Molybdenum-Catalyzed Enantioselective Synthesis of Planar-Chiral (η5-Phosphacyclopentadienyl)manganese(I) Complexes and Application in Asymmetric Catalysis
| Autor: | Tamotsu Takahashi, Ken Kamikawa, Naoki Ohya, Mizuho Uryu, Ninghui Chang, Sachie Arae, Hiroto Ishimoto, Ya-Yi Tseng, Masamichi Ogasawara |
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| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Chemistry Stereochemistry Organic Chemistry Chiral ligand Enantioselective synthesis chemistry.chemical_element Manganese 010402 general chemistry Metathesis 01 natural sciences Medicinal chemistry Desymmetrization 0104 chemical sciences Catalysis Inorganic Chemistry Tsuji–Trost reaction Molybdenum Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 36(20):4061-4069 |
| ISSN: | 0276-7333 |
| Popis: | Enantioselective desymmetrization of Cs-symmetric (η5-2,5-dialkenylphospholyl)(allyldiphenylphosphine)manganese(I) dicarbonyl complexes 1 was realized by the molybdenum-catalyzed asymmetric ring-closing metathesis (ARCM), and the corresponding bridged planar-chiral phosphacymantrene derivatives 2 were obtained in good yields with excellent enantioselectivity. The enantioselectivity of the ARCM reaction was strongly influenced by the structures of the phospholyl-bound alkenyl groups, and the highest enantioselectivity of up to 99% ee was achieved in the reaction of 1d and 1e, which possess the 2-methylpropenyl substituents at the 2- and 5-positions of the η5-phospholides. Single-enantiomeric planar-chiral 2d, which was obtained by the recrystallization of the highly enantiomerically enriched ARCM product, can serve as a chiral ligand for the palladium-catalyzed asymmetric allylic alkylation to show good enantioselectivity in up to 74 % ee. |
| Databáze: | OpenAIRE |
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