| Autor: |
Si, Xu‐Ge, Feng, Shi‐Xiong, Wang, Zhuo‐Yan, Chen, Xiaoyu, Xu, Meng‐Meng, Zhang, Yu‐Zhen, He, Jun‐Xiong, Yang, Limin, Cai, Quan |
| Předmět: |
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| Zdroj: |
Angewandte Chemie International Edition; 8/7/2023, Vol. 62 Issue 32, p1-12, 12p |
| Abstrakt: |
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/CuII 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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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