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A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)–H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 4/14/2018, Vol. 47 Issue 14, p4893-4901, 9p
- Publication Year :
- 2018
-
Abstract
- The detailed mechanism of palladium-catalyzed γ-C(sp<superscript>3</superscript>)–H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp<superscript>3</superscript>)–H bond cleavage, alkene insertion and ‘reductive β-hydride elimination’. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C–H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed. [ABSTRACT FROM AUTHOR]
- Subjects :
- BICARBONATE ions
CHEMICAL reactions
RING formation (Chemistry)
Subjects
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 47
- Issue :
- 14
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 128883442
- Full Text :
- https://doi.org/10.1039/c8dt00015h