Copper compounds benzylic amination

Compounds with several hydroxyl groups at suitable distances from one another may cyclize to cyclic amines in these reactions.1040,1041 For instance, 1-benzylpyrrolidine is obtained in 76% yield from 1,4-butanediol and benzyl-, amine in the presence of copper chromite in an autoclave at 250°,1040 and... 

The reaction of zinc-copper reagents with acid chlorides has a remarkable generality [7,19] and has found many applications in synthesis (Scheme 9-30) [16,59-64]. The treatment of silyl-protected o-aminated benzylic zinc-copper derivatives such as 33 with an acid chloride leads to a 2-substituted indole 34. Aromatic and heterocyclic zinc compounds provide polyfunctional aromatic or heterocyclic ketones like 35 (see Section 9.6.8 Scheme 9-31) [60]. 

When CoCl2 is used as a co-catalyst, the CDC reactions of allylic sp3 C—H and 1,3-dicarbonyl compounds smoothly afford Trost—Tsuji-type products, which are traditionally prepared from allyl halides or acetates (Equation 11.4) [14]. Moreover, when NBS is used instead of TBHP, selective C—H cleavage of tertiary aliphatic amines is possible (Equation 11.5) [15]. For benzylic C—H bonds, direct C—C bond formation can be achieved using copper perchlorate (Equation 11.6) [16]. 

---