The synthesis of glycosyl carboranes and carboranyl diacids and diamines as precursors to reagents for boron neutron capture therapy

Chapter 2. The synthesis of a series of O-glycosyl carboranes is described. The reactions of hydroxyalkyl carboranes and esterified carbohydrates, in the presence of a Lewis-acid catalyst, provided to be stereoselective. Reactions of these carboranes with tri-O-acetyl-D-glucal or di-O-acetyl-D-xylal and catalytic amounts of BF;Chapter 3. In model studies, carboranyl monoacids were prepared from lithiated ortho-carborane and cyclic acid anhydrides, such as succinic, tetramethylsuccinic and phthalic anhydrides. The reactivity of one such compound (14) was investigated and several derivatives of this compound were prepared. Diacids were synthesized by reacting Li;Chapter 4. The preparation of carborane-containing diamines was approached by two independent synthetic strategies. The first involved blocking the nitrogen of aromatic imides with the t-BOC group, followed by addition of lithiated carboranes to the imide carbonyls. Results of these reactions were disappointing: 1-(t-butoxycarbonyl)-1,2-dicarbadodecaborane was the single major product. The second strategy focused on the preparation of carboranyl diamines by Gabriel synthesis. Reaction of the sodium salt of Di-(tert-butoxy)-iminodicarboxylate with 1.2-bis-(3-bromoprophyl)-1,2-dicarbododecaborane (41) in DMF and removal of the tert-butoxycarbonyl groups under acidic conditions gave 1,2-bis-(3-aminopropyl)-1,2-dicarbododecaborane (40) in good yield.