Periodinane-Mediated Cyclization of Anilides 261
O
HN
Ph
CO 2 Me
THF-d 8 / DMSO8 8
d 6 (10/1)
6
IBX
'
O
CO 2 Me
DN
Ph
IBX
'
THF/DMSO (10/1)
CO 2 Me
O
HN
Ph
IBX, DMSO
'
IBX
THF/ F F DMSO-d
/
6 (10/1)
'
CO 2 Me
Ph h h
N
O
CO 2 Me
D
N
O
Ph h h
3
4
5
6
3
NO REACTION
Scheme 39.3
2 2.
2. K Ki Ki Ki K Ki Ki K Kin i in in in i i e et ti ti ti t ti ti t tic ic ic
ic i i S St tu u
tud di di di d di di d die ie i ie ie ie i ies s
2.1 The effect of the substituents on the reaction rates were studied on a series of
p-aryl-substituted anilides 7. Electron-donating substituents (R = MeO) resulted in an increase in the reaction rate, whereas electron-withdrawing substituents caused a decrease in the reaction rate (R = Cl, COMe) or had no significant effect on the rate (R = F). For anilides with R = NO 2 or CF 3 no
reaction occurred. The Hammett plot gave a linear graph with a negative
slope and the better correlations were found with V
+ parameters (Fig. 39.1).
O
HN
Ph
CO 2 Me
THF-d 8 / DMSO8 8
d 6 (10/1)
6
IBX
'
O
CO 2 Me
DN
Ph
IBX
'
THF/DMSO (10/1)
CO 2 Me
O
HN
Ph
IBX, DMSO
'
IBX
THF/ F F DMSO-d
/
6 (10/1)
'
CO 2 Me
Ph h h
N
O
CO 2 Me
D
N
O
Ph h h
3
4
5
6
3
NO REACTION
Scheme 39.3
2 2.
2. K Ki Ki Ki K Ki Ki K Kin i in in in i i e et ti ti ti t ti ti t tic ic ic
ic i i S St tu u
tud di di di d di di d die ie i ie ie ie i ies s
2.1 The effect of the substituents on the reaction rates were studied on a series of
p-aryl-substituted anilides 7. Electron-donating substituents (R = MeO) resulted in an increase in the reaction rate, whereas electron-withdrawing substituents caused a decrease in the reaction rate (R = Cl, COMe) or had no significant effect on the rate (R = F). For anilides with R = NO 2 or CF 3 no
reaction occurred. The Hammett plot gave a linear graph with a negative
slope and the better correlations were found with V
+ parameters (Fig. 39.1).