Organometallics
Organometallics
3 years ago

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

Molybdenum-Catalyzed Enantioselective Synthesis of Planar-Chiral (η5-Phosphacyclopentadienyl)manganese(I) Complexes and Application in Asymmetric Catalysis
Masamichi Ogasawara, Naoki Ohya, Sachie Arae, Mizuho Uryu, Tamotsu Takahashi, Ya-Yi Tseng, Hiroto Ishimoto, Ken Kamikawa, Ninghui Chang
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.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00704

DOI: 10.1021/acs.organomet.7b00704

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