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Lewis acid mediated asymmetric 2,3 -sigmatropic rearrangement of allylic amines. Scope and mechanistic investigation
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
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.

Place, publisher, year, edition, pages
2007. Vol. 72, no 4, 1294-1300 p.
Keyword [en]
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: urn:nbn:se:kth:diva-16374DOI: 10.1021/jo062178vISI: 000244071100029Scopus ID: 2-s2.0-33847000590OAI: oai:DiVA.org:kth-16374DiVA: diva2:334416
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Development of New Methodology in Organic Synthesis: Lewis Acid-Mediated Rearrangements of Ammonium Ylides and Addition of 1, 3-bis(silyl) propenes to Aldehydes
Open this publication in new window or tab >>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)
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
asymmetric, amino acid, ammonium ylide, Lewis acid, microwave irradiation
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-10317 (URN)978-91-7415-268-5 (ISBN)
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

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