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
[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.
2, 3 sigmatropic rearrangement, generated metal carbenoids, ammonium ylides, <2, 3>-sigmatropic rearrangement, diazo-compounds, intramolecular reaction, catalytic methods, oxonium ylides, n-allyl, tandem
IdentifiersURN: urn:nbn:se:kth:diva-16374DOI: 10.1021/jo062178vISI: 000244071100029ScopusID: 2-s2.0-33847000590OAI: oai:DiVA.org:kth-16374DiVA: diva2:334416
QC 201005252010-08-052010-08-052010-12-14Bibliographically approved