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1. Draw all the DMAPP alkylation steps in the biosynthesis of hyperforin. 2. Identify the differences...

1. Draw all the DMAPP alkylation steps in the biosynthesis of hyperforin.

2. Identify the differences in the post-PKS modifications between isousnic acid and usnic acid.

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Answer #1

1. Malonyl CoA and isobytyril CoA are added to form Phlorisobutyrophenone which combines with DMAPP

CafifeG CoAS oH-t COAS DMAPP OPP Isaburyiyl cA CES malonyl CaA Dimetly! lalyl bransfer Phloxisabuty tophonone 2-methy-1 tryro

2. Methylphloracetophenone being the precursor of usnic acid, undergoes phenol oxidative coupling followed by cyclization to complete the ether linkage. There is a hypothetical assumption that usnic acid biosynthesis is associated with polyketide synthases enzymes or PKS that catalyse the polyketide synthesis in fungi. PKSs contain multidomain proteins and catalyse multiple carboxylic acid condensation reactions. The modifications that the polyketides undergo include reduction, oxygenation, esterification etc. These modifications are catalysed by enzymes other than PKS.

The isousnic acid is formed from usnic acid as a result of base catalysis. It is isomer of usnic acid.

The usnic acid and isousnic acid behave differently. Isousnic acid gives a deep blue green coloration with Ehrlich's reagent whereas usnic acid gives a blue coloration. They differ in NMR sectra also.

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