Ogasawara, Masamichi Tokushima University|Hokkaido University Tokushima University Educator and Researcher Directory
Tseng, Ya-Yi Osaka Prefecture University
Uryu, Mizuho Tokushima University|Hokkaido University
Ohya, Naoki Osaka Prefecture University
Chang, Ninghui Hokkaido University
Ishimoto, Hiroto Hokkaido University
Arae, Sachie Hokkaido University
Takahashi, Tamotsu Hokkaido University
Kamikawa, Ken Osaka Prefecture University
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.
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.7b00704.
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organomet_36_20_4061.pdf 1.79 MB
Science and Technology