140483-59-6Relevant articles and documents
Pd-Catalyzed Regio- and Stereoselective sp3 C?H Arylation of Primary Aliphatic Amines: Mechanistic Studies and Synthetic Applications
Ha, Hyeonbin,Choi, Ho Jeong,Park, Hahyoun,Gwon, Yunyeong,Lee, Jiin,Kwak, Jaesung,Kim, Min,Jung, Byunghyuck
, p. 1136 - 1145 (2021/02/12)
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.
Palladium-catalyzed redox cascade for direct β-arylation of ketones
Huang, Zhongxing,Dong, Guangbin
supporting information, p. 3253 - 3265 (2018/05/04)
Herein we report a full article about the detailed design and development of two palladium-catalyzed redox cascade methods that enable direct β-arylation of ketones. Palladium-catalyzed ketone dehydrogenation, aryl-X bond activation and conjugate addition were merged into a redox-neutral catalytic cycle. Non-metal-based aryl electrophiles were used as both the oxidant and the aryl source. The β-arylation with aryl iodides was achieved site-selectively with Pd(TFA)2/P(i-Pr)3 as the precatalyst and AgTFA as the iodide scavenger. Both cyclic and linear ketones can react to give β-aryl ketones with excellent functional group tolerance. The β-arylation with diaryliodonium salts was realized without stoichiometric heavy metal additives, and proved to be redox-neutral. A wider substrate scope regarding aryl groups and ketones was obtained for the arylation with diaryliodonium salts, and the possible involvement of palladium nanoparticles as the active catalyst was examined and discussed.
DIRECT B-ARYLATION OF CARBONYL COMPOUNDS
-
Paragraph 0123-0125; 128, (2016/09/12)
Disclosed is a method for the β-C—H H functionalization of carbonyl compounds that is both selective and broadly applicable. The methods provide direct β-arylation of carbonyl compound with a diverse array of aryl or heteroaryl halides, aryl or heteroryl tosylate, aryl or heteroaryl triflates, or diaryliodonium salts, by palladium catalysis in the presence of a ligand and promoter.