AI Article Synopsis
- The study presents a method combining Birch reduction and a catalytic asymmetric Diels-Alder reaction to synthesize cis-decalin scaffolds, which are important for various chemical applications.
- Using a specialized chiral bis(oxazoline) ligand/Cu complex, researchers efficiently produced a variety of polysubstituted cis-decalin structures, some with up to six stereocenters.
- The synthetic capabilities were highlighted by creating the sesquiterpene (+)-occidentalol and an intermediate for seven triterpenes, with mechanistic studies indicating that certain cyclohexadienes play a crucial role in the reaction process.
Article Abstract
Herein, we show that the combination of the Birch reduction of readily available anisole derivatives and the catalytic asymmetric inverse-electron-demand Diels-Alder reaction of 2-pyrones can serve as a powerful platform for the diverse synthesis of synthetically important cis-decalin scaffolds. Enabled by a well-modified chiral bis(oxazoline) ligand/Cu complex, a wide range of polysubstituted cis-decalin scaffolds with up to six contiguous stereocenters were generated efficiently. The synthetic potential of this method is demonstrated by the concise synthesis of the sesquiterpene (+)-occidentalol and a key intermediate for seven triterpenes. Mechanistic studies suggest the 1,3-cyclohexadienes formed in situ are the key intermediates, and efficient kinetic resolution occurs when C2- and/or C3-substituted 1,4-cyclohexadienes are utilized as substrates. DFT calculations elucidated that the Diels-Alder reaction proceeds in a stepwise fashion and revealed the origins of the stereoselectivities.
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| http://dx.doi.org/10.1002/anie.202303876 | DOI Listing |
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