From Hydrindane to Decalin: A Mild Transformation through a Dyotropic Ring Expansion

Area of Science:

• Organic Chemistry
• Stereoselective Synthesis

Background:

• Hydrindane and decalin frameworks are prevalent in natural products and pharmaceuticals.
• Efficient methods for constructing decorated decalins with defined stereochemistry are highly sought after.

Purpose of the Study:

• To report a new ring expansion reaction converting hydrindane cores to decalins.
• To investigate the mechanism of this transformation, focusing on mild conditions and stereochemical control.

Main Methods:

• Exploration of reaction conditions for hydrindane to decalin conversion.
• Stereochemical analysis to determine the fidelity of chiral information transfer.
• Mechanistic studies, including computational analysis, to elucidate the reaction pathway.

Main Results:

• An unexpected ring expansion of hydrindanes to decalins was achieved.
• The reaction proceeds under very mild conditions with excellent transfer of chiral information.
• Access to decorated decalins with complete stereocontrol was demonstrated.
• An unprecedented dyotropic reaction involving a mesylate group was identified as the key mechanistic feature.

Conclusions:

• The discovered ring expansion offers a new route to stereodefined decalins.
• The reaction's mild conditions and high stereoselectivity are attributed to a unique dyotropic rearrangement.
• This work provides valuable insights into stereocontrolled synthesis and reaction mechanisms.