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O
Ph
CuCl (10 mol %)
H
2
O (10 equiv)
Ph
R
1
R
1
DMF, air, 14 h
95 °C
O
62
63
R
2
CHO
R
1
O
O
Ph
O
O
Ph
Ph
O
Ph
n
O
63a
, n = 1, 64%
63b
, n = 2, 68%
63c
, n = 3, 69%
63d
, n = 4, 68%
63e
, 58%
63f
, 65%
Scheme 7.15 Copper-catalyzed cyclization-oxidation tandem.
Cu
I
R
3
Cu
I
R
3
R
3
R
1
5-exo-dig
Cu
I
R
1
R
1
cyclization
O
+
62
O
XII
R
2
R
2
CHO
XI
R
2
H
H
+
H
2
O
O
HO
copper
catalyzed
R
3
R
3
H
conjugate
R
3
R
1
R
1
R
1
aerobic
oxidation
O
O
addition
O
+
R
2
R
2
R
2
63
XIV
XIII
Scheme 7.16 Proposed mechanism of tandem cyclization-oxidation.
R
Ag/C (1 mol %)
KOH (2 equiv)
OH
O
DMSO
air (1atm), rt, 4 h
R
(7.14)
R
4
64b
64c
64d
65a
65b
65c
65d
R = H
R = MeO
R = Me
R = Cl
R = H
R = MeO
R = Me
R = Cl
93%
92%
87%
84%
The reaction featured a single carbon transfer and C=C and C-O
bond formation. Control experiments established DMSO as the carbon source
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