Kinetic Resolution of Planar-Chiral Ferrocenylphosphine Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis and Their Application in Asymmetric Catalysis
| Autor: | Kiyohiko Nakajima, Tamotsu Takahashi, Susumu Watanabe, Masamichi Ogasawara, Sachie Arae |
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| Rok vydání: | 2016 |
| Předmět: |
Addition reaction
010405 organic chemistry Enantioselective synthesis General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences Kinetic resolution chemistry.chemical_compound Ring-closing metathesis chemistry Salt metathesis reaction Organic chemistry Enantiomer Phosphine |
| Zdroj: | ACS Catalysis. 6:1308-1315 |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.5b02692 |
| Popis: | Highly enantioselective kinetic resolution of racemic planar-chiral metallocenylphosphine sulfides was realized by the molybdenum-catalyzed asymmetric ring-closing metathesis reaction with the krel values of up to 147. The enantiomerically enriched 1,4-but-2-enylene-bridged ferrocenylphosphine sulfides thus obtained could be purified to enantiomerically pure forms by simple recrystallization from hot methanol, and subsequent reduction of the phosphine sulfides provided the corresponding planar-chiral phosphines with retention of the enantiomeric homogeneity. This is a rare example of preparing planar-chiral ferrocenylphosphines by catalytic asymmetric reactions. The single-enantiomer planar-chiral ferrocenylphosphines were applied as chiral ligands in the rhodium-catalyzed asymmetric 1,4-addition reaction (the Hayashi–Miyaura conjugate addition reaction) of phenylboronic acid to 2-cyclohexenone to show excellent enantioselectivity and high yields. The NMR studies clarified that the butenylene-bridged ferr... |
| Databáze: | OpenAIRE |
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