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Discrepancy between Proline and Homoproline in Chiral Recognition and Diastereomeric Photoreactivity with Iridium(III) Complexes
- Source :
- Inorganic chemistry. 60(8)
- Publication Year :
- 2021
-
Abstract
- The chiral-recognition processes of homoproline (hpro) and [Ir(pq)2(MeCN)2](PF6) (pq is 2-phenylquinoline; MeCN is acetonitrile) are investigated, in favor of formation of the thermodynamically stable diastereomers Λ-[Ir(pq)2(d-hpro)] and Δ-[Ir(pq)2(l-hpro)]. Moreover, the diastereoselective photoreactions of Δ-[Ir(pq)2(d-hpro)] and Δ-[Ir(pq)2(l-hpro)] are reported in the presence of O2 at room temperature. Diastereomer Δ-[Ir(pq)2(l-hpro)] is dehydrogenatively oxidized into imino acid complex Δ-[Ir(pq)2(hpro-2H2)] (hpro-2H2 is 3,4,5,6-tetrahydropicalinate), while diastereomer Δ-[Ir(pq)2(d-hpro)] occurs by interligand C-N cross-coupling and dehydrogenative oxidation reactions, affording three products: Δ-[Ir(pq)(d-pqh)] [pqh is N-(2-phenylquinolin-8-yl)homoproline], Δ-[Ir(pq)2(hpro-2H2)], and Δ-[Ir(pq)2(d-hpro-2H6)] [hpro-2H6 is 2,3,4,5-tetrahydropicalinate]. The C-N cross-coupling and dehydrogenative oxidation reactions are competitive, and the dehydrogenative oxidation reactions are regioselective. By optimization of the photoreaction parameters such as the diastereomeric substrate, solvent, and temperature as well as base, each possible competitive product is selectively controlled. In addition, density functional theory calculations are performed to elucidate the distinctly chiral recognition between proline and hpro with an iridium(III) complex.
- Subjects :
- chemistry.chemical_classification
Imino acid
010405 organic chemistry
Diastereomer
Regioselectivity
chemistry.chemical_element
Substrate (chemistry)
010402 general chemistry
01 natural sciences
Medicinal chemistry
Redox
0104 chemical sciences
Inorganic Chemistry
Solvent
chemistry.chemical_compound
chemistry
Iridium
Physical and Theoretical Chemistry
Acetonitrile
Subjects
Details
- ISSN :
- 1520510X
- Volume :
- 60
- Issue :
- 8
- Database :
- OpenAIRE
- Journal :
- Inorganic chemistry
- Accession number :
- edsair.doi.dedup.....51ac145ac8f4446212ec77ba95da38d4