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Asymmetric [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The thesis describes the realization of an asymmetric [2,3]-sigmatropic rearrangement of achiral allylic amines. It is divided into two parts; the first part deals with the development of a Lewis acid-mediated [2,3]-sigmatropic rearrangement and the second the asymmetric version thereof. Quaternization of an -amino amide with various Lewis acids established BBr3 and BF3 to be the most appropriate ones. Various allylic amines were subsequently rearranged into the corresponding homoallylic amines in good to excellent syn-diastereoselectivities, revealing the endo-transition state to be the preferred pathway. The structures of the intermediate Lewis acid-amine complexes were confirmed by NMR spectroscopy studies and DFT calculations.

Based on this investigation a chiral diazaborolidine was chosen as Lewis acid and was shown to efficiently promote the asymmetric [2,3]-sigmatropic rearrangement furnishing homoallylic amines in good yields and excellent enantiomeric excesses. In contrast to the achiral rearrangement mediated by BBr3 and BF3, the asymmetric version gave the opposite major diastereomer, revealing a preference for the exo-transition state in the asymmetric rearrangement. To account for the observed selectivities, a kinetic and thermodynamic pathway was presented. On the basis of a deuterium exchange experiment on a rearranged Lewis acid-amine complex and an NMR spectroscopic investigation, the kinetic pathway was shown to be favored.

Place, publisher, year, edition, pages
Stockholm: KTH , 2005. , 68 p.
Series
Trita-IOK, ISSN 1100-7974 ; 2005:97
Keyword [en]
asymmetric, [2, 3]-sigmatropic rearrangement, allylic amine, ammonium ylide, Lewis acid, enantioselective, boron, phosphazene base, NMR spectroscopy, DFT-calculations
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-430ISBN: 91-7178-135-8 (print)OAI: oai:DiVA.org:kth-430DiVA: diva2:11708
Public defence
2005-10-07, Salongen, KTHB, KTH, Stockholm, 09:00
Opponent
Supervisors
Note
QC 20100927Available from: 2005-09-27 Created: 2005-09-27 Last updated: 2010-09-27Bibliographically approved
List of papers
1. Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides
Open this publication in new window or tab >>Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides
2003 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 44, no 15, 3159-3162 p.Article in journal (Refereed) Published
Abstract [en]

An investigation of the Lewis acid mediated [2,3]-sigmatropic rearrangement of allylic ammonium ylides has been conducted by employing various bases and boron Lewis acids. Using BBr3 together with the phosphazene base 6, various allylic amines could be rearranged in good yields with low to excellent diastereoselectivity.

Keyword
[2, 3]-sigmatropic rearrangement, ammonium ylide, Lewis acid
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6872 (URN)10.1016/S0040-4039(03)00510-0 (DOI)000181978800032 ()
Note
QC 20100921Available from: 2005-09-27 Created: 2005-09-27 Last updated: 2017-12-14Bibliographically approved
2. Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic alpha-Amino Amides
Open this publication in new window or tab >>Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic alpha-Amino Amides
2004 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 69, no 9, 3043-3049 p.Article in journal (Refereed) Published
Abstract [en]

 Boron trifluoride and BBr3 mediated [2,3]-sigmatropic rearrangements of allylic alpha-amino amides have been developed affording secondary amines in good yields. (E)-Crotyl and (E)-cinnamyl alpha-amino amides 2b and 2c exhibit excellent syn-diastereoselectivity upon rearrangement with either Lewis acid. The allylic amine 2a forms upon treatment with BF3 or BBr3 a five-membered heterocylic complex in which a single halide anion has been displaced by the carbonyl oxygen atom. The structures of the Lewis acid-amine complexes were elucidated using NMR spectroscopy. A plausible reaction mechanism, based on DFT calculations, is presented. Thus, BF3- or BBr3-complexed allylic amines 2 are shown to preferentially proceed, after deprotonation, via an endo transition state.

Keyword
Complexation, Nuclear magnetic resonance spectroscopy, Oxygen, Probability density function, Reaction kinetics, Stereochemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6873 (URN)10.1021/jo035618g (DOI)000221268200017 ()2-s2.0-2142659321 (Scopus ID)
Note
QC 20100921Available from: 2005-09-27 Created: 2005-09-27 Last updated: 2017-12-14Bibliographically approved
3. Asymmetric [2,3]-sigmatropic rearrangement of allylic ammonium ylides
Open this publication in new window or tab >>Asymmetric [2,3]-sigmatropic rearrangement of allylic ammonium ylides
2005 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 26, 9352-9353 p.Article in journal (Refereed) Published
Abstract [en]

An asymmetric Lewis acid-mediated [2,3]-sigmatropic rearrangement of allylic amines has been developed, affording the corresponding homoallylic amines in good yield and excellent enantioselectivities. The rearrangement proceeds by complexation of the chiral Lewis acid to the amine followed by deprotonation and rearrangement.

Keyword
allyl compound, ammonium derivative, article, chirality, diastereoisomer, quantum yield, reaction analysis, stereochemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6874 (URN)10.1021/ja0510562 (DOI)000230220900021 ()2-s2.0-21644453480 (Scopus ID)
Note
QC 20100831Available from: 2005-09-27 Created: 2005-09-27 Last updated: 2017-12-14Bibliographically approved
4. Asymmetric [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides: Scope and Mechanistic Investigation
Open this publication in new window or tab >>Asymmetric [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides: Scope and Mechanistic Investigation
(English)Manuscript (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6875 (URN)
Note
QC 20100927Available from: 2005-09-27 Created: 2005-09-27 Last updated: 2010-09-27Bibliographically approved

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