The crystal structures of the bromomagnesium phenolate 5 and its complex 7 with para-isopropylbenzaldehyde are reported; for the first time it has been possible to demonstrate that the reactive complex 7, responsible for the complete ortho-regioselective control in the alkylation of phenoxymagnesium bromides with aldehydes, is not obtained by simple replacement of the ethereal ligand but by expansion of the metal coordination sphere from 4 (usual tetrahedral configuration) to 5. We infer from 1HNMR studies that the magnesium coordination of complex 7 in solution is analogous to that shown in the solid state, with a complexed ethereal molecule.
Metal-template electrophilic substitution on phenols: Synthesis and crystal structure of bromomagnesium phenolate and its reactive complex with para-isopropylbenzaldehyde / Bocelli, G.; Cantoni, A.; Sartori, G.; Maggi, R.; Bigi, F.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 3:8(1997), pp. 1269-1272. [10.1002/chem.19970030814]
Metal-template electrophilic substitution on phenols: Synthesis and crystal structure of bromomagnesium phenolate and its reactive complex with para-isopropylbenzaldehyde
Sartori G.;Maggi R.;Bigi F.
1997-01-01
Abstract
The crystal structures of the bromomagnesium phenolate 5 and its complex 7 with para-isopropylbenzaldehyde are reported; for the first time it has been possible to demonstrate that the reactive complex 7, responsible for the complete ortho-regioselective control in the alkylation of phenoxymagnesium bromides with aldehydes, is not obtained by simple replacement of the ethereal ligand but by expansion of the metal coordination sphere from 4 (usual tetrahedral configuration) to 5. We infer from 1HNMR studies that the magnesium coordination of complex 7 in solution is analogous to that shown in the solid state, with a complexed ethereal molecule.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.