145
+
10 mol% AgNO 3
Na 2 S 2 O 8
H
O
HP OEt
OEt
R
O
P OEt
OEt
R
R = Me, OMe, Cl, F, CN
Scheme 4.66 Oxidative C-P coupling between simple arenes and diethylphosphite
+
10 mol% Ag 2 SO 4
3 equiv. K 2 S 2 O 8
H
O
HP OEt
OEt
O
P OEt
OEt
R
R
CH 3 CN/H 2 O, air
90 o C, 1-3 h
O
P (OEt) 2
CONEt 2
O
P (OEt) 2
CONEt 2
Br
77%
6 4%
O
P (OEt) 2
CONMe 2
55%
O
P (OEt) 2
NHCOMe
54%
O
P (OEt) 2
SO 2 NEt 2
75%
MeO
O
P (OEt) 2
NO 2
50%
O
HP OEt
OEt
K 2 S 2 O 8
O
P OEt
OEt
SO 4
A
B
C
CONEt 2
CONEt 2
PO(OEt) 2
H
CH 2 ONEt 2
PO(OEt) 2
H
SET
CONEt 2
PO(OEt) 2
SO 4
2Scheme 4.67 Phosphonation of arenes bearing electron-withdrawing directing groups
4 Oxidative Radical Couplings