Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/37933
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Título : Synthesis of Transient and Stable C-Amino Phosphorus Ylides and Their Fragmentation into Transient and Stable Carbenes
Autor : Canac, Yves, Conejero Iglesias, Salvador, Soleilhavoup, Michèle, Donnadieu, Bruno, Bertrand, Guy
Palabras clave : Synthesis
C-amino phosphorus
Carbenes
β-Amino phosphonium salts
Fecha de publicación : 17-Dec-2005
Editor: American Chemical Society
Citación : Journal of the American Chemical Society 128(2): 459-464 (2006)
Resumen: Only basic phosphines, such as tris(dimethylamino)phosphine, allow for the synthesis of a stable acyclic β-amino phosphonium salt 1c, which upon deprotonation with butyllithium affords the corresponding stable C-amino phosphorus ylide 2c. In contrast, cyclic β-amino phosphonium salts 5a and 5b are stable despite the presence of weakly basic triarylphosphine fragments. They are prepared by intramolecular insertion of the carbene center of (amino)(phosphonio)carbenes into the CH bond of a phosphorus substituent. Deprotonation of 5a leads to the corresponding cyclic C-amino phosphorus ylide 6a, which has been fully characterized including an X-ray diffraction study. Deprotonation of 5b affords enamine 8, probably via fragmentation of ylide 6b into transient carbene 7b and a subsequent 1,2-hydrogen shift. Transient cyclic C-amino phosphorus ylides 6c and 6d have been prepared by intramolecular addition of a carbanion generated by deprotonation of a phosphorus substituent. Three-membered heterocycle 6c rearranges into alkene 9, whereas the four-membered ring system undergoes a ring opening affording the stable carbene 7d. The latter results pave the route for the synthesis of various mixed carbene−phosphine bidentate ligands.
Descripción : 6 páginas, 1 figura, 5 esquemas.
Versión del editor: http://dx.doi.org/10.1021/ja055863c
URI : http://hdl.handle.net/10261/37933
ISSN: 0002-7863
DOI: 10.1021/ja055863c
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