Enantiomerically pure acetylene-containing α-amino acids were used as versatile starting materials for the synthesis of a variety of heterocycles via Pd-mediated cyclization reactions. Depending on the protecting group strategy, both the carboxylate and the amine function of the amino acids could participate in the cyclizations, thus giving rise to oxygen heterocycles (α-aminolactones) and nitrogen heterocycles (cyclic α-amino acid derivatives), respectively. Beside the straightforward cyclization, cyclization/cross-coupling reactions were also successfully carried out to provide the corresponding substituted cyclic amino acid derivatives.

A set of both enantiomeric forms of non-proteinogenic, unsaturated α-H-α-amino acids was efficiently synthesized using a biocatalytic pathway. This route involved the straightforward synthesis of the required unsaturated amino acid amides, followed by resolution with an aminopeptidase present in Pseudomonas putida ATCC 12633 and/or a genetically modified organism, leading to the ( S )-acids and ( R )-amides. Undesired amino acid racemase activity was identified in the wild-type strain, which was absent in the newly developed organism. The ( R )-amides were hydrolyzed under mild conditions using an amidase present in whole cells from Rhodococcus erythropolis NCIMB 11540 to the ( R )-acids. The viability of this procedure was demonstrated with the multi-gram synthesis of a variety of unsaturated amino acids in excellent enantiopurity.

ADVERTISEMENT RETURN TO ISSUEPREVNoteNEXTSynthesis of Diaminosuberic Acid Derivatives via Ring-Closing Alkyne MetathesisBegoña Aguilera, Larissa B. Wolf, Piotr Nieczypor, Floris P. J. T. Rutjes, Herman S. Overkleeft, Jan C. M. van Hest, Hans E. Schoemaker, Bing Wang, Johannes C. Mol, Alois Fürstner, Mark Overhand, Gijs. A. van der Marel, and Jacques H. van BoomView Author Information Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA Leiden, The Netherlands, Institute of Molecular Chemistry,University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands, Department of Organic Chemistry, University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands, DSM Research, Life Science Products, PO Box 18, 6160 MD Geleen, The Netherlands, and Max Planck Institut für Kohlenforschung, Mulheim a/d Ruhr, Germany %[email protected]Cite this: J. Org. Chem. 2001, 66, 10, 3584–3589Publication Date (Web):April 19, 2001Publication History Received13 December 2000Published online19 April 2001Published inissue 1 May 2001https://pubs.acs.org/doi/10.1021/jo001734xhttps://doi.org/10.1021/jo001734xbrief-reportACS PublicationsCopyright © 2001 American Chemical SocietyRequest reuse permissionsArticle Views1191Altmetric-Citations57LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Adducts,Disulfides,Metathesis,Peptides and proteins,Reaction products Get e-Alerts

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

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Covering the literature from 1990 to May 2000.

[reaction: see text] By choosing the right substituents either highly functionalized unusual four-membered ring amino acids or the isomeric pipecolic acid derivatives are obtained in enantiomerically pure form. Starting material is a linear allene-containing amino acid that has been resolved via biocatalysis.

Acetylene-containing amino acids, obtained in enantiopure form via an enzymatic resolution process, serve as versatile intermediates in the synthesis of various highly functionalized heterocycles. The key transformations, intramolecular OC- and NC-bond formation, proceed via Pd-catalysis.