Page 27 of 56
The Journal of Organic Chemistry
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dichloromethane and poured into a chromatographic column (50 × 2.5 cm), prepared
22
with 40 g of silica and 2:8 diethyl ether/petroleum ether. Orange oil, [
.5, CHCl , 88 ( ):12 ( ) dr).
NMR (isomeric mixture, 88 ( ):12 (
MHz) = 0.82 (t, = 7.4 Hz, 3 H), 1.02–1.15 (m, 2 H), 1.20–1.28 (m, 3 H), 1.32–1.49
m, 2 H), 1.38 (d, = 6.9 Hz, 3 H), 1.70–1.80 (m, 1 H), 2.49 (dt, = 13.0, 3.6 Hz, 1
H), 2.91 (ddd, = 16.5, 10.4, 6.9 Hz, 1 H), 3.15–3.22 (m, 2 H), 3.50 (dd, = 8.3, 4.2
= 6.9 Hz, 1 H), 6.85–6.89 (m, 1 H), 7.02–7.12 (m, 3 H), 7.18–7.30
):12 ( ) dr, major diastereoisomer,
= 14.1 (p), 21.0 (p), 22.7 (s), 23.9 (s), 26.1 (s), 31.9 (s), 36.8 (s),
39.0 (s), 58.54 (t), 58.58 (t), 126.7 (t), 127.6 (t), 128.1 (t), 128.2 (t), 128.7 (t), 134.8
α]
D
= –30 (
c
1
0
3
S
,S
R
,S
R
f
= 0.8 (diethyl ether/petroleum ether, 2:8). H
S
,S
R,S) dr, major diastereoisomer, CDCl , 400
3
δ
J
10
11
12
13
14
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(
J
J
J
J
Hz, 1 H), 3.75 (q,
J
13
(
m, 5 H). C NMR (isomeric mixture, 88 (
S
,S
R,S
3
CDCl , 100 MHz) δ
+
+
(
q), 139.6 (q), 146.5 (q). HRMS, (ESI , MeOH, C22
found 308.2373. Anal. Calcd for C22 29N (307.48): C, 85.94; H, 9.51; N, 4.56. Found:
C, 86.19; H, 9.73; N, 4.67.
H30N, [M + H] ) calcd for 308.2378,
H
(1S,1’S)-(–)-1-heptyl-2-(1-phenylethyl)-1,2,3,4-tetrahydroisoquinoline,
(–)-1d,
new compound. The synthesis of THIQ (–)ꢀ1d (1.23 g, 60%, 87:13 dr) was carried
out according to procedure A, but with 2.75 g, (12.20 mmol, 2.0 equiv.) of 1ꢀ
iodoheptane as the alkylating agent. The crude oily residue was diluted with 5 mL of
dichloromethane and poured into a chromatographic column (50 × 2.5 cm), prepared
22
with 40 g of silica and 2:8 diethyl ether/petroleum ether. Orange oil, [
.5, CHCl , 87 ( ):13 ( ) dr).
NMR (isomeric mixture, 87 ( ):13 (
MHz) = 0.86 (t, = 7.4 Hz, 3 H), 1.02–1.15 (m, 2 H), 1.16–1.35 (m, 8 H), 1.37 (d,
6.9 Hz, 3 H), 1.40–1.48 (m, 1 H ), 1.70–1.80 (m, 1 H), 2.50 (dt, = 13.0, 3.6 Hz, 1
H), 2.91 (ddd, = 16.5, 10.4, 6.9 Hz, 1 H), 3.15–3.22 (m, 2 H), 3.52 (dd, = 8.3, 4.2
= 6.9 Hz, 1 H), 6.85–6.89 (m, 1 H), 7.02–7.12 (m, 3 H), 7.18–7.30
):13 ( ) dr, major diastereoisomer,
= 14.1 (p), 20.9 (p), 22.7 (s), 24.0 (s), 26.5 (s), 29.3 (s), 29.7 (s),
α]
D
= –23 (
c
1
0
3
S
,S
R
,S
R
f
= 0.85 (diethyl ether/petroleum ether, 2:8). H
S
,S
3
R,S) dr, major diastereoisomer, CDCl , 400
δ
J
J
=
J
J
J
Hz, 1 H), 3.75 (q,
J
13
(
m, 5 H). C NMR (isomeric mixture, 87 (
S
,S
R,S
CDCl , 100 MHz)
δ
3
31.9 (s), 36.9 (s), 39.1 (s), 58.6 (t), 125.5 (t) 125.6 (t), 126.7 (t), 127.6 (t), 128.1 (t),
+
+
1
28.2 (t), 128.7 (t), 134.8 (q), 139.7 (q), 146.5 (q). HRMS (ESI , MeOH, [M + H] ,
C
24
H
34N) calcd for 336.2685, found 336.2686. Anal. Calcd for C24 33N (335.53): C,
H
85.91; H, 9.91; N, 4.17. Found: C, 85.72; H, 9.84; N, 4.27.
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