Adamantanes with Side Chains

At even higher pH values, metal catalysis is required for chlorination to proceed. Thus, at pH =11, nickel(salen) catalyzes the chlorination of adamantane, cyclohexane and toluene785 and manganese porphyrin promotes the chlorination of cyclohexane786. Selective side-chain chlorination by sodium hypochlorite under PTCs at pH = 8.5 has been used for benzylic chlorinations787,788 and for the functionalization of poly(4-methyl-styrene)789,790. Similarly, with calcium hypochlorite in acetic acid, ring chlorination is reported for toluene, xylenes, anisole and other activated aromatics791. 

Ate-complexes of 1-boraadamantane containing a halogen atom in the y-position of either the side chain (132) or of the adamantane framework (133) undergo y-elimination at room temperature leading to the formation of cyclopropanes (134) and (135), respectively (Scheme 53). These 1,3-elimination reactions presumably proceed synchronously, i.e., simultaneously with the halogen elimination the B—C bond is cleaved and the cyclopropane ring is created. Moreover, the elimination proceeds with the inversion of both of the reaction centers (Scheme 53) <88IZV415>. 

---