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Synlett 2014; 25(11): 1616-1620
DOI: 10.1055/s-0033-1339123
letter
© Georg Thieme Verlag Stuttgart · New York

New Synthetic Approach to C5-Hydroxymethyl-Substituted Polyhydroxylated Pyrrolizidines

Daniela Beňadiková
a   Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic   Email: robert.fischer@stuba.sk
,
Michal Medvecký
a   Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic   Email: robert.fischer@stuba.sk
,
Alexandra Filipová
a   Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic   Email: robert.fischer@stuba.sk
,
Ján Moncoľ
b   Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic
,
Milan Gembický
c   Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, WI 53711-5373, USA
,
Naďa Prónayová
d   Institute of Analytical Chemistry, Department of NMR Spectroscopy and Mass Spectrometry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic
,
Robert Fischer*
a   Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic   Email: robert.fischer@stuba.sk
› Author Affiliations
Further Information

Publication History

Received: 20 March 2014

Accepted after revision: 21 April 2014

Publication Date:
03 June 2014 (online)

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Abstract

A new approach to C5-hydroxymethyl-substituted pyrrolizidines involving 1,3-dipolar cycloaddition of a d-mannose-derived cyclic nitrone and the SN-reaction of a silyl ketene acetal is presented. The synthesis shows good stereoselectivity as a result of the presence of a dioxolane substituent at C5 of the nitrone, the bulkiness of the silyl ketene acetal, and the shape of the pyrrolizidinylium intermediate formed during intramolecular reductive amination. This approach provides access to pyrrolizidines with the same relative configuration as that found in hyacinthacines C2 and C3, and in (+)-pochonicine.

Key words

carbohydrates - heterocycles - nitrones - pyrrolizidines - stereoselective synthesis
 

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