Chemistry Reference
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OTf
-
+
N
Cu(I)
NMI
d
n
4
r
4
n
g
|
1
N
OH
+
1/2 O
2
N
R
O
substrate
oxidation
catalyst
oxidation
+ H
2
O
R
OH
OTf
-
+
N
NMI
Cu(II)
N
OH
+
O
N
.
OH
Cu(II)
OH +
N
catalyst oxidation
O
N
Cu(I)
O
Cu(II)
Cu(I)
O
Cu(II)
O
2
Cu(II)
- Cu(I),1/2 O
2
O
N
substrate oxidation
OH
H
N
H
R
OH
Cu(II)
Cu(I)
Cu(II)
O
OH
+
H
2
O
R
R
O
Benzylic alcohols
- Catalyst oxidation is turn over limiting
- Cu(I)/TEMPOH resting state
Aliphatic alcohols
multiple steps (catalyst and substrate oxidation) control rate
Cu(I), Cu(II), TEMPOH and TEMPO present during turnover
Scheme 1.2 Proposed catalytic cycle for Cu(
I
)/TEMPO-catalyzed aerobic alcohol
oxidation.
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