# Chemoenzymatic Generation of Thio-analogues of δ‑Cadinene, δ‑Cadinol, and a Thio-diquinane Using 8‑Thio-farnesylpyrophosphate

## TL;DR

Scientists created thio-analogues of certain terpenoids using a modified farnesylpyrophosphate and observed their distinct odors.

## Contribution

The novel synthesis of 8-thio-farnesylpyrophosphate and its biotransformation into thio-terpenoids with unique olfactory properties.

## Key findings

- 8-thio-farnesylpyrophosphate was successfully synthesized and used in biotransformations.
- Thio-analogues of δ-cadinene and δ-cadinol were produced by Cop4 and Omp7 synthases.
- A ketothiol diquinane with a spicy aroma was formed by BcBOT2, differing from natural product pathways.

## Abstract

The synthesis of 8-thio-farnesylpyrophosphate is reported,
which
was subjected to biotransformations with different sesquiterpene synthases.
The 9-thio-analogues of δ-cadinene and δ-cadinol were
formed by the sesquiterpene synthases Cop4 and Omp7. In contrast,
the fungal sesquiterpene synthase BcBOT2 yielded a diquinane terpenoid
that contains a keto and thiol group. The formation of the two former
“sulfo”-terpenoids can be rationalized by following
the route proposed for δ-cadinene and δ-cadinol. The latter
can be regarded by the result of a late-stage hydrolysis product during
the analogous pathway to presilphiperfolan-8β-ol, the natural
product of BcBOT2. The olfactoric analysis of the three “sulfo”-sesuiterpenoids
revealed a stale odor for the cadinene derivatives, whereas the ketothiol
diquinane exhibits a spicy aroma with a subtle chili note.