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Me
Me
[Pd
II
]
N
N
+oxone
N
Me
Me
N
Pd
IV
Pd
IV
Me
Me
N
N
Me
N
Figure 12.7 Plausible mechanism of
Pd-catalyzed
cross-dehydrogenative
dimerization.
Pd(OAc)
2
(10 mol%)
NaHCO
3
,Ag
2
CO
3
Benzoquinone
H
2
O(5equiv)
Ar-BPin (1.5 equiv)
DMSO (0.5 equiv)
t
AmylOH, 100 °C, N
2
,12h
Pd(OAc)
2
(10 mol%)
Li
2
CO
3
(2 equiv)
Ag
2
CO
3
(1.5 equiv)
Benzoquinone
alkyl-BF
3
K(1.5equiv)
THF, 120 °C, N
2
,12h
F
F
O
O
O
Ar
Ar
N
H
H
CF
3
N
H
Ar
H
Alkyl
F
F
Pd(OAc)
2
(10 mol%)
NaHCO
3
(3 equiv)
Ag
2
CO
3
(1.5 equiv)
Benzoquinone (0.5 equiv)
vinyl-BPin (1.2 equiv)
THF, 120 °C, N
2
,12h
O
Ar
H
vinyl
Scheme 12.20 Amide-directed C-H functionalization reactions.
NHAr
Me
R
1
NHAr
O
PhO
2
S
SO
2
Ph
O
Pd(OAc)
2
,DMF(2equiv)
NFSI (1.5 equiv)
70 °C
R
1
F
NFSI
H
H
Me
Scheme 12.21 Amide group-directed para-selective C-H arylation.
typically obtained.
35
The excellent selectivity achieved by Yu and co-workers
can be attributed primarily to the acidic nature of the amide group, pro-
moting stronger coordination to the metal center after deprotonation.
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