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Metal‐Template Electrophilic Substitution on Phenols: Synthesis and Crystal Structure of Bromomagnesium Phenolate and Its Reactive Complex with para ‐Isopropylbenzaldehyde
Author(s) -
Bocelli Gabriele,
Cantoni Andrea,
Sartori Giovanni,
Maggi Raimondo,
Bigi Franca
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030814
Subject(s) - regioselectivity , electrophile , chemistry , ligand (biochemistry) , crystal structure , substitution reaction , metal , coordination sphere , molecule , alkylation , coordination complex , electrophilic substitution , stereochemistry , combinatorial chemistry , crystallography , medicinal chemistry , catalysis , organic chemistry , biochemistry , receptor
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 1 H NMR studies that the magnesium coordination of complex 7 in solution is analogous to that shown in the solid state, with a complexed ethereal molecule.