meso-Functionalization of Boron(III) Subporphyrin with Boron(III) meso-Lithiosubporphyrin

Yosuke Bekki; Daiki Shimizu; Keisuke Fujimoto; Atsuhiro Osuka

doi:10.1002/chem.201802339

meso-Functionalization of Boron(III) Subporphyrin with Boron(III) meso-Lithiosubporphyrin

Chemistry. 2018 Aug 27;24(48):12708-12715. doi: 10.1002/chem.201802339. Epub 2018 Jul 19.

Authors

Yosuke Bekki¹, Daiki Shimizu¹, Keisuke Fujimoto¹, Atsuhiro Osuka¹

Affiliation

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.

PMID: 29882368
DOI: 10.1002/chem.201802339

Abstract

Boron(III) meso-lithiosubporphyrin was prepared by bromine-lithium exchange of B-tolyl B^III meso-bromosubporphyrin with n-butyllithium at -98 °C. The resulting subporphyrinyllithium was treated with various electrophiles such as benzophenone, N,N-dimethylformamide, CO₂ , chlorotrimethylsilane, N-fluorobenzenesulfonimide, and dimesitylboryl fluoride to give the corresponding meso-functionalized B^III subporphyrins. The nucleophile was also used to construct B^III subporphyrin dimers such as bis(B^III subporphyrinyl)ketone, bis(B^III subporphyrinyl)carbinol, and disilane-bridged B^III subporphyrin dimer. The structural, optical, and electrochemical properties of these meso-functionalized B^III subporphyrins were examined by UV/Vis absorption and fluorescence spectroscopy, electrochemical studies, and DFT calculations.

Keywords: halogen-metal exchange; lithium; nucleophilic reactions; porphyrinoids; subporphyrins.