# Biocatalytic Synthesis of Diamondoid Diols by the Brown‐Rot Fungus Wolfiporia cocos

## TL;DR

This study explores how the fungus Wolfiporia cocos can oxidize diamondoid compounds, producing unique diols that are rare in traditional chemistry.

## Contribution

The discovery of unusual selectivity in diamantane oxidation by Wolfiporia cocos, forming rare diol products not typically seen in conventional chemical reactions.

## Key findings

- Wolfiporia cocos produces typical diols from adamantane derivatives similar to chemical oxidation.
- Diamantane-4-ol is selectively oxidized to form rare 4,9- and 1,9-diols, attacking a highly deactivated CH-position.
- Oxidative activity is observed in 4–6-day-old fungal cultures in water or at pH 2, but not at higher pH.

## Abstract

The CH‐oxidative activity of Wolfiporia cocos cultures of different ages was studied utilizing diamondoid derivatives as conformationally rigid models. Adamantane‐1‐ol and 1‐bromoadamantane, traditional precursors for the synthesis of polysubstituted adamantanes, gave qualitatively similar reaction mixtures in which adamantane diols dominated. While the reactions occurred with high preparative yields, the biotransformation does not display clear differences from classic electrophilic or radical adamantane functionalization reactions. In contrast, the fungal oxidation of diamantane‐4‐ol occurred with unexpected selectivity yielding diamantane‐4,9‐diol and diamantane‐1,9‐diol. The latter product is quite uncharacteristic for diamantane chemistry because the most deactivated CH‐position is attacked. To elucidate the active fungal component, additional experiments were performed with supernatant and resting cells harvested at various culture ages. Oxidative activity was detected in resting cells from 4‐ and 6‐day‐old cultures in pure water medium, and from 6‐day‐old cultures in buffer at pH 2, but disappeared at higher pH values.

Wolfiporia cocos cultures were tested for CH‐oxidative activity using rigid diamondoid substrates. Adamantane derivatives gave typical diols similar to known chemical oxidations, while diamantane‐4‐ol showed unusual selectivity, forming rare 4,9‐ and 1,9‐diols. Tests with supernatants and resting cells showed that oxidation occurred only in cells from 4–6‐d cultures, active in water or at pH 2, but lost at higher pH.© 2026 WILEY‐VCH GmbH