# Overriding Stereochemical Outcomes in Cyclase Phase Total Synthesis: Enantioselective Synthesis of Habiterpenol and Dasyscyphin A

## TL;DR

Scientists developed a new method to control the 3D shape of complex natural compounds during their synthesis, allowing for the creation of unusual molecular structures.

## Contribution

A quaternary carbon stereocenter epimerization protocol was introduced to override stereochemical bias in cyclization reactions.

## Key findings

- The enantioselective total syntheses of habiterpenol and dasyscyphin A were achieved.
- The method enables the construction of polycyclic scaffolds with a cis-hydrindane motif.
- Stereocenter remodeling was shown to reprogram biomimetic cyclization outcomes.

## Abstract

Herein, we report
the enantioselective total syntheses of habiterpenol
and dasyscyphin A. By exploiting a quaternary carbon stereocenter
epimerization protocol, we could override the intrinsic stereochemical
bias of polyolefin cyclization reactions. Accordingly, we achieved
the efficient and selective construction of the polycyclic scaffolds
of both meroterpenoid natural products that bear an unconventional cis-hydrindane motif. This work demonstrates the utility
of stereocenter remodeling in reprogramming the outcomes of biomimetic
cyclizations, thus enabling the rapid synthesis of terpenoid frameworks
that deviate from the prototypical all-trans-ring
fusions.