaturated delta-Valerolactones through RCM-Isomerization Sequence}, series = {Synlett : accounts and rapid communications in synthetic organic chemistry}, journal = {Synlett : accounts and rapid communications in synthetic organic chemistry}, number = {6}, publisher = {Thieme}, address = {Stuttgart}, issn = {0936-5214}, doi = {10.1055/s-0031-1290488}, pages = {851 -- 854}, year = {2012}, abstract = {alpha,beta-Unsaturated d-lactones are accessible via a sequential ring-closing metathesis (RCM) double-bond migration reaction starting from butenoates of allyl alcohols. This approach proceeds efficiently with lower catalyst loadings and higher initial substrate concentrations compared to the alternative RCM of acrylates derived from homoallylic alcohols.}, language = {en} } @article{KreyeTueruencSehlingeretal.2012, author = {Kreye, Oliver and T{\"u}r{\"u}nc, Oguz and Sehlinger, Ansgar and Rackwitz, Jenny and Meier, Michael A. R.}, title = {Structurally diverse polyamides obtained from monomers derived via the Ugi multicomponent reaction}, series = {Chemistry - a European journal}, volume = {18}, journal = {Chemistry - a European journal}, number = {18}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201103341}, pages = {5767 -- 5776}, year = {2012}, abstract = {The combination of the Ugi four-component reaction (Ugi-4CR) with acyclic diene metathesis (ADMET) or thiolene polymerization led to the formation of poly-1-(alkylcarbamoyl) carboxamides, a new class of substituted polyamides with amide moieties in the polymer backbone, as well as its side chains. 10-Undecenoic acid, obtained by pyrolysis of ricinoleic acid, the main fatty acid of castor oil, was used as the key renewable building block. The use of different primary amines, as well as isonitriles (isocyanides) for the described Ugi reactions provided monomers with high structural diversity. Furthermore, the possibility of versatile post-modification of functional groups in the side chains of the corresponding polymers should be of considerable interest in materials science. The obtained monomers were polymerized by ADMET, as well as thiolene, chemistry and all polymers were fully characterized. Finally, ortho-nitrobenzylamide-containing polyamides obtained by this route were shown to be photoresponsive and exhibited a dramatic change of their properties upon irradiation with light.}, language = {en} } @article{SchmidtKrehlSoteloMeza2012, author = {Schmidt, Bernd and Krehl, Stefan and Sotelo-Meza, Veronica}, title = {Synthesis of chromanes through RCM-Transfer hydrogenation}, series = {Synthesis}, volume = {44}, journal = {Synthesis}, number = {11}, publisher = {Thieme}, address = {Stuttgart}, issn = {0039-7881}, doi = {10.1055/s-0031-1289758}, pages = {1603 -- 1613}, year = {2012}, abstract = {A sequential ruthenium-catalyzed ring-closing metathesis-transfer hydrogenation sequence has been established as a synthesis of chromanes starting from 2-(allyloxy)styrenes. The sequence requires only one precatalyst, the first-generation Grubbs catalyst, which is converted into a ruthenium hydride species in situ. Propan-2-ol serves as a chemical trigger for the formation of the ruthenium hydride and as hydrogen source.}, language = {en} } @article{SchmidtKunz2013, author = {Schmidt, Bernd and Kunz, Oliver}, title = {Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C-2-symmetric building block: a strategy for the synthesis of decanolide natural products}, series = {Beilstein journal of organic chemistry}, volume = {9}, journal = {Beilstein journal of organic chemistry}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {1860-5397}, doi = {10.3762/bjoc.9.289}, pages = {2544 -- 2555}, year = {2013}, abstract = {Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.}, language = {en} }