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Development of New Methodology in Organic Synthesis: Lewis Acid-Mediated Rearrangements of Ammonium Ylides and Addition of 1, 3-bis(silyl) propenes to Aldehydes
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

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.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:13
Keyword [en]
asymmetric, amino acid, ammonium ylide, Lewis acid, microwave irradiation
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-10317ISBN: 978-91-7415-268-5 (print)OAI: oai:DiVA.org:kth-10317DiVA: diva2:214655
Public defence
2009-04-24, F3. KTH, Lindstedtsvägen 26, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
QC 20100812Available from: 2009-05-06 Created: 2009-05-06 Last updated: 2010-08-12Bibliographically approved
List of papers
1. Lewis acid mediated 1,2 -rearrangement of ammonium ylides
Open this publication in new window or tab >>Lewis acid mediated 1,2 -rearrangement of ammonium ylides
2007 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 48, no 28, 4947-4949 p.Article in journal (Refereed) Published
Abstract [en]

The first example of Lewis acid mediated [1,2]-rearrangement of various glycine derivatives has been developed. A brief study of steric and electronic properties of the migrating group is presented. The corresponding amides were obtained in good yields and in the case of substrate 4d, moderate diastereoselectivity was observed.

Keyword
[1, 2]-rearrangement, ammonium ylide, Lewis acid, microwave irradiation, amide, stevens 1, 2, rearrangement
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-16773 (URN)10.1016/j.tetlet.2007.04.151 (DOI)000247848900034 ()2-s2.0-34250003216 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
2. Asymmetric Lewis Acid Mediated 1,2 -Rearrangement of Proline-Derived Ammonium Ylides
Open this publication in new window or tab >>Asymmetric Lewis Acid Mediated 1,2 -Rearrangement of Proline-Derived Ammonium Ylides
2009 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 11, no 4, 919-921 p.Article in journal (Refereed) Published
Abstract [en]

The first example of asymmetric Lewis acid mediated [1,2]-rearrangement of N-benzylic proline amides to form quaternary proline derivatives is reported. The presented reaction is shown to proceed with remarkable high C-N-C chirality transfer. Various quaternary proline derivatives have been prepared in good to excellent yields and high enantiomeric purity.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-18170 (URN)10.1021/ol8028803 (DOI)000263299000034 ()2-s2.0-62749167066 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
3. Lewis acid mediated asymmetric 2,3 -sigmatropic rearrangement of allylic amines. Scope and mechanistic investigation
Open this publication in new window or tab >>Lewis acid mediated asymmetric 2,3 -sigmatropic rearrangement of allylic amines. Scope and mechanistic investigation
2007 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 72, no 4, 1294-1300 p.Article in journal (Refereed) Published
Abstract [en]

[GRAPHIC] The first asymmetric [2,3]-sigmatropic rearrangement of achiral allylic amines has been realized by quaternization of the amines with an enantiomerically pure diazaborolidine and subsequent treatment with Et3N. The resultant homoallylic amines were obtained in good yields and excellent ee's. The observed diastereo- and enantioselectivities were rationalized by invoking a kinetically controlled process, and support for this model was obtained from an NMR spectroscopic investigation of the chiral Lewis acid-substrate complex. The structure of the Lewis acid-product complex was established by X-ray crystallographic analysis and supported the proposed mechanism.

Keyword
2, 3 sigmatropic rearrangement, generated metal carbenoids, ammonium ylides, <2, 3>-sigmatropic rearrangement, diazo-compounds, intramolecular reaction, catalytic methods, oxonium ylides, n-allyl, tandem
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-16374 (URN)10.1021/jo062178v (DOI)000244071100029 ()2-s2.0-33847000590 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
4. Lewis acid-promoted carbonyl addition of 1,3-bis(silyl)propenes
Open this publication in new window or tab >>Lewis acid-promoted carbonyl addition of 1,3-bis(silyl)propenes
2008 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 49, no 48, 6882-6884 p.Article in journal (Refereed) Published
Abstract [en]

A novel synthetic protocol for Lewis acid-promoted addition of 1,3-bis(silyl)propenes to N-phenyl glyoxylamide and ethyl glyoxylate is developed. The reaction does not appear to be influenced by the steric bulk of the 1,3-bis(silyl)propenes, and represents a new approach to vinylation of glyoxylates; the products are obtained in good yields.

Keyword
Vinylation; Allylsilane; [1, 3]-Brook rearrangement; N-Phenyl glyoxylamide; Ethyl glyoxylate; Tin tetrachloride
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-17960 (URN)10.1016/j.tetlet.2008.09.099 (DOI)000260843500040 ()2-s2.0-53549083769 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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