Germyl linker cleavage with carbon-based electrophiles.

This thesis describes the successful identification of a novel cross-coupling protocol
for alkylaryldichlorogermanes, as part of an investigation towards the development of
organogermanium linkers for solid phase synthesis. The application of Friedel-Crafts
acylation towards the ipso degermylation of aromatic molecules with concomitant
introduction of acyl functionality is also described.
By way of introduction, an in depth review of the literature surrounding Group 14
organometallic cross-couplings is presented, concentrating on the recent
developments in the area of organosilicon and organogermanium cross-coupling
chemistry. This is followed by a review of the literature precedent for ipso
acyldesilylation and acyldestannylation of aromatic molecules.
Results are then presented that detail the work carried out towards successful
arylgermane cross-coupling. Following extensive study and attempted optimisation
of trialkylarylgermane cross-couplings, it was discovered that the incorporation of
heteroatoms onto the germanium centre was necessary to obtain synthetically
acceptable cross-coupling yields.
Further results are also presented In relation to acyldegermylation studies that
illustrate the reactivity of arylgermanes towards acyl electrophiles, and the effect on
acyldegermylation of varying the electronic nature of the aryl group attached to
germanium.