Light‐Induced Chiral Aldehyde/Palladium Catalysis‐Enabled Asymmetric Allylic C─H Alkylation of Alkenes With NH <sub>2</sub> ‐Unprotected Amino Acid Derivatives
Abstract
ABSTRACT The catalytic asymmetric allylic C–H alkylation of alkenes with the α‐carbon of readily available amino acid derivatives represents an ideal strategy for constructing chiral nonproteinogenic α,α‐disubstituted amino acids. However, such synthetic methodologies remain unexplored. Herein, we report a light‐induced, chiral aldehyde/palladium catalysis‐enabled direct allylic C–H alkylation of allyl arenes and 1,4‐enynes using NH 2 ‐unprotected amino acid esters. The results demonstrate that competing allylic C–H amination is completely suppressed, and the desired alkylation products—bearing either allyl or conjugated enyne moieties—are obtained in 32%–93% yields with 80%–98% ee values. Mechanistic studies reveal that enantiocontrol is achieved through the cooperative action of the chiral aldehyde and the chiral ligand, and the latter primarily dictates the absolute configuration of the product by forming noncovalent C–H···π and C–H···O interactions with the chiral aldehyde‐involved Zn complex.
Article Details
Authors (7)
Hong‐Lin Guan
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft‐Matter Material Chemistry and Function Manufacturing School of Chemistry and Chemical Engineering Southwest University Chongqing China
Bo‐Xuan Yao
College of Chemistry & Chemical Engineering and Key Laboratory For Preparation and Application of Ordered Structural Materials of Guangdong Province Shantou University Shantou China
Wei Wen
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China
Zhu‐Lian Wu
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft‐Matter Material Chemistry and Function Manufacturing School of Chemistry and Chemical Engineering Southwest University Chongqing China
Tian Cai
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China
Shao‐Fei Ni
College of Chemistry & Chemical Engineering and Key Laboratory For Preparation and Application of Ordered Structural Materials of Guangdong Province Shantou University Shantou China
Qi‐Xiang Guo
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft‐Matter Material Chemistry and Function Manufacturing School of Chemistry and Chemical Engineering Southwest University Chongqing China