异构化
烯丙基重排
钯
烯烃纤维
筑地反应
亲核细胞
催化作用
取代反应
配体(生物化学)
化学
磷酰胺
亲核取代
光化学
组合化学
药物化学
有机化学
生物化学
受体
寡核苷酸
DNA
作者
Jiandong Liu,Wenbin Cao,Shu‐Li You
出处
期刊:Chem
[Elsevier]
日期:2024-02-29
卷期号:10 (4): 1295-1305
被引量:3
标识
DOI:10.1016/j.chempr.2024.02.006
摘要
The palladium-catalyzed allylic substitution (Tsuji-Trost) reaction is widely applied in organic synthesis, especially for the synthesis of stereochemically well-defined olefins. However, the synthesis of Z-olefins via the Tsuji-Trost reaction has been challenging due to the thermodynamic instability of the corresponding anti-π-allyl-palladium intermediate. Here, we report a ligand-enabled palladium-catalyzed Z-retentive allylic substitution reaction that retains Z-olefin geometries. Palladium catalysts derived from sterically bulky phosphoramidite ligands well differentiate the reaction rates between the nucleophilic attack step and the π-σ-π isomerization process. The Z-retentive allylic substitution results from the nucleophilic attack occurring much faster than the isomerization process. The isomerization of anti-π-allyl-palladium intermediate into its syn-counterpart has been observed at a low temperature. These results provide a prospective approach for the preparation of chiral Z-olefin compounds.
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