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Molybdenum-Catalyzed Enantioselective Synthesis of Planar-Chiral (η5‑Phosphacyclopentadienyl)manganese(I) Complexes and Application in Asymmetric Catalysis

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journal contribution
posted on 12.10.2017 by Masamichi Ogasawara, Ya-Yi Tseng, Mizuho Uryu, Naoki Ohya, Ninghui Chang, Hiroto Ishimoto, Sachie Arae, Tamotsu Takahashi, Ken Kamikawa
Enantioselective desymmetrization of Cs-symmetric (η5-2,5-dialkenylphospholyl)­(allyldiphenylphosphine)­manganese­(I) dicarbonyl complexes 1 was realized by 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,e, 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.