Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2021, Issue 7, Pages 1136-1145Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.202001428
Keywords
Aliphatic amines; γ -Arylation; C− H Activation; Homogeneous catalysis; Palladium; Transient directing groups
Categories
Funding
- DGIST R&D Program of the Ministry of Science and ICT [20-BRP-05]
- Basic Science Research Program [2020R1G1A1004460, 2019R1A2C4070584]
- Science Research Center through the National Research Foundation of Korea (NRF) - Ministry of Science, and ICT [2016R1A5A1009405]
- Korea Research Institute of Chemical Technology [KK2032-00]
- NRF - Ministry of Education [2019R1A6A3A13095922]
- National Research Council of Science & Technology (NST), Republic of Korea [KK2032-00] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- National Research Foundation of Korea [2019R1A6A3A13095922] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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The research reveals the use of 3-bromo-2-hydroxybenzaldehyde as a transient directing group in the Pd-catalyzed gamma-position sp(3)-C-H arylation of primary amines, and detailed the reaction mechanism and high selectivity origins through density functional theory calculations and X-ray crystal structure analysis.
The Pd-catalyzed gamma-position sp(3)-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 gamma-position sp(3)-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 degrees-amines into gamma-aryl-substituted ketones demonstrates synthetic utility. Density functional theory (DFT)-based calculations revealed the detailed reaction mechanism and the origins of the high selectivity (gamma-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.
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