title: C-H-Activated Direct Arylation of Strong Benzothiadiazole and Quinoxaline-Based Electron Acceptors.
abstract: Electron acceptors are important components of π-conjugated materials, but the strong electron-withdrawing properties of the required synthetic intermediates often make them poor substrates in synthetic schemes designed around conventional organometallic cross-coupling. Here, strong benzodiimine-based acceptors, including 5,6-difluoro[2,1,3]benzothiadiazole, 5,6-dicyano[2,1,3]benzothiadiazole, 5,6-dicyanobenzo[d][1,2,3]triazole, 6,7-dicyanoquinoxaline, and 6,7-dinitroquinoxaline, are shown to undergo facile palladium-catalyzed C-H direct arylation with a variety of bromoarenes in moderate to high yields. The electrochemical characteristics of di-2-thienyl derivatives synthesized using this methodology are compared and suggest that, in an electron-transfer sense, 5,6-dicyano[2,1,3]benzothiadiazole is a comparably strong acceptor to benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazole. The synthetic results suggest that high electron-withdrawing ability, which has traditionally limited reaction yields and structural variety in organic electronic materials, may be advantageous when employing C-H activated direct arylation in certain circumstances.
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Junxiang
authors.initials: J
authors.lastname: Zhang
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Parker
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Wayne
authors.initials: W
authors.lastname: Chen
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: LaRita
authors.initials: L
authors.lastname: Williams
authors.affiliation: Department of Chemistry, New Mexico Highlands University , Las Vegas, New Mexico 87701, United States.
authors.forename: Victor N
authors.initials: VN
authors.lastname: Khrustalev
authors.affiliation: Department of Chemistry, New Mexico Highlands University , Las Vegas, New Mexico 87701, United States.
authors.forename: Evgheni V
authors.initials: EV
authors.lastname: Jucov
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Stephen
authors.initials: S
authors.lastname: Barlow
authors.affiliation: Department of Chemistry, New Mexico Highlands University , Las Vegas, New Mexico 87701, United States.
authors.forename: Tatiana V
authors.initials: TV
authors.lastname: Timofeeva
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Seth R
authors.initials: SR
authors.lastname: Marder