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Pd-Catalyzed Regio- and Stereoselective sp3 C−H Arylation of Primary Aliphatic Amines: Mechanistic Studies and Synthetic Applications

Title
Pd-Catalyzed Regio- and Stereoselective sp3 C−H Arylation of Primary Aliphatic Amines: Mechanistic Studies and Synthetic Applications
Authors
Ha, HyeonbinChoi, Ho JeongPark, HahyounGwon, YunyeongLee, JiinKwak, JaesungKim, MinJung, Byunghyuck
DGIST Authors
Jung, Byunghyuck
Issue Date
2021-02
Citation
European Journal of Organic Chemistry, 2021(7), 1136-1145
Type
Article
Article Type
Article
Author Keywords
Aliphatic aminesγ-ArylationC−H ActivationHomogeneous catalysisPalladiumTransient directing groups
ISSN
1434-193X
Abstract
The Pd-catalyzed γ-position sp3−C−H arylation of primary amines bearing an aliphatic chain or cycloalkyl substituent and related mechanistic studies are disclosed. 3-Bromo-2-hydroxybenzaldehyde plays a key role in γ-position sp3−C−H arylation as a transient directing group (TDG) to assist the regio- and stereoselective C−H activation of a Pd catalyst, and the development of a tandem reaction to transform 1°-amines into γ-aryl-substituted ketones demonstrates synthetic utility. Density functional theory (DFT)-based calculations revealed the detailed reaction mechanism and the origins of the high selectivity (γ-position and cis-only). The X-ray crystal structure of the isolated endo-palladacycle intermediate supported the DFT results, and a kinetic isotope experiment confirmed the results of DFT calculations indicating that the C−H activation step via simultaneous palladation and deprotonation is rate-determining. © 2021 Wiley-VCH GmbH
URI
http://hdl.handle.net/20.500.11750/12977
DOI
10.1002/ejoc.202001428
Publisher
John Wiley & Sons Ltd.
Related Researcher
  • Author Jung, Byunghyuck Asymmetric Organic Synthesis and Drug Synthesis Laboratory
  • Research Interests Organic Synthesis; Organo-transition metal chemistry; Catalytic Asymmetric Synthesis; Synthetic Methodologies; Synthesis of Natural Products and Drugs
Files:
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Collection:
Department of Physics and ChemistryAsymmetric Organic Synthesis and Drug Synthesis Laboratory1. Journal Articles


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