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Ketone Asymmetric Hydrogenation Catalyzed by P-NH-P′ Pincer Iron Catalysts: An Experimental and Computational Study
- Source :
- ACS Catalysis. 7:316-326
- Publication Year :
- 2016
- Publisher :
- American Chemical Society (ACS), 2016.
-
Abstract
- Our group previously reported the development of iron carbonyl catalysts bearing chiral tridentate P–N–P′ ligands for the asymmetric hydrogenation of prochiral ketones in THF. An NMR study into the activation process identified the amine hydride alkoxide complexes Fe(P-NH-P′)(CO)(H)(OR1) with R1 = Me, tBu, or tAmyl and P-NH-P′ = PPh2CH2CH2NHCH2CH2PiPr2 or (S,S)-PPh2CHPhCHMeNHCH2CH2PCy2. These still required treatment with excess KOtBu and H2(g) to be catalytically active in THF. Both experimental methods and density functional theory (DFT) calculations were used to show that this treatment leads to the formation of a hydride amide complex Fe(P–N–P′)(CO)(H), which reacts with dihydrogen to form cis and trans dihydride complexes Fe(P-NH-P′)(CO)(H)2, identified by NMR spectroscopy. In the presence of KOtBu, NaOtBu, or KOtBu/2,2,2-cryptand and H2(g), these species are active for the catalytic hydrogenation of acetophenone, whereas in the absence of H2(g), inactive Fe(0) complexes are formed. Ketone hydrogenat...
- Subjects :
- chemistry.chemical_classification
Ketone
010405 organic chemistry
Hydride
Asymmetric hydrogenation
Noyori asymmetric hydrogenation
General Chemistry
010402 general chemistry
01 natural sciences
Medicinal chemistry
Catalysis
0104 chemical sciences
3. Good health
chemistry.chemical_compound
chemistry
Amide
Alkoxide
Organic chemistry
Acetophenone
Subjects
Details
- ISSN :
- 21555435
- Volume :
- 7
- Database :
- OpenAIRE
- Journal :
- ACS Catalysis
- Accession number :
- edsair.doi...........6e28e3b00a1f85e20f0a5f87be6a93b1