Jump to main content
Jump to site search

Issue 16, 1999

Utilization of industrial waste materials. Part 14.† Synthesis of β-amino alcohols and thiols with a 2-azabicyclo[3.3.0]octane backbone and their application in enantioselective catalysis

Abstract

New, chiral β-tert-amino tert-alcohols have been synthesized from the enantiomerically pure sec-amine (all-R)-1b via the new glycine, alanine and phenylglycine derivatives 2–6. Grignard additions to these esters provided the new rigid amino alcohols 7–11 in fair yields. The absolute configurations of the stereogenic centers, which arose during the alkylation step, were assigned by an independent route leading to some of the optical antipodes of 7–10. Condensation of enantiomerically pure β-amino alcohols 13a–g, 16 and 17 with γ-ketoester rac-12 afforded the N,O-acetals 14a–g, 18 and 19, which were subsequently reduced to the β-tert-amino alcohols 10a,c and 15a–g. X-Ray analysis of compound 19 was performed to verify the stereochemistry observed by chemical correlation. The nucleophilic ring opening of enantiomerically pure styrene oxide by amine 1b resulted in the formation of regioisomeric amino alcohols 9a, 21a, and 10a, 21b. Amino thiol derivatives 22 and 25a,b were prepared by treatment of 10a and 15a,b, respectively, with methanesulfonyl chloride followed by regio- and stereoselective cleavage of the in situ formed aziridinium ions with potassium thioacetate. Reduction of these compounds to thiols 23 and 26a,b and subsequent oxidation afforded amino disulfides 24 and 27a,b. Finally, the bicyclic β-amino alcohols and thiols were used as chiral ligands in the enantioselective addition of diethylzinc to benzaldehyde and ee values up to 96% were found.

Supplementary files

Article information


J. Chem. Soc., Perkin Trans. 1, 1999, 2353-2365
Article type
Paper

Utilization of industrial waste materials. Part 14.† Synthesis of β-amino alcohols and thiols with a 2-azabicyclo[3.3.0]octane backbone and their application in enantioselective catalysis

M. Kossenjans, M. Soeberdt, S. Wallbaum, K. Harms, J. Martens and H. Günter Aurich, J. Chem. Soc., Perkin Trans. 1, 1999, 2353 DOI: 10.1039/A902362C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Search articles by author

Spotlight

Advertisements