Formaldehyde-Extruding Homolytic Aromatic Substitution via C→O Transposition: Selective 'Traceless-Linker' access to Congested Biaryl Bonds

Pabhon Poonpatana; Gabriel Dos Passos Gomes; Thomas Hurrle; Kimhoa Chardon; Stefan Bräse; Kye-Simeon Masters; Igor Alabugin

doi:10.1002/chem.201700085

Formaldehyde-Extruding Homolytic Aromatic Substitution via C→O Transposition: Selective 'Traceless-Linker' access to Congested Biaryl Bonds

Chemistry. 2017 Jul 6;23(38):9091-9097. doi: 10.1002/chem.201700085. Epub 2017 Jun 19.

Authors

Pabhon Poonpatana¹, Gabriel Dos Passos Gomes², Thomas Hurrle³, Kimhoa Chardon¹, Stefan Bräse^{3

4}, Kye-Simeon Masters¹, Igor Alabugin²

Affiliations

¹ Discipline of Nanotechnology and Molecular Sciences, Chemistry, Physics and Mechanical Engineering School, Queensland University of Technology (QUT), GPO Box 2434, Brisbane, Queensland, 4001, Australia.
² Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, 32306-4390, USA.
³ Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany.
⁴ Institute of Toxicology & Genetics (ITG), Karlsruhe Institute of Technology (KIT), Kaiserstrasse 12, 76131, Karlsruhe, Germany.

PMID: 28399331
DOI: 10.1002/chem.201700085

Abstract

A new, selective way to form C-C bonds has been developed. In this report, we disclose the homolytic aromatic substitution via C→O transposition coupled with the elimination of formaldehyde (as a traceless linker). Computational analysis indicates the selectivity can be tuned by sterics in the starting materials following an ipso-attack that leads to the C→O transposition.

Keywords: C−C coupling; density functional calculations; radicals; reaction mechanisms; spiro compounds.