Page 1073 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Amination of tosylates has been achieved using a hindered ferrocenyldiphosphine 1049
ligand. 172
SECTION 11.3
1 mol % (PhCN) PdCl 2 Transition
2
1 mol % ligand Metal–Catalyzed
OSO C H + H N(CH ) CH 3 NH(CH ) CH 3 Aromatic Substitution
2 7
2
2 7 7
2 7
Reactions
2 h, 25°C
74%
CH 3
CHP[C(CH ) ]
3 3 2
P(c-C H )
6 11 2
Fe
ligand
Similar reactions have been used for substitution by alkoxide and phenoxide
nucleophiles. Hindered binaphthyl ligands have proven useful in substitutions by
alcohols. 173

2 mol % Pd(OAc) 2
2.5 mol % ligand
CH 3 Br + HO(CH ) CH 3 CH 3 O(CH ) CH 3
2 3
2 3
2.5 eq Cs CO 3
2
70°C
CH 3 CH 3 84%
P(t-Bu) 2
(CH ) N
3 2
ligand

Palladium acetate in conjunction with a diphosphine ligand, xantphos, is active
for arylation of amides, ureas, oxazolidinones and sulfonamides. 174

1 mol % Pd(OAc) 2 N N
Br + 3 mol % xanthphos
HN NH O OCH 3
CH O O 1.4 equiv Cs CO 3 CH 3 O 92%
2
3
CH 3 CH 3 dioxane, 100°C
O
PPh 2 PPh 2
xanthphos

172
A. H. Roy and J. F. Hartwig, J. Am. Chem. Soc., 125, 8704 (2003).
173 K. E. Torraca, X. Huang, C. A. Parrish, and S. L. Buchwald, J. Am. Chem. Soc., 123, 10770 (2001).
174
J. Yin and S. L. Buchwald, J. Am. Chem. Soc., 124, 6043 (2002).