Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration

Deprotonative directed ortho cupration of aromatic/heteroaromatic C–H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox...

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 138; no. 29; pp. 9166 - 9171
Main Authors Tezuka, Noriyuki, Shimojo, Kohei, Hirano, Keiichi, Komagawa, Shinsuke, Yoshida, Kengo, Wang, Chao, Miyamoto, Kazunori, Saito, Tatsuo, Takita, Ryo, Uchiyama, Masanobu
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 27.07.2016
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
OXIDATION
METALATION
PALLADIUM-CATALYZED HYDROXYLATION
AMMONIA
MONOARYLATION
TERTIARY AMIDE
LITHIUM
ARYL CHLORIDES
TMP-ZINCATE
BOND-FORMATION
Online AccessGet full text

Cover

More Information
Summary:Deprotonative directed ortho cupration of aromatic/heteroaromatic C–H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox mechanism. Application of this reaction to aromatic C–H amination using BnONH2 efficiently afforded the corresponding primary anilines. These reactions show broad scope and good functional group compatibility. Catalytic versions of these transformations are also demonstrated.
Bibliography:KAKEN
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b03855