Type of Publication: | Journal article |
URI (citable link): | http://nbn-resolving.de/urn:nbn:de:bsz:352-opus-47758 |
Author: | Schöllkopf, Ulrich; Groth, Ulrich; Gull, Martin-Reinhold; Nozulak, Joachim |
Year of publication: | 1983 |
Published in: | Liebigs Annalen der Chemie ; 7 (1983), 7. - pp. 1133-1151. - ISSN 0170-2041. - eISSN 1099-0690 |
DOI (citable link): | https://dx.doi.org/10.1002/jlac.198319830706 |
Summary: |
The lithiated bis(1actim) ether 8a furnishes with aldehydes and ketones in good yields the addition products 11 with (3R) configuration. The asymmetric inductions at C-3 of 11 (d.e. values) amount to more than 95% with ketones, with aldehydes they are somewhat smaller. With unsymmetrical ketones or aldehydes C-3' also becomes a chiral center. For the (3R)-major diastereomers the "second induction" at C-3' varies from about 4 to about 87% (for benzaldehyde or isobutyraldehyde, respectively), preferably the (3R,3'S) epimers are formed. - Acid hydrolysis of 11 yields (besides methyl L-valinate) the (2R)-serine methyl esters 26. Their e.e. values correspond with the d.e. values of 11. - Dehydratation of 11 furnishes the "Hofmann olefins" 32 and/or the "Saytzeff olefins" 33 which can be transformed in various ways into optically active amino acids.
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Summary in another language: |
Der lithiierte Bislactimether 8a liefert mit Aldehyden oder Ketonen in guten Ausbeuten die Produkte 11 mit (3R)-Konfiguration. Die asymmetrischen lnduktionen an C-3 (d.-e.-Werte von 11) betragen bei Ketonen mehr als 95%, bei Aldehyden sind sie etwas geringer (Tabelle 1). Bei unsymmetrischen Ketonen oder Aldehyden wird auch C-3' zu einem Chiralitatszentrum. Bei den (3R)-Hauptdiastereomeren übetragen die "Zweitinduktionen" an C-3'ca. 4 bis ca. 87% (z. B. Benzaldehyd oder Isobutyraldehyd); vorzugsweise entstehen die (3R,3'S)-Epimeren (Tabelle 1). - Bei der sauren Hydrolyse der Addukte 11 erhält man (neben Methyl-L-valinat) die (2R)-Serin-methylester 26, deren e.-e.-Werte an C-2 der asymmetrischen Induktion an C-3 von 11 entsprechen. - Die Dehydratisierung von 11 führt zu den "Hofmann-Olefinen" 32 und/oder den "Saytzeff-Olefinen" 33, die verschiedenartig zu optisch aktiven Aminosauren abwandelbar sind.
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Subject (DDC): | 540 Chemistry |
Link to License: | Attribution-NonCommercial-NoDerivs 2.0 Generic |
SCHÖLLKOPF, Ulrich, Ulrich GROTH, Martin-Reinhold GULL, Joachim NOZULAK, 1983. Zur enantioselektiven Synthese von (2R)-Serin-methylestern oder (2R)-Serinen ausgehend vom Bislactimether von cyclo-(-L-Val-Gly-). In: Liebigs Annalen der Chemie. 7(7), pp. 1133-1151. ISSN 0170-2041. eISSN 1099-0690. Available under: doi: 10.1002/jlac.198319830706
@article{Schollkopf1983enant-9737, title={Zur enantioselektiven Synthese von (2R)-Serin-methylestern oder (2R)-Serinen ausgehend vom Bislactimether von cyclo-(-L-Val-Gly-)}, year={1983}, doi={10.1002/jlac.198319830706}, number={7}, volume={7}, issn={0170-2041}, journal={Liebigs Annalen der Chemie}, pages={1133--1151}, author={Schöllkopf, Ulrich and Groth, Ulrich and Gull, Martin-Reinhold and Nozulak, Joachim} }
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