Palladium catalyzed regioselective B-C(sp) coupling via direct cage B-H activation: synthesis of B(4)-alkynylated o-carboranes.

Abstract

Pd-catalyzed carboxylic acid guided regioselective alkynylation of cage B(4)-H bonds in o-carboranes has been achieved for the first time using two different catalytic systems. In the presence of 5 mol% Pd(OAc)2 and 3 equiv. of AgOAc, the reaction of 1-COOH-2-R1-C2B10H10 with R3SiC[triple bond, length as m-dash]CBr in ClCH2CH2Cl gives 4-(R3SiC[triple bond, length as m-dash]C)-2-R1-o-C2B10H10 in moderate to high yields. This reaction is compatible with alkynes possessing sterically bulky silyl groups such as iPr3Si or t BuMe2Si. Meanwhile, another catalytic system of Pd(OAc)2/AgOAc/K2HPO4 can catalyze the direct B(4)-alkynylation of 1-COOH-2-R1-C2B10H10 with terminal alkynes R2C[triple bond, length as m-dash]CH in moderate to high yields. The latter has a broader substrate scope from bulky silyl to aromatic to carboranyl substituents. Desilylation of the resultant products affords carboranyl acetylene 4-(HC[triple bond, length as m-dash]C)-2-R1-o-C2B10H10 which can undergo further transformations such as Sonogashira coupling, dimerization and click reactions. It is suggested that the above two catalytic systems may proceed via Pd(ii)-Pd(iv)-Pd(ii) and Pd(ii)-Pd(0)-Pd(ii) catalytic cycles, respectively. In addition, the silver salt is found to promote the decarboxylation reaction and thereby controls the mono-selectivity.