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Asymmetric [2,3]-sigmatropic rearrangement of allylic ammonium ylides
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
2005 (engelsk)Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, nr 26, s. 9352-9353Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2005. Vol. 127, nr 26, s. 9352-9353
Emneord [en]
allyl compound, ammonium derivative, article, chirality, diastereoisomer, quantum yield, reaction analysis, stereochemistry
HSV kategori
Identifikatorer
URN: urn:nbn:se:kth:diva-6874DOI: 10.1021/ja0510562ISI: 000230220900021Scopus ID: 2-s2.0-21644453480OAI: oai:DiVA.org:kth-6874DiVA, id: diva2:11706
Merknad
QC 20100831Tilgjengelig fra: 2005-09-27 Laget: 2005-09-27 Sist oppdatert: 2017-12-14bibliografisk kontrollert
Inngår i avhandling
1. Asymmetric [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides
Åpne denne publikasjonen i ny fane eller vindu >>Asymmetric [2,3]-Sigmatropic Rearrangement of Allylic Ammonium Ylides
2005 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: KTH, 2005. s. 68
Serie
Trita-IOK, ISSN 1100-7974 ; 2005:97
Emneord
asymmetric, [2, 3]-sigmatropic rearrangement, allylic amine, ammonium ylide, Lewis acid, enantioselective, boron, phosphazene base, NMR spectroscopy, DFT-calculations
HSV kategori
Identifikatorer
urn:nbn:se:kth:diva-430 (URN)91-7178-135-8 (ISBN)
Disputas
2005-10-07, Salongen, KTHB, KTH, Stockholm, 09:00
Opponent
Veileder
Merknad
QC 20100927Tilgjengelig fra: 2005-09-27 Laget: 2005-09-27 Sist oppdatert: 2010-09-27bibliografisk kontrollert

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