Cafestol to Tricalysiolide B and Oxidized Analogues: Biosynthetic and Derivatization Studies Using Non-heme Iron Catalyst Fe(PDP)

Abstract

The tricalysiolides are a recently isolated class of di­terpene natural products featuring the carbon backbone of the well-known coffee extract, cafestol. Herein we validate the use of our non-heme iron complex, Fe(PDP), as an oxidative tailoring enzyme mimic to test the proposal that this class of natural products derives from cafestol via cytochrome P-450-mediated furan oxidation. Thereafter, as predicted by computational analysis, C–H oxidation derivatization studies provided a novel 2° alcohol product as a single diastereomer.

Key words

C–H oxidation - functionalization - aliphatic - non-heme iron - natural product diversification - biosynthesis - cafestol

• References and Notes

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• 27 These steric and electronic property analyses were all based on calculations of the reactant molecule. Density functional theory (DFT) calculations of transition-state structures and selectivities are under way in our labs to verify these selectivity rules.