[en] The title species have been shown to rearrange under the influence of the electrophile PhSCl to give tetrasubstituted vinylaluminium compounds protonolysis of which led to the corresponding vinyl sulfides in a highly stereoselective manner.
Disciplines :
Chemistry
Author, co-author :
Debuigne, Antoine ; University of Namur (FUNDP) > Department of Chemistry
Gérard, Julien; University of Namur (FUNDP) > Department of Chemistry
Hevesi, Làszlo; University of Namur (FUNDP) > Department of Chemistry
Language :
English
Title :
Electrophile induced rearrangement of 1-alkynylaluminium ate complexes
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The E stereochemistry has been assigned by comparison of the 1H NMR spectrum with that of the same compound obtained via similar rearrangement of the analogous boron ate complex, see ref. 9. It is worth noting that the Z stereoisomer was not present in the crude product mixture; we assume that it originates from the prolonged contact with silica gel during purification.
The strongly suspected presence (on the basis of GC/MS scrutiny) of the internal alkynes 6 in most product mixtures is in favor of this interpretation; however, the sometimes uncorrelated relative amounts of 6 and 8 indicate that it isn't entirely satisfactory.
