In this study, we described in detail a combinatorial
enzymatic
synthesis approach to produce a series of unnatural long-chain β-branch
pyrones. We attempted to investigate the catalytic potential of a
highly promiscuous enzyme type III PKS to catalyze the non-decarboxylative
condensation reaction by two molecules of fatty acyl diketide-N-acetylcysteines (diketide-NACs) units. Two non-natural
long-chain (C16, C18) fatty acyl diketide-NACs
were prepared successfully for testing the ability of non-decarboxylative
condensation. In vitro, 12 novel naturally unavailable long-chain
β-branch pyrones were generated by one-pot formation and characterized
by ultraviolet–visible spectroscopy and high-resolution liquid
chromatography–mass spectrometry. Interestingly, enzymatic
kinetics result displays that this enzyme exhibits the remarkable
compatibility to various non-natural long-chain substrates. These
results would be useful to deeply understand the catalytic mechanism
of this enzyme and further extend the application of enzymatic synthesis
of non-natural products.
In this review, we present the recent advances in unusual novel ketosynthases catalyzing
the non-decarboxylative Claisen condensations, including CsyB, MxnB/CorB, Ppys and StlD. The
differences are summarized between these non-decarboxylative ketosynthases and the typical decarboxylative
ketosynthases. Furthermore, the detailed enzymatic characteristics, structural basis, and
catalytic mechanismof these novel ketosynthasesare described. Finally, the prospect of these kind of
ketosynthases is discussed.
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