Ligand-Enabled β-C(sp3)-H Olefination of Free Carboxylic Acids

被引：92
|
作者：
Zhuang, Zhe [1 ]
Yu, Chang-Bin [1 ]
Chen, Gang [1 ]
Wu, Qing-Feng [1 ]
Hsiao, Yi [2 ]
Joe, Candice L. [2 ]
Qiao, Jennifer X. [3 ]
Poss, Michael A. [3 ]
Yu, Jin-Quan [1 ]
机构：
[1] Scripps Res Inst, Dept Chem, 10550 North Torrey Pines Rd, La Jolla, CA 92037 USA
[2] Bristol Myers Squibb, Chem & Synthet Dev, 1 Squibb Dr, New Brunswick, NJ 08903 USA
[3] Bristol Myers Squibb Co, Discovery Chem, POB 4000, Princeton, NJ 08543 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 32期
关键词：
C-H BONDS; ALPHA-AMINO-ACIDS; HECK REACTION; STEREOSELECTIVE-SYNTHESIS; ALKYL-HALIDES; ARYLATION; C(SP(3))-H; ARYL; FUNCTIONALIZATION; ALKENYLATION;
D O I：
10.1021/jacs.8b06527
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
An acetyl-protected aminoethyl phenyl thioether has been developed to promote C(sp(3))-H activation. Significant ligand enhancement is demonstrated by the realization of the first Pd(II)-catalyzed olefination of C(sp(3))-H bonds of free carboxylic acids without using an auxiliary. Subsequent lactonization of the olefinated product via 1,4 addition provided exclusively monoselectivity in the presence of multiple beta-C-H bonds. The product gamma-lactone can be readily opened to give either the highly valuable beta-olefinated or gamma-hydroxylated aliphatic acids. Considering the challenges in developing Heck couplings using alkyl halides, this reaction offers a useful alternative.
引用
收藏
页码：10363 / 10367
页数：5
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