Chemistry Reference
In-Depth Information
Table 5.1 CDC reaction of
tetrahydroisoquinolines with nitroalkanes by ball
milling.
a
R
1
R
1
DDQ
N
O
2
N
R
+
R
2
Ar
N
Silica gel
ball milling
R
2
Ar
R
NO
2
1
2
3
1a
: R
1
= R
2
= H, Ar = Ph
1b
: R
1
= R
2
= H, Ar = 4-MeOC
6
H
4
1c
: R
1
= R
2
= H, Ar = 4-MeC
6
H
4
1d
: R
1
= R
2
= OMe, Ar = Ph
1e
: R
1
= R
2
= OMe, Ar = 4-MeC
6
H
4
2a
: R = H
2b
: R = Me
2c
: R = Et
N
N
N
O
2
N
O
2
N
O
2
N
3a
3b
3c
85%, 10 min,
(89%, 120 min)
b
75%, 15 min
(78%, 180 min)
b
76%, 15 min
(70%, 180 min)
b
N
N
N
O
2
N
OMe
O
2
N
OMe
O
2
N
OMe
3d
3e
3f
80%, 20 min
(75%, 120 min)
b
70% 30 min
(65%, 210 min)
b
70% 30 min
(60%, 210 min)
b
MeO
MeO
N
N
N
MeO
MeO
O
2
N
O
2
N
O
2
N
3g
3h
3i
75%, 30 min
(70%, 270 min)
b
65%, 15 min
(68%, 210 min)
b
60%, 30 min
(30%, 210 min)
b
a
Reactions were carried out with 1 (1.0 mmol), 2 (2 mmol), DDQ (1.0 mmol), silica gel (0.5 g) and
two stainless steel balls (d
ΒΌ
8.0 mm) at 30 Hz, 10-30 min. Isolated yields based on 1.
b
Comparative experiments were carried out with 1 (1 mmol), 2 (10 mL), DDQ (1 mmol) under
stirring conditions. Isolated yields based on 1.
Cu(
I
) and Cu(
II
) were used to promote the reactions, and good results were
obtained in all cases.
13
Various a-alkynylamine derivatives were generated in good yields with
various kinds of substituted aromatic alkynes, aliphatic alkynes and pro-
piolate as substrates (Table 5.2). When N-(4-methoxyphenyl)tetrahydro-
isoquinoline (1b) or 6,7-dimethoxy-N-aryl-tetrahydro-isoquinoline 1d/1e was
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