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Updated: Jul 8, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Au-catalyzed cyclization of monoallylic diols
Aaron Aponick1, Chuan-Ying Li, Berenger Biannic
1Department of Chemistry, University of Florida, Gainesville, Florida 32611, USA. aponick@chem.ufl.edu
A new gold-catalyzed cyclization efficiently synthesizes tetrahydropyrans from monoallylic diols. This reaction is fast, works at low temperatures, and shows high diastereoselectivity for cis products.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Tetrahydropyrans are prevalent structural motifs in natural products and pharmaceuticals.
- Efficient and selective synthesis of tetrahydropyrans remains a key challenge in organic chemistry.
Purpose of the Study:
- To develop a novel catalytic system for the synthesis of tetrahydropyrans.
- To investigate the scope and diastereoselectivity of the developed reaction.
Main Methods:
- Gold(I)-catalyzed cyclization of monoallylic diols using Ph3PAuCl/AgOTf.
- Screening of reaction conditions including temperature and catalyst loading.
- Evaluation of substrate scope and diastereoselectivity.
Main Results:
- The Ph3PAuCl/AgOTf catalyst system efficiently cyclizes monoallylic diols to tetrahydropyrans.
- Reactions proceed rapidly at low temperatures (-78 °C) with low catalyst loadings (0.1 mol %).
- Yields range from 79-99% with high diastereoselectivity for the 2,6-cis product in the synthesis of 2,6-disubstituted tetrahydropyrans.
Conclusions:
- A highly efficient and diastereoselective gold-catalyzed method for tetrahydropyran synthesis has been established.
- The methodology is applicable to a broad range of structurally diverse substrates.
- This method offers a valuable tool for accessing complex tetrahydropyran derivatives.
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