Chemical and biochemical studies indicated the possible involvement of N-acetyltryptophan and 4-nitrotryptophan as intermediates in biosynthesis of the thaxtomin phytotoxins. A search for other potential pathways indirectly resulted in the identification of three unusual thaxtomin analogues derived from the o-thaxtomin A isomer. Investigations to resolve the identity of a previously described thaxtomin A di-glucoside were not supportive of the proposed structure.