The manufacture of high mechanical strength cellulose‐based carbon fibers (CFs) is accomplished in a continuous process at comparably low temperatures and with high carbon yields. Applying a sulfur‐based carbonization agent, i.e., ammonium tosylate (ATS), carbon yields of 37% (83% of theory), and maximum tensile strengths and Young's moduli up to 2.0 and 84 GPa are obtained already at 1400 °C. For comparison, the use of the well‐known carbonization aid ammonium dihydrogenphosphate ((NH4)H2PO4), ADHP, is also investigated. Both the precursor and the CFs are characterized via elemental analysis, wide‐angle X‐ray scattering, Raman spectroscopy, scanning electron microscopy, and tensile testing. Thermogravimetric analysis coupled with mass spectrometry/infrared spectroscopy discloses differences in structure formation between ATS and ADHP‐derived CFs during pyrolysis.
The first catalytic, enantioselective vinylogous Mannich reaction of acyclic silyl dienolates is reported. A second-generation 2,2'-dihydroxy-1,1'-binaphthyl (BINOL)-based phosphoric acid has been developed and further optimized as an enantioselective organocatalyst. Upon protonation of the imines, chiral contact ion pairs are generated in situ and attacked highly diastereoselectively by the nucleophile. gamma-Substituted silyl dienolates that lead to more highly substituted Mannich products with a second stereogenic center in good diastereoselectivity have been employed in these reactions. The reaction path has been elucidated with NMR spectroscopy and mass spectrometry, which suggest that the protic reaction medium found to be optimal in these reactions serves to trap the cationic silicon species as silanol. A crystal structure of a phosphoric acid bound imine was obtained that provides insight into the binding mode and a rationale for the stereochemical course of the reaction.
Recent progress in the field of catalytic, enantioselective vinylogous Michael reactions of latent dienolates is described which furnish optically highly enriched chiral 1,7-dioxo compounds of great utility in one synthetic operation. Emphasis is given to new catalysis modes which realise this challenging transformation with high regio- as well as enantioselectivity.
Sixteen indolizidine-based alkaloids (IBAs) that were isolated as poison constituents of the skin of frogs were synthesized in a highly flexible and stereoselective manner. As a key step, a three-component, organocatalytic, highly enantio- and diastereoselective vinylogous Mukaiyama-Mannich reaction was employed furnishing optically highly enriched butyrolactams as central intermediates on a multigram scale. The attached six-membered ring was constructed through cyclization of the pendant enoate moiety onto the pyrrolidine ring. The absolute configuration of the bridgehead chiral center and the adjacent 8-position was established in the initial vinylogous Mannich reaction, whereas the 3- and 5-substituents were introduced through organometallic addition at a late stage of the synthesis with full stereochemical control from the substrate. With this strategy, simple as well as even more complex alkaloids were accessible in good overall yields as single stereoisomers. These syntheses also served to establish the absolute and relative configuration of those IBAs that had never been synthesized before.
Four indolizidine based alkaloids (IBAs) have been synthesized in a highly enantioselective, straightforward, and flexible manner. As a key step our previously developed Brønsted acid catalyzed vinylogous Mannich reaction was employed which easily afforded gram amounts of an optically pure central intermediate which can be converted into a wide range of diversely substituted IBAs.
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