A chiral analog of the bicyclic guanidine TBD : synthesis, structure and Brønsted base catalysis

Starting from (S)-β-phenylalanine, easily accessible by lipase-catalyzed kinetic resolution, a chiral triamine was assembled by a reductive amination and finally cyclized to form the title compound 10. In the crystals of
Starting from (S)-β-phenylalanine, easily accessible by lipase-catalyzed kinetic resolution, a chiral triamine was assembled by a reductive amination and finally cyclized to form the title compound 10. In the crystals of the guanidinium benzoate salt the six membered rings of 10 adopt conformations close to an envelope with the phenyl substituents in pseudo-axial positions. The unprotonated guanidine 10 catalyzes Diels–Alder reactions of anthrones and maleimides (25–30% ee). It also promotes as a strong Brønsted base the retro-aldol reaction of some cycloadducts with kinetic resolution of the enantiomers. In three cases, the retro-aldol products (48–83% ee) could be recrystallized to high enantiopurity (≥95% ee). The absolute configuration of several compounds is supported by anomalous X-ray diffraction and by chemical correlation.
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Metadaten
Author:Mariano Goldberg, Denis Sartakov, Jan W. Bats, Michael Bolte, Michael W. Göbel
URN:urn:nbn:de:hebis:30:3-445417
DOI:http://dx.doi.org/10.3762/bjoc.12.176
ISSN:1860-5397
Pubmed Id:http://www.ncbi.nlm.nih.gov/pubmed?term=27829893
Parent Title (English):Beilstein journal of organic chemistry
Publisher:Beilstein-Institut zur Förderung der Chemischen Wissenschaften
Place of publication:Frankfurt, Main
Contributor(s):M. Rueping
Document Type:Article
Language:English
Year of Completion:2016
Date of first Publication:2016/08/19
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2017/12/05
Tag:absolute configuration; anthrone; cycloaddition; kinetic resolution; lipase
Volume:12
Pagenumber:7
First Page:1870
Last Page:1876
Note:
License and Terms: This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
HeBIS PPN:424939096
Institutes:Biochemie und Chemie
Dewey Decimal Classification:540 Chemie und zugeordnete Wissenschaften
Sammlungen:Universitätspublikationen
Licence (German):License LogoCreative Commons - Namensnennung 4.0

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