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Harnessing Chalcogen-bonding Interactions To Establish Conformational Control in Dirhodium(II) Paddlewheel Complexes

preprint
submitted on 23.06.2020 and posted on 25.06.2020 by Takuya Murai, Wenjie Lu, Toshifumi Kuribayashi, Kazuhiro Morisaki, Yoshihiro Ueda, Shohei Hamada, Takahiro Sasamori, Norihiro Tokitoh, Takeo Kawabata, Takumi Furuta
Novel well-defined D2-symmetric dirhodium(II) carboxylate complexes that bear axially chiral binaphthothiophene delta-amino acid derivatives have been developed. Conformational control was achieved through chalcogen-bonding interactions between sulfur and oxygen atoms in each ligand, providing well-defined and uniform asymmetric environments around the catalytically active Rh(II) centers. These structural properties render such complexes excellent catalysts for the inside-type asymmetric intramolecular C–H insertion into alpha-aryl-alpha-diazoacetates to yield a variety of cis- alpha, beta-diaryl gamma-lactones, as well as the corresponding trans-isomers through epimerization, in high diastereo- and enantioselectivities. Short total syntheses of the naturally occurring gamma-lactones cinnamomumolide, cinncassin A7, and cinnamomulactone were also accomplished using this conformationally controlled catalyst.

History

Email Address of Submitting Author

furuta@mb.kyoto-phu.ac.jp

Institution

Kyoto Pharmaceutical University

Country

Japan

ORCID For Submitting Author

0000-0003-1037-9715

Declaration of Conflict of Interest

No conflict of interest

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