Improved synthesis of icosahedral carboranes containing exopolyhedral B–C and C–C bonds

Kierstyn P. Anderson, Harrison A. Mills, Chantel Mao, Kent O. Kirlikovali, Jonathan C. Axtell, Arnold L. Rheingold, Alexander M. Spokoyny*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

24 Scopus citations


Carboranes are boron-rich molecular clusters possessing electronic characteristics that allow for orthogonal approaches to vertex-selective modifications. We report improved functionalization methods utilizing orthogonal chemistry to achieve efficient substitution at electron-rich B-vertices and electron-poor C-vertices of carborane. Functionalization of B-vertices with alkyl and (hetero)aryl groups using the corresponding Grignard reagents has been improved through the use of a Pd-based precatalyst featuring an electron-rich biaryl phosphine ligand, resulting in reduced reaction times. Importantly, this method is tolerant towards alkyl-based Grignard reagents containing β-hydrogens. Furthermore, a transition metal-free approach to the substitution of carborane C-vertices with (hetero)aryl substrates has been developed under nucleophilic aromatic substitution (SNAr) conditions. The selective substitution of carboranes afforded by these methods holds potential for the rational synthesis of heterofunctionalized boron clusters with substituents on both boron and carbon-based vertices.

Original languageEnglish (US)
Pages (from-to)187-191
Number of pages5
Issue number2
StatePublished - Jan 11 2019


  • Boron clusters
  • Carborane
  • Catalysis
  • Cross-coupling
  • Nucleophilic aromatic substitution

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry


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