An Unusual and Diastereoselective Rearrangement during an Intramolecular Ene Reaction Involving a Disilane

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 LiCH2Cl was observed for the first time with this element, leading to unexpected products of the benzo-oxa (or benzo-aza) germol-type.

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ChemInform Abstract: An Unusual and Diastereoselective Rearrangement During an Intramolecular Ene Reaction Involving a Disilane.

Giros

Guillot

Blanco

et al. 2014

ChemInform

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An Unusual and Diastereoselective Rearrangement During an Intramolecular Ene Reaction Involving a Disilane. -The intramolecular ene reaction of compound (I) gives the expected reaction product (II) and also the unexpected one (III) with high diastereoselectivity. Possible mechanisms for these observations are presented. -(GIROS, A.; GUILLOT, R.; BLANCO, L.; DELOISY*, S.; Eur. J. Org. Chem. 2013, 26, 5809-5813, http://dx.doi.org/10.1002/ejoc.201300849 ; Lab. Synth. Org. Methodol., Inst. Chim. Mol. Mater., Univ. Paris-Sud, F-91405 Orsay, Fr.; Eng.) -M. Zastrow

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An Unusual and Diastereoselective Rearrangement during an Intramolecular Ene Reaction Involving a Disilane

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References 31 publications

Molecular Rearrangements

Molecular Rearrangements

Anionic Access to Silylated and Germylated Binuclear Heterocycles

ChemInform Abstract: An Unusual and Diastereoselective Rearrangement During an Intramolecular Ene Reaction Involving a Disilane.

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