Chiral Macrocycles Having C3 Symmetry Resulting from Orientation of Thiophene Rings

Tomoya Miura; Takayuki Nakamuro; Yumi Ishihara; Yuuya Nagata; Masahiro Murakami

doi:10.1002/anie.202009781

Chiral Macrocycles Having C₃ Symmetry Resulting from Orientation of Thiophene Rings

Angew Chem Int Ed Engl. 2020 Nov 9;59(46):20475-20479. doi: 10.1002/anie.202009781. Epub 2020 Sep 15.

Authors

Tomoya Miura¹, Takayuki Nakamuro^{1

2}, Yumi Ishihara¹, Yuuya Nagata^{1

3}, Masahiro Murakami¹

Affiliations

¹ Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto, 615-8510, Japan.
² Present address: Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
³ Present address: Institute for Chemical Reaction Design and Discovery, Hokkaido University, Kita 21 Nishi 10, Kita-Ku, Sapporo, Hokkaido, 001-0021, Japan.

PMID: 32770591
DOI: 10.1002/anie.202009781

Abstract

An chiral Rh^II -catalyzed cyclooligomerization reaction of thiophenes having triazolyl and vinyl substituents at the 2- and 4-positions was studied. Structurally interesting cyclic trimers, having chirality that is ascribed only to the orientation of the 2,4-disubstituted thiophene rings, are obtained. The 2,4-disubstitution of the starting thiophene monomer allows production of each of the enantiomers. The observed electronic circular-dichroism spectra are in accord with those simulated by density-functional theory calculations.

Keywords: asymmetric synthesis; chirality; heterocycles; macrocycles; rhodium.

Abstract

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