Chemoenzymatic pathways for the synthesis of biologically active natural products

The whole-cell biotransformation of mono-nuclear aromatic compounds using certain genetically-engineered micro-organisms that over-express the enzyme toluene dioxygenase (TDO) allows for the large scale production of compounds known as cis-1,2-dihydrocatechols. These metabolites, which are normally obtained in enantiomerically pure form, can be manipulated, by chemical means, in a range of distinct (and predictable) ways with the result that they have proven to be especially versatile starting materials for the assembly of a range of structurally diverse and biologically active systems. Herein we describe, on a case-by-case basis, the recent applications of various combinations of TDO-mediated and chemical steps in so-called chemoenzymatic total syntheses of a range of organic compounds with therapeutic potential.