Ligand-controlled Regiodivergent C-H Alkenylation of Pyrazoles and its Application to the Synthesis of Indazoles

被引：42

作者：

Kim, Hyun Tae ^{[1
,2
]}

Ha, Hyeri ^{[1
,2
]}

Kang, Geunhee ^{[1
,2
]}

Kim, Og Soon ^{[1
,2
]}

Ryu, Ho ^{[3
,4
]}

Biswas, Abul Kalam ^{[3
,4
]}

Lim, Sang Min ^{[5
,6
]}

Baik, Mu-Hyun ^{[3
,4
]}

Joo, Jung Min ^{[1
,2
]}

机构：

[1] Pusan Natl Univ, Dept Chem, Busan 46241, South Korea

[2] Pusan Natl Univ, Chem Inst Funct Mat, Busan 46241, South Korea

[3] Korea Adv Inst Sci & Technol, Dept Chem, Daejeon 34141, South Korea

[4] Inst for Basic Sci Korea, Ctr Catalyt Hydrocarbon Functionalizat, Daejeon 34141, South Korea

[5] Korea Inst Sci & Technol, Ctr Neuromed, Brain Sci Inst, Seoul 02792, South Korea

[6] Korea Univ Sci & Technol, Div Biomed Sci & Technol, Daejeon 34113, South Korea

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 51期

基金：

新加坡国家研究基金会;

关键词：

alkenylation; C-H activation; indazole; palladium; pyrazole; AMINO-ACID LIGANDS; DIRECT ARYLATION; ACTIVATION; FUNCTIONALIZATION; OXIDATION; MECHANISM; INDOLES; ARENES; AZOLES; ROUTE;

D O I：

10.1002/anie.201709162

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Regioselective C4-, C5-, and di-alkenylations of pyrazoles were achieved. An electrophilic Pd catalyst generated by trifluoroacetic acid (TFA) and 4,5-diazafluoren-9-one (DAF) leads to C4-alkenylation, whereas KOAc and mono-protected amino acid (MPAA) ligand Ac-Val-OH give C5-alkenylation. A combination of palladium acetate, silver carbonate, and pivalic acid affords dialkenylation products. Annulation through sequential alkenylation, thermal 6 pi-electrocyclization, and oxidation gives functionalized indazoles. This comprehensive strategy greatly expands the range of readily accessible pyrazole and indazole derivatives, enabling useful regiodivergent C-H functionalization of pyrazoles and other heteroaromatic systems.

引用

页码：16262 / 16266

页数：5

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