Intermolecular Tin-Free Aminations of Aryl Halides

1 Initial Intermolecular Tin-Free Aminations of Aryl Halides 

In 1995, Hartwig and Buchwald published concurrently their respective groups results on tin-free amination of aryl halides [98, 99]. Instead of isolating or generating a tin amide in situ, the amination reactions were conducted by allowing an aryl halide to react with a combination of an amine and either an alkoxide or silylamide base (Eq. (5)). 

orp-alkyl, phenacyl, amino, alkoxy base = NaO-f-Bu, or LiN(SiMe3)2 

These reactions were typically conducted between 80 and 100 °C in toluene solution. The catalysts used initially were 1, 3, or a combination of [Pd2(dba)3] (5a) (dba = trans,trans- 

---