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Synthesis 2016; 48(11): 1684-1692
DOI: 10.1055/s-0035-1561432
DOI: 10.1055/s-0035-1561432
special topic
Studies on the Second-Generation Approach to Loline Alkaloids: Synthesis of N-Bus-norloline through N-tert-Butanesulfinyl Imine Based Asymmetric Vinylogous Mannich Reaction
Further Information
Publication History
Received: 16 February 2016
Accepted after revision: 17 March 2016
Publication Date:
13 April 2016 (online)
Abstract
A strategy is outlined for the synthesis of loline alkaloids. This second-generation approach features direct access to the requisite vicinal diamino motif by a Cu(OTf)2-mediated highly trans-diastereoselective vinylogous Mannich reaction (VMR) of Ellman N-tert-butanesulfinyl imine derived from isopropylidene-protected (S)-glyceraldehyde, with N-Boc-2-tert-(butyldimethylsilyloxy)pyrrole (TBSOP). Fleming’s method was employed for the introduction of a hydroxyl group at C4 of the adduct, which gave the undesired diastereomer in 40% yield. The intramolecular SN reaction of the pyrrolizidine derivative to build the etheral bridge proved to be difficult, and produced N-Bus-norloline in only 20% yield. In light of the valuable information gained during this investigation, an improved version of the second-generation approach is being investigated, which is expected to provide a concise and efficient access to the challenging loline alkaloids.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561432.
- Supporting Information
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For synthetic studies, see:
For racemic total syntheses, see:
For enantioselective total syntheses, see:
Compound (R,RS )-7a was prepared by following the procedure described by Ellman.21a Yield: 65%; [α]D 20 –239.5 (c 1.0, EtOH) {Lit.21b [α]D 23 +248 (c 0.49, EtOH) for its enantiomer (S,SS )-7a}. The spectral data of (R,RS )-7a are identical with those of its enantiomer (S,SS )-7a, see: