PdII-Catalyzed ?-C(sp3)-H (Hetero)arylation of Ketones Enabled by Transient Directing Groups

被引：18
|
作者：
Li, Yi-Hao [1 ]
Ouyang, Yuxin [1 ]
Chekshin, Nikita [1 ]
Yu, Jin-Quan [1 ]
机构：
[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
来源：
ACS CATALYSIS | 2022年 / 12卷 / 17期
关键词：
C-H activation; palladium; ketones; transient directing group; arylation; pyridone ligands; palladacycle; C-H ARYLATION; C(SP(3))-H ARYLATION; INTERMOLECULAR AMIDATION; AMINO AMIDE; FUNCTIONALIZATION; ALDEHYDES; BONDS; ALKYLATION; AUXILIARY;
D O I：
10.1021/acscatal.2c03400
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Pd(II)-catalyzed gamma-C(sp3)-H (hetero)arylation of aliphatic ketones is developed using alpha-amino acids as transient directing groups (TDG). A variety of aliphatic ketones were (hetero)arylated at the gamma-position via a 5,6-membered fused cyclopalladation intermediate to afford the remotely arylated products in up to 88% yield. The crucial ligand effect of 2-pyridone is further enhanced by reducing the loading of acid additives. Consequentially, the improved reactivity of this catalytic system has also made possible the cyclic gamma-methylene C(sp3)-H arylation of ketones. Mechanistic investigation and comparison to the gamma-C-H arylation of aldehydes revealed a structural insight for designing site-selective TDG.
引用
收藏
页码：10581 / 10586
页数：6
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