Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Synthetic Studies Toward the Polyhydroxylated Alkaloids DGDP and (+)-Alexine utilizing a [3 + 2]-Annulation Reaction of N-Ts-α-Amino Aldehydes and 1,3-Bis(silyl)propenes
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
(English)Manuscript (Other academic)
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-6622OAI: oai:DiVA.org:kth-6622DiVA: diva2:11380
Note
QC 20100917Available from: 2006-12-15 Created: 2006-12-15 Last updated: 2010-09-17Bibliographically approved
In thesis
1. Stereoselective Nucleophilic Additions to α-Amino Aldehydes: Application to Natural Product Synthesis
Open this publication in new window or tab >>Stereoselective Nucleophilic Additions to α-Amino Aldehydes: Application to Natural Product Synthesis
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis deals with the development and application of new synthetic methodology for stereo- or regioselective construction of carbon-carbon bonds in organic synthesis.

The first part of this thesis describes the development of a divergent protocol for stereoselective synthesis of chiral aminodiols by employing Mukaiyama aldol additions to syn- and anti-α-amino-β-silyloxy aldehydes. The stereoselectivity of the nucleophilic attack is governed by either chelation to the α-amino moiety or by nucleophilic attack in the Felkin-Anh sense. This study is also directed towards the elucidation of the factors that dictate aldehyde π-facial selectivity in substrate-controlled nucleophilic additions to these and similar systems.

In the second part, a highly stereoselective [3 + 2]-annulation reaction of N-Ts-α-amino aldehydes and 1,3-bis(silyl)propenes for stereoselective construction of densely functionalized pyrrolidines is presented. In addition, this methodology is also implemented as a keystep in a synthetic approach towards the polyhydroxylated pyrrolidine and pyrrolizidine alkaloids DGDP and (+)-alexine from a common late pyrrolidine intermediate.

Finally, a divergent protocol for regioselective opening of vinyl epoxides using alkyne nucleophiles is described, in which the regioselectivity of the nucleophilic attack is controlled by the choice of reaction conditions. The regioselectivities of the SN2 and SN2’ processes are, however, significantly influenced by the nature of the alkyne substituents and the best results are obtained using ethoxyacetylene. The SN2 opening of vinyl epoxides with ethoxyacetylene as nucleophile is also shown to provide a straightforward entry to functionalized γ-butyrolactones.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. 52 p.
Series
Trita-IOK, ISSN 1100-7974 ; 2006:105
Keyword
Stereoselective synthesis, Substrate-control, α-Amino aldehydes, Mukaiyama aldol, Allylsilanes, [3 + 2]-Annulation, (+)-Alexine, DGDP, Vinyl epoxides, Regioselectivity, Alkyne nucleophiles
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4233 (URN)91-7178-494-2 (ISBN)
Public defence
2006-12-18, F3, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100917Available from: 2006-12-15 Created: 2006-12-15 Last updated: 2010-09-17Bibliographically approved

Open Access in DiVA

No full text

Search in DiVA

By author/editor
Restorp, PerSomfai, Peter
By organisation
Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

urn-nbn

Altmetric score

urn-nbn
Total: 24 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf