Synthesis of B-organo-substituted 1,2-, 1,7-, and 1,12-dicarbaclosododecarboranes(12)

Four Decades of Organic Chemistry of closo-Boranes: A Synthetic Toolbox for Constructing Liquid Crystal Materials. A Review

“…B-Iodo compounds undergo Pd-catalyzed cross-coupling reactions with alkyl [171][172][173][174][175][176] , aryl 123,126,139,[173][174][175][176][177][178] (e.g. 37) 123 hetaryl 177 , and acetylenyl 126,174,179 (e.g.…”

“…39) 126 organometallic reagents. First demonstrated for iodocarboranes 175 , the reaction has also been applied to charged species derived from [B 12 [173][174][175]177,178 ), and para-carborane 6 (refs 126,175,179 …”

“…Several types of organometallic compounds, including organic derivatives of Mg (refs 123,126,[171][172][173][175][176][177][178] ), Zn (refs 18,174,181 ), and B (ref. 182 ) have been used and the choice of the metal depends on the iodide structure and the type of organic residue.…”

Unprecedented B–H Activation Through Pd‐Catalysed B–Cvinyl Bond Coupling on Borane Systems

“…Reactions found in the literature are based mostly on Kumada C-C couplings, with few examples in which the bond has been formed by the Heck, Negishi or Suzuki-Miyaura reaction conditions. The methodology using Kumada reaction conditions was first applied to iodocarboranes by Zakharkin et al [6] and further developed by Jones, [7] Hawthorne, [8] Bregadze [9] and our group. [10] The reaction of the anionic monoiodo derivative [8-I-3,3Ј-Co-(1,2-C 2 B 9 H 10 )(1Ј,2Ј-C 2 B 2-with alkyl and aryl reagents has been report-ed.…”

Carbon Extrusion/Cluster Contraction: Synthesis of the Fluorinated Cyano‐closo‐Undecaborate K2[3‐NC‐closo‐B11F10]

“…The only examples of exchange reactions of halogeno substituents at boron clusters by organyl substituents are palladium-catalyzed coupling reactions of iodinated clusters with Grignard reagents and related species. [9,[24][25][26][27] When K[1-H 2 N-closo-CB 11 F 11 ] is treated with an excess of methyllithium, anions containing up to seven methyl groups (i.e. formation of [NC-closo-B 11 F 3 Me 7 ] 2À ) were observed by MALDI mass spectrometry of the reaction mixture.…”