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Anionic Access to Silylated and Germylated Binuclear Heterocycles
Author(s) -
Boddaert Thomas,
François Cyril,
Mistico Laetitia,
Querolle Olivier,
Meerpoel Lieven,
Angibaud Patrick,
Durandetti Muriel,
Maddaluno Jacques
Publication year - 2014
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.201402597
Subject(s) - hypervalent molecule , regioselectivity , chemistry , silicon , selectivity , ligand (biochemistry) , combinatorial chemistry , electron transfer , stereochemistry , medicinal chemistry , organic chemistry , catalysis , receptor , biochemistry , reagent
A simple access to silylated and germylated binuclear heterocycles, based on an original anionic rearrangement, is described. A set of electron‐rich and electron‐poor silylated aromatic and heteroaromatic substrates were tested to understand the mechanism and the factors controlling this rearrangement, in particular its regioselectivity. This parameter was shown to follow the rules proposed before from a few examples. Then, the effect of the substituents borne by the silicon itself, in particular the selectivity of the ligand transfer, was studied. Additionally, this chemistry was extended to germylated substrates. A hypervalent germanium species, comparable to the putative intermediate proposed with silicon, seems to be involved. However, a pathway implicating the elimination of LiCH 2 Cl was observed for the first time with this element, leading to unexpected products of the benzo‐oxa (or benzo‐aza) germol‐type.