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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, Hyeonbin; Choi, Ho Jeong; Park, Hahyoun; Gwon, Yunyeong; Lee, Jiin; Kwak, Jaesung; Kim, Min; Jung, 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 amines; γ-Arylation; C−H Activation; Homogeneous catalysis; Palladium; Transient 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
-
-
Jung, Byunghyuck
Asymmetric Organic Synthesis and Drug Synthesis Laboratory
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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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