A cyclohexadiene ligand prepared by microbial arene 1,2-dihydroxylation undergoes spontaneous rearrangement upon complexation to tricarbonyliron(0). Subsequent iron removal affords a novel route to formal arene 2,3-dihydroxylation products enantiomeric to those obtainable by direct microbial arene oxidation.
Metabolism of meta-bromobenzoic acid by the blocked mutant Ralstonia eutrophus B9 affords an enantiopure dearomatised halodiene-diol which we demonstrate is a versatile chiron for organic synthesis. The presence of the halogen leads to reactivity that is distinct to that observed for the non-halogenated analogue and also serves as a synthetic handle for… (More)
We report the synthesis and biological evaluation of three analogues of the natural product (+)-grandifloracin (+)-1. All three analogues exhibit enhanced antiproliferative activity against PANC-1 and HT-29 cells compared to the natural product. The retention of activity in an analogue lacking the enone functional group, 9, implies this structural element… (More)
Rhamnolipids (RLs) are heterogeneous glycolipid molecules that are composed of one or two l-rhamnose sugars and one or two β-hydroxy fatty acids, which can vary in their length and branch size. They are biosurfactants, predominantly produced by Pseudomonas aeruginosa and are important virulence factors, playing a major role in P. aeruginosa pathogenesis.… (More)
The dearomatising dihydroxylation of aromatic molecules mediated by arene dioxygenase enzymes can provide cyclohexadiene-diols that are versatile starting materials for organic synthesis. Whereas oxidation of a substituted arene to give its ortho,meta-dihydrodiol has been demonstrated for numerous substrates and dioxygenases, formation of… (More)
The functionalisation of decalin by means of an "aliphatic Friedel-Crafts" reaction was reported over fifty years ago by Baddeley et al. This protocol is of current relevance in the context of C-H activation and here we demonstrate its applicability to a range of other saturated hydrocarbons. Structural elucidation of the products is described and a… (More)
We report the first synthesis of a cobalt Cp diene complex wherein the diene is derived by microbial dearomatising dihydroxylation of an aromatic ring. The complex has been characterised crystallographically and its structure is compared to that of an uncomplexed diene precursor.
Unsaturated epsilon-lactones bearing an alpha-arylsulfonyl or alpha-arylsulfoximinyl substituent undergo stereoselective transannular, decarboxylative Claisen rearrangement to give substituted vinylcyclopropanes.