Triphenylsilyl as a protecting group in the synthesis of 1, 12-heterodisubstituted p-carboranes
A triphenylsilyl group is used as an auxiliary in the synthesis of heterodisubstituted p-carboranes via triphenylsilyl-p-carborane (1). The preparation of 1 is statistical, but with recovery of the starting p-carborane, the effective conversion to 1 is about 90%. Carborane 1 has been easily converted to its lithium and copper derivatives, which were reacted with a range of electrophiles including alkyl halides: an aryl iodide, an acetylene bromide, and a sulfenyl chloride. The derivatives of 1 are crystalline and UV active, which facilitates their isolation and purification. The Ph(3)Si group is efficiently removed with fluoride to give monosubstituted p-carboranes I, which upon further nucleophilic substitution yield p-carboranes II. The yields of heterodisubstituted products II are higher than for direct, "statistical" syntheses. For example, 12-pentyl-1, 12-dicarba-closo-dodecaborane-1-carboxylic acid was synthesized from p-carborane via 1 in 62% overall yield, a considerable improvement over the 44% yield obtained by direct methods.
Douglass
AG
Organic Materials Research Group, Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA.
Pakhomov
S
Reeves
B
Janousek
Z
Kaszynski
P