Development of New Methodology in Organic Synthesis: Lewis Acid-Mediated Rearrangements of Ammonium Ylides and Addition of 1, 3-bis(silyl) propenes to Aldehydes
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
This thesis deals with the development of new methodologies in organicsynthesis. The main focus is on the development of Lewis acid-mediated [1,2]-rearrangements of ammonium ylides and the novel addition of 1,3-bis(silyl)propenes to carbonyl compounds.The first part of this thesis describes the development of a Lewis acidmediated[1,2]-Stevens rearrangement of various glycine derivatives. Thismethodology was then applied to the development of an asymmetric Lewis acid mediated [1,2]-Stevens rearrangement of cyclic ammonium ylides. There markably high degree of C→N→C chirality transfer is described. In addition, this methodology was successfully applied to the synthesis of various quaternary proline derivatives in enantiomerically pure form.Secondly, a brief study of the asymmetric [2,3]-rearrangement of α-substitutedglycine derivatives is presented. The investigation revealed a severely limitedreaction scope. The subsequent study on developing super-reactive cationicLewis acid also met with little success.Finally, an addition reaction of various 1,3-bis(silyl)propenes to glyoxalates has been developed. The reaction products correspond to the direct vinylation ofglyoxalates. The corresponding highly functionalized δ-hydroxy allylsilanes were obtained in high yields.
Place, publisher, year, edition, pages
Stockholm: KTH , 2009. , 63 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2009:13
asymmetric, amino acid, ammonium ylide, Lewis acid, microwave irradiation
IdentifiersURN: urn:nbn:se:kth:diva-10317ISBN: 978-91-7415-268-5OAI: oai:DiVA.org:kth-10317DiVA: diva2:214655
2009-04-24, F3. KTH, Lindstedtsvägen 26, Stockholm, 13:00 (English)
Koskinen, Ari, Professor
Somfai, Peter, Professor
QC 201008122009-05-062009-05-062010-08-12Bibliographically approved
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