Acetals addition reactions with alkylaluminum

Several important homogeneous catalytic reactions (e.g. hydroformylations) have been accomplished in water by use of water-soluble catalysts in some instances water can act as a solvent and as a reactant for hydroformylation. In addition, formation of aluminoxanes by partial hydrolysis of alkylaluminum halides results in very high activity bimetallic Al/Ti or Al/Zr metallocene catalysts for ethene polymerization which would be otherwise inactive. Polymerization of aryl diiodides and acetylene gas has recently been achieved in water with palladium catalysts. Finally, nickel-containing enzymes, such as carbon monoxide dehydrogenase (CODH) and acetyl-CoA synthase, operate in water with reaction mechanisms comparable with those of the WGSR or of the Monsanto methanol-to-acetic-acid process. ... 

Transesterification of resin-bound esters to give thioesters is also a ht-erature known procedure. Swinnen et al. released thioesters from sohd-supported esters by addition of ethanethiol and Me2AlCl (in situ formation of alkylaluminum thiolate) [115]. This strategy does not afford special linkers and can be performed for example on Wang or PAM resins. The reaction sequence favors side reaction of the ester species to thio-orthoesters and ketene thio acetals that could be transformed into the desired thioesters via treatment with TFA. 

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