Camouflaged Carboranes as Surrogates for C₆₀:  Syntheses of Functionalized Derivatives by Selective Hydroxyalkylation

Camouflaged Carborarods Derived from B‐Permethyl‐1,12‐diethynyl‐para‐ and B‐Octamethyl‐1,7‐diethylnyl‐meta‐carborane Modules

“…Recently, a method for preparing C-hydroxyalkyl derivatives of 6 in high yields was reported, [23] which provides an attractive route to useful carborarod precursors. The 1,12-bis(2-hydroxyethyl) derivative 7, prepared in a 65 % yield by the reaction of 1,12-dilithiated 6 and ethylene oxide, was used as the precursor to the corresponding bis(ethynyl) derivative.…”

A Camouflagednido-Carborane Anion: Facile Synthesis of Octa-B-methyl-1,2-dicarba-closo-dodecaborane(12) and Its Deboration Reaction

“…In contrast, the metalation of both C ± H vertices of 4 as well as the reaction of the bismetalated intermediate with bulky electrophiles is less facile due to adverse steric effects. [18] The reactivity of both of the carbon vertices of 6 was demonstrated by deprotonation with two equivalents of nBuLi followed by the addition of two equivalents of MeI to yield 1,2,4,5,7,8,9,10,11,12-decamethyl-1,2-dicarba-closo-dodecaborane(12) (11) (Scheme 3). As expected, 6 was remarkably resistant to the basemediated deboration reaction.…”

“…However, slow degradation was observed ( 11 B NMR spectroscopy) when 6 was heated in xylene at the reflux temperature with KOEt in the presence of [18]crown-6. Complete conversion of 6 to the corresponding nido species was observed after 15 h in boiling diglyme containing five equivalents of KOEt.…”

5-O-tert-Butyldiphenylsilyl-2-C-hydroxymethyl-2,3-O-isopropylidene-2′-O-trifluoromethanesulfonyl-D-ribono-1,4-lactone

“…The first crystal structure of a secondary trifluoromethanesulfonate was reported by Barnes et al (1996) and a further two have been reported (Hung et al, 2001;Tremmel et al, 2003). Although two crystal structures of primary trifluoromethanesulfonates of carboranes have been published (Herzog et al, 1999;Kalinin et al, 2005), the present paper reports the first example of the crystal structure of a primary trifluoromethanesulfonate, (3).…”