ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
4 files

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

preprint
submitted on 23.06.2020, 22:48 and posted on 25.06.2020, 12:12 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

Exports

ChemRxiv

Exports