Chemically unprecedented biocatalytic (AuaG) retro-[2,3]-Wittig rearrangement: a new insight into aurachin B biosynthesis.

AuaG is flavin-dependent monooxygenase responsible for the conversion of aurachin C to aurachin B, a reaction thought to resemble semipinacol migration of the farnesyl substituent. A study of the substrate tolerance of AuaG reveals that it has the peculiar ability to oxidise short-chain analogues of aurachin D. Unexpectedly, a novel retro-[2,3]-Wittig rearrangement was observed with an isoprenyl substrate analogue, thus leading to the 1,1-dimethylallyl ether. Additionally, we found that saturated-chain analogues of N-oxidised aurachin C were not transformed by the C3→C4 semipinacol reaction, as might have been expected for such substrates. Based on this and the unique retro-[2,3]-Wittig rearrangement, we discuss an alternative biosynthetic route for the conversion of aurachin C to aurachin B.