28978-07-6Relevant articles and documents
Action and timing of BacC and BacD in the late stages of biosynthesis of the dipeptide antibiotic bacilysin
Parker, Jared B.,Walsh, Christopher T.
, p. 889 - 901 (2013)
Biosynthesis of the dipeptide antibiotic bacilysin, encoded by the seven Bacillus subtilis genes bacA-G, involves diversion of flux from prephenate to the noncognate amino acid anticapsin. The anticapsin warhead is then ligated to the C-terminus of l-alanine to produce mature bacilysin. We have previously noted the formation of two diastereomers of tetrahydrotyrosine (4S- and 4R-H4Tyr) by tandem action of the four purified enzymes BacABGF. BacC (oxidase) and BacD (ligase) have been hypothesized to be remaining late stage enzymes in bacilysin biosynthesis. Using a combination of BacCD in vitro studies, B. subtilis deletion mutants, and isotopic feeding studies, we were able to determine that the H4Tyr diastereomers are actually shunt products that are not on-pathway to bacilysin biosynthesis. Dihydroanticapsin and dihydrobacilysin accumulate in extracts of a ΔbacC strain and are processed to anticapsin and then bacilysin upon addition of BacC and BacD, respectively. These results suggest the epoxide group in bacilysin is installed in an earlier step of bacilysin biosynthesis, while BacC oxidation of the C 7-hydroxyl and the subsequent BacD ligation of anticapsin to l-Ala are the penultimate and ultimate steps of bacilysin biosynthesis, respectively.
Stereocontrolled enantiospecific synthesis of anticapsin
Baldwin, Jack E.,Adlington, Robert M.,Mitchell, Mark B.
, p. 5193 - 5206 (2007/10/02)
A stereocontrolled enantiospecific synthesis of the revised structure of anticapsin (3) is described. The carbonyl group of anticapsin has also been observed to be markedly electrophilic, showing a high propensity for hydration and enolisation. A possible role for the hydrated form of anticapsin during the inhibition of glucosamine synthetase is proposed.
Enantioselective total synthesis of the antifungal natural products chorotetaine, bacilysin, and anticapsin and of related compounds: Revision of the relative configuration
Wild
, p. 2748 - 2761 (2007/10/02)
Enantioselective and diastereoselective syntheses of the title antifungal natural products and some of their diastereoisomers are described. Key steps include the diastereoselective 1,6-addition of bislactim ether 14 and a stereoselective deprotonation of
