0000000001301013
AUTHOR
Lars Andernach
showing 29 related works from this author
Crystal structure analysis of a star-shaped triazine compound: a combination of single-crystal three-dimensional electron diffraction and powder X-ra…
2017
The solid-state structure of star-shaped 2,4,6-tris{(E)-2-[4-(dimethylamino)-phenyl]ethenyl}-1,3,5-triazine is determined from a powder sample by exploiting the respective strengths of single-crystal three-dimensional electron diffraction and powder X-ray diffraction data. The unit-cell parameters were determined from single crystal electron diffraction data. Using this information, the powder X-ray diffraction data were indexed, and the crystal structure was determined from the powder diffraction profile. The compound crystallizes in a noncentrosymmetric space group,P212121. The molecular conformation in the crystal structure was used to calculate the molecular dipole moment of 3.22 Debye,…
Synthesis of Optically Active Hydroxyalkyl Cycloheptatrienes: A Key Step in the Total Synthesis of 6,11-Methylene-LXB4
2020
AbstractStarting from methyl cycloheptatrienyl-1-carboxylate, 6-acylation was successfully achieved employing glutaryl chloride in the presence of AlCl3 under controlled reaction conditions to furnish keto carboxylic acid product. After protection of this keto carboxylic acid as tert-butyl ester, reagent-controlled enantioselective reductions delivered configuration-defined methyl-6-hydroxylalkyl cycloheptatriene-1-carboxylates with up to 80% ee. Whereas simple NaBH4 reduction of the keto carboxylic acid and subsequent lactonization afforded a methyl-6-tetrahydropyranonyl cycloheptatriene-1-carboxylate. Resolution using chiral HPLC delivered the product enantiomers with up to >99% ee Fin…
ChemInform Abstract: Assignment of the Absolute Configuration and Total Synthesis of (+)-Caripyrin.
2015
The antifungal secondary metabolite (+)-caripyrin was studied by vibrational circular dichroism spectroscopy. Analysis of the recorded data, with the Boltzmann weighted-average of the spectra calculated at the B3LYP/6-311G(d,p) level of theory for all relevant conformers, unequivocally proved the (R,R)-configuration for the dextrorotatory natural product. Based on this finding, a short enantioselective synthesis of (+)-caripyrin was developed.
Absolute Configuration Determination of 2,3-Dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles Using Chiroptical Methods at Different Wavelengths
2016
A correlation between the absolute configuration and chiroptical properties of nonracemic 1,6,7-trisubstituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles was studied. A series of 16 novel representatives were prepared by Cu-catalyzed [3 + 2] cycloadditions of racemic (Z)-2-benzylidene-5-oxopyrazolidin-2-ium-1-ides to tert-butyl (S)-(3-oxopent-4-yn-2-yl)carbamate, and their structures were determined by NMR, VCD, ECD, and X-ray diffraction. A clear correlation between the sign of specific rotation and configuration at position C(1) allows for easy determination of the absolute configuration of 1,6,7-trisubstituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles by ECD and NMR. While VCD, requirin…
ChemInform Abstract: Synthesis and Isolation of Enantiomerically Enriched Cyclopenta[b]benzofurans Based on Products from Anodic Oxidation of 2,4-Dim…
2015
Tetramer (I) is obtained by anodic oxidation of 2,4-dimethylphenol as reported in a previous paper.
Assignment of the Absolute Configuration and Total Synthesis of (+)-Caripyrin
2014
The antifungal secondary metabolite (+)-caripyrin was studied by vibrational circular dichroism spectroscopy. Analysis of the recorded data, with the Boltzmann weighted-average of the spectra calculated at the B3LYP/6-311G(d,p) level of theory for all relevant conformers, unequivocally proved the (R,R)-configuration for the dextrorotatory natural product. Based on this finding, a short enantioselective synthesis of (+)-caripyrin was developed.
Chromatographically separable rotamers of an unhindered amide
2014
Surprisingly stable formamide rotamers were encountered in the tetrahydroisoquinoline and morphinan series of alkaloids. We investigated the hindered rotation around the amide bond by dynamic high-performance liquid chromatography (DHPLC) and kinetic measurements of the interconversion of the rotamers which can readily be separated by HPLC as well as TLC. The experimental results of the different methods were compared to each other as well as to results obtained by DFT calculations.
Separation, isolation and stereochemical assignment of imazalil enantiomers and their quantitation in an in vitro toxicity test
2016
A simple method for the separation of the enantiomers of the fungicide imazalil was developed. Racemic imazalil was separated into its enantiomers with an enantiomeric purity of 99% using HPLC-UV with an enantioselective column (permethylated cyclodextrin) operated in reversed phase mode (water with 0.2% trimethylamine and 0.08% acetic acid and methanol). The absolute configuration of the separated enantiomers was assigned and unequivocally confirmed by optical rotation as well as by vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) combined with ab-initio calculations. The same enantioselective column was also used to develop an HPLC-MS/MS method for the quantifi…
ChemInform Abstract: Iodocyclization of o-Alkynylbenzamides Revisited: Formation of Isobenzofuran-1(3H)-imines and 1H-Isochromen-1-imines Instead of …
2013
Remarkably, isobenzofuran and benzopyran derivatives are obtained by the title reaction and not as described in earlier publications five- or six-membered lactams.
Total Synthesis of (±)-Oxalicumone C and Chiral Resolution and Elucidation of Its Absolute Configuration
2014
The racemic total synthesis, the chiral resolution, and the elucidation of the absolute configuration of the natural product oxalicumone C were investigated. The goal was achieved by a synthetic strategy beginning with the synthesis of a 5-hydroxy-7-methylchromone precursor. Further modification possibilities were achieved by introduction of a vinyl moiety into the chromone, which was based on a selective iodination step in the 3-position. Further transformations furnished the racemic natural product. To determinate the absolute configuration of naturally occurring oxalicumone C, both enantiomers were separated by chiral HPLC. Comparison of the calculated and experimental vibrational circul…
Assignment of Configuration in a Series of Dioxolanone-Type Secondary Metabolites fromGuignardia bidwellii- A Comparison of VCD and ECD Spectroscopy
2013
The absolute configurations of a series of phytotoxic dioxolanone-type secondary metabolites isolated from culture filtrates of the grape black rot fungus Guignardia bidwellii were determined by vibrational circular dichroism (VCD) spectroscopy in the mid-IR frequency range. Comparison of the recorded data with DFT calculations showed good agreement between experiment and theory for VCD, whereas electronic circular dichroism (ECD) data for the compounds matched poorly with the predicted spectra obtained by time-dependent DFT (TDDFT) calculations at the same level of theory.
Total Synthesis of epi-Trichosetin.
2018
The natural 3-decalinoyltetramic acid epi-trichosetin was synthesized in ten steps starting from ( R)-(+)-citronellal using an intramolecular Diels-Alder reaction and a Lacey-Dieckmann cyclization as the key steps. The use of a 2-nitrobenzyl protecting group resulted in an efficient synthetic endgame. The natural product was obtained in 4.1% overall yield.
ChemInform Abstract: Total Synthesis of (-)-Hymenosetin.
2016
Hymenosetin (I) and its N-methyl analogue are prepared in 11 and 8 steps, respectively, from citronellal employing an intramolecular Diels-Alder reaction as the key step.
Total Synthesis of (-)-Hymenosetin.
2015
The 3-decalinoyltetramic acid (−)-hymenosetin and its N-methyl analogue were prepared in 11 and 8 steps, respectively, from (+)-citronellal using an intramolecular Diels–Alder reaction as the key step. This method represents the first example for the synthesis of a 3-decalinoyltetramic acid with a free NH moiety. The stereochemistry of the title compound, an unnatural diastereomer, and of a decalin building block was studied in detail using circular dichroism spectroscopy in the IR and UV/VIS freqeuncy range. This allowed to determine the absolute configuration of the natural product and to plan the synthetic route.
Iodocyclization of o-Alkynylbenzamides Revisited: Formation of Isobenzofuran-1(3H)-imines and 1H-Isochromen-1-imines Instead of Lactams
2012
The iodocyclization of o-alkynylbenzamides with various electrophiles has been reported to yield five- or six-membered lactams by nucleophilic attack of the amide nitrogen onto the triple bond. While the formation of an isobenzofuran-1(3H)-imine with two bulky substituents under Larock conditions was initially attributed to steric hindrance, we found out that cyclization via the amide oxygen is the rule rather than the exception. Thus, the structures of the products reported in the literature need to be revised.
Terphenyl Derivatives from Allantophomopsis lycopodina.
2016
Three secondary fungal metabolites 1–3 with a benzo[b]naphtho[2,1-d]furan skeleton were isolated from submerged cultures of the ascomycete Allantophomopsis lycopodina. The NMR-based structure elucidation was challenging due to a low H/C ratio of only 0.64 and 0.68, respectively. NMR measurements in two different solvents and the use of NMR experiments such as HSQC-TOCSY and LR-HSQMBC proved to be helpful in this respect. The proposed structures obtained from the comprehensive analysis of the NMR data were verified by comparison of recorded and computed NMR chemical shifts from quantum chemical calculations of several constitutional isomers and were further analyzed with the aid of the DP4 a…
Synthesis and Isolation of Enantiomerically Enriched Cyclopenta[b]benzofurans Based on Products from Anodic Oxidation of 2,4-Dimethylphenol
2015
The anodic treatment of 2,4-dimethylphenol offers a powerful and direct method for the construction of a dehydrotetramer with four contiguous stereocentres on a multigram scale. The installation of propellanes on this scaffold using enantiomerically pure carbonyl compounds leads to a mixture of diastereomers. This mixture is easily separable using standard chromatography and gives rise to optically pure cyclopenta[b]benzofurans which are important scaffolds in a variety of natural products. The synthesis is easy to perform and allows a reliable access to chiral compounds with very high enantiomeric excess. It was possible to determine the absolute configuration of these compounds by compari…
CCDC 897109: Experimental Crystal Structure Determination
2013
Related Article: Claudine Schlemmer , Lars Andernach , Dieter Schollmeyer, Bernd F. Straub , and Till Opatz|2012|J.Org.Chem.|77|10118|doi:10.1021/jo3017378
CCDC 898755: Experimental Crystal Structure Determination
2013
Related Article: Claudine Schlemmer , Lars Andernach , Dieter Schollmeyer, Bernd F. Straub , and Till Opatz|2012|J.Org.Chem.|77|10118|doi:10.1021/jo3017378
CCDC 1047644: Experimental Crystal Structure Determination
2017
Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600
CCDC 1497003: Experimental Crystal Structure Determination
2016
Related Article: Eva Pušavec Kirar, Uroš Grošelj, Amalija Golobič, Franc Požgan, Stefan Pusch, Carina Weber, Lars Andernach, Bogdan Štefane, Till Opatz, Jurij Svete|2016|J.Org.Chem.|81|11802|doi:10.1021/acs.joc.6b02270
CCDC 1047645: Experimental Crystal Structure Determination
2017
Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600
CCDC 897110: Experimental Crystal Structure Determination
2013
Related Article: Claudine Schlemmer , Lars Andernach , Dieter Schollmeyer, Bernd F. Straub , and Till Opatz|2012|J.Org.Chem.|77|10118|doi:10.1021/jo3017378
CCDC 897106: Experimental Crystal Structure Determination
2013
Related Article: Claudine Schlemmer , Lars Andernach , Dieter Schollmeyer, Bernd F. Straub , and Till Opatz|2012|J.Org.Chem.|77|10118|doi:10.1021/jo3017378
CCDC 1497004: Experimental Crystal Structure Determination
2016
Related Article: Eva Pušavec Kirar, Uroš Grošelj, Amalija Golobič, Franc Požgan, Stefan Pusch, Carina Weber, Lars Andernach, Bogdan Štefane, Till Opatz, Jurij Svete|2016|J.Org.Chem.|81|11802|doi:10.1021/acs.joc.6b02270
CCDC 1047647: Experimental Crystal Structure Determination
2017
Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600
CCDC 1497005: Experimental Crystal Structure Determination
2016
Related Article: Eva Pušavec Kirar, Uroš Grošelj, Amalija Golobič, Franc Požgan, Stefan Pusch, Carina Weber, Lars Andernach, Bogdan Štefane, Till Opatz, Jurij Svete|2016|J.Org.Chem.|81|11802|doi:10.1021/acs.joc.6b02270
CCDC 897107: Experimental Crystal Structure Determination
2013
Related Article: Claudine Schlemmer , Lars Andernach , Dieter Schollmeyer, Bernd F. Straub , and Till Opatz|2012|J.Org.Chem.|77|10118|doi:10.1021/jo3017378
CCDC 1047646: Experimental Crystal Structure Determination
2017
Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600