M.C. White/Q. Chen Chem 153 Cross-Coupling-128 Week of october 8. 2002 Selective c-n bond formation K COyglycol 140℃C thermal amination (selectivity 1: 2=6: 1) NH Pddba,, BINAP NaOt Bu 85C Pd-catalyzed amination proposed intermediate in Pd-catalyzed amination The thermal reaction showed selectivity for the more nucleophilic secondary amine to produce I In contrast, Pd-catalyzed amination showed lectivity for amination with the primary amine to produce 2 Senanayake TL 1998.39. 3121-2124M.C. White/Q. Chen Chem 153 Cross-Coupling -128- Week of October 8, 2002 N N F Cl N H NH2 2HCl N N F N NH2 N N F N H NH + . 1 2 norastemizole K2CO3/glycol 140 oC thermal amination Pd2dba3, BINAP, NaOtBu, 85 oC Pd-catalyzed amination (selectivity 1:2 = 6:1) (selectivity 2:1 > 35:1) PPh2 PPh2 Pd L L N N H N F NH L L = proposed intermediate in Pd-catalyzed amination The thermal reaction showed selectivity for the more nucleophilic secondary amine to produce 1. In contrast, Pd-catalyzed amination showed selectivity for amination with the primary amine to produce 2. Senanayake TL 1998, 39, 3121-2124. Selective C-N bond formation