Reductive decomplexation of pi-allyltricarbonyliron lactone complexes using sodium naphthalenide as a route to stereodefined 1,7-diols and 2,3-diene-1,7-diols.

Treatment of pi-allyltricarbonyliron lactone complexes, that contain an adjacent leaving group, with lithium naphthalenide causes decomplexation to acyclic dienols in excellent yield and without any stereochemical scrambling of the allylic centre. When an endo complex is employed (E,E)-geometry prevails with good selectivity whereas (Z,E)-geometry dominates in the case of exo complexes. A mechanism consistent with the observed stereo- and regiochemistry is proposed.

1,5-asymmetric induction of chirality using pi-allyltricarbonyliron lactone complexes: highly diastereoselective synthesis of alpha-functionalised carbonyl compounds.

Silyl enol ethers derived from ketone functionalised rho-allyltricarbonyliron lactone complexes undergo highly diastereoselective carbon-fluorine and carbon-oxygen bond formation reactions with excellent control at the alpha-stereogenic centre.

Synthesis of (-)-gloeosporone, a fungal autoinhibitor of spore germination using a pi-allyltricarbonyliron lactone complex as a templating architecture for 1,7-diol construction.

The synthesis of the germination self-inhibitor (-)-Gloeosporone is reported. The embedded 1,7-diol motif in the product is constructed by an ironcarbonyl tether controlled Mukaiyama aldol reaction. The key step in the synthesis is the reductive removal of the ligating iron species by treatment of an acetoxycomplex 6 with lithium naphthalenide.

Use of pi-allyltricarbonyliron lactone complexes in the synthesis of taurospongin A: a potent inhibitor of DNA polymerase beta and HIV revers transcriptase.

The total synthesis of taurospongin A by two new approaches has been achieved where pi-allyltricarbonyliron lactone complexes have been used to control highly stereoselective additions of the nucleophiles to a carbonyl unit located in the side chain of these complexes.

Reductive decomplexation of pi-allyltricarbonyliron lactone complexes; a new route to stereo-defined 1,7-diols and 2,3-diene-1,7-diols.

Treatment of pi-allyltricarbonyliron lactone complexes bearing an adjacent leaving group, with lithium naphthalenide causes decomplexation to acyclic dienols in excellent yield and without any scrambling of the allylic centre.

Synthesis of taurospongin A: a potent inhibitor of DNA polymerase and HIV reverse transcriptase, using pi-allyltricarbonyliron lactone complexes.

The synthesis of taurospongin A has been achieved using, as a key step, a pi-allyltricarbonyliron lactone complex to control a highly stereoselective addition of a methyl group to a carbonyl unit located in the side chain of the complex.