H
Synthesis
A. G. Amador et al.
Paper
IR (ATR): 2975, 2935, 1724, 1672, 1478, 1448, 1392, 1367, 1225, 1151,
1
1 H), 3.17–3.04 (m, 1 H), 2.73 (dt, J = 13.7, 8.7 Hz, 1 H), 2.52 (dt, J =
16.1, 5.0 Hz, 1 H), 2.40–2.22 (m, 4 H), 1.73 (ddd, J = 13.1, 9.4, 3.4 Hz, 1
H), 1.67–1.49 (m, 3 H), 1.49 (s, 9 H).
002, 849, 756, 732, 691 cm–1
.
1
H NMR (CDCl , 400 MHz): δ = 7.49 (d, J = 7.0 Hz, 2 H), 7.40–7.32 (m, 2
3
13
H), 7.26 (m, 1 H), 7.17 (t, J = 7.8 Hz, 2 H), 7.09 (t, J = 7.3 Hz, 1 H), 6.93
C NMR (CDCl , 101 MHz): δ = 202.08, 175.59, 141.75, 138.18,
3
(
d, J = 6.9 Hz, 1 H), 3.91 (dd, J = 10.4, 6.9 Hz, 1 H), 3.06 (dt, J = 17.3, 8.3
137.82, 132.34, 129.00, 128.31, 127.96, 127.36, 126.41, 125.88, 80.36,
58.12, 50.62, 49.53, 42.83, 32.01, 31.97, 30.32, 28.16, 20.50.
Hz, 1 H), 2.73–2.60 (m, 2 H), 2.44 (dd, J = 13.3, 9.1 Hz, 1 H), 2.38–2.22
(
1
m, 4 H), 1.93–1.83 (m, 1 H), 1.48 (s, 9 H).
+
+
HRMS (ESI): m/z [M + NH ] calcd for [C26H34NO ] : 408.2533; found:
408.2529.
4
3
3
C NMR (CDCl , 101 MHz): δ = 201.23, 174.36, 149.28, 143.69,
3
137.38, 132.57, 128.16, 128.02, 127.08, 126.62, 124.69, 122.27, 80.35,
5
9.06, 56.04, 44.49, 43.23, 36.75, 33.47, 30.97, 28.12.
tert-Butyl 3-Benzoyl-4-(9H-carbazol-9-yl)cyclopentanecarboxyl-
ate (19)
HRMS (ESI): m/z [M + H]+ calcd for [C25H29O ] : 377.2111; found:
+
3
377.2107.
Yield: 63.5 mg (71%, 2:1 dr); R = 0.3 (acetone/pentanes, 1:29).
f
Minor Diastereomer
Major Diastereomer
Colorless oil.
Colorless oil.
IR (ATR): 2976, 2932, 1720, 1671, 1448, 1367, 1220, 1150, 908, 846,
IR (ATR): 2976, 1724, 1682, 1597, 1484, 1453, 1367, 1337, 1227, 1154,
–1
–1
729, 690 cm
.
847, 750, 724, 698 cm
.
1
1
H NMR (CDCl , 400 MHz): δ = 7.49–7.41 (m, 3 H), 7.31 (t, J = 7.4 Hz, 1
H NMR (CDCl , 400 MHz): δ = 8.04 (d, J = 7.7 Hz, 2 H), 7.62 (d, J = 7.2
3
3
H), 7.26–7.18 (m, 1 H), 7.11 (t, J = 7.8 Hz, 2 H), 7.03 (t, J = 7.6 Hz, 1 H),
Hz, 2 H), 7.57 (d, J = 8.3 Hz, 2 H), 7.44 (t, J = 7.8 Hz, 2 H), 7.35 (t, J = 7.5
Hz, 1 H), 7.27–7.14 (m, 4 H), 5.94 (q, J = 9.1 Hz, 1 H), 4.66 (q, J = 9.1 Hz,
1 H), 3.40 (p, J = 8.1 Hz, 1 H), 2.85–2.57 (m, 3 H), 2.38 (dt, J = 13.3, 9.1
Hz, 1 H), 1.50 (s, 9 H).
6
6
.84 (d, J = 7.5 Hz, 1 H), 4.05 (t, J = 8.7 Hz, 1 H), 3.11 (tdd, J = 9.9, 7.6,
.1 Hz, 1 H), 2.71 (dt, J = 13.6, 9.7 Hz, 1 H), 2.67–2.57 (m, 1 H), 2.54
(
(
1
dd, J = 12.8, 9.8 Hz, 1 H), 2.47–2.25 (m, 2 H), 2.27–2.09 (m, 2 H), 1.76
dt, J = 12.4, 8.9 Hz, 1 H), 1.50 (s, 9 H).
13
C NMR (CDCl , 101 MHz): δ = 199.53, 173.42, 139.31, 136.18,
3
3
C NMR (CDCl , 101 MHz): δ = 201.42, 175.61, 147.06, 143.90,
133.14, 128.39, 128.26, 125.66, 123.41, 120.39, 119.08, 109.76, 81.12,
56.17, 49.49, 44.09, 34.36, 31.36, 28.10.
3
1
6
37.16, 132.45, 128.14, 127.82, 127.19, 126.54, 124.57, 122.60, 80.39,
0.28, 55.35, 46.18, 42.58, 34.90, 31.96, 30.78, 28.17.
HRMS (ESI): m/z [M + H]+ calcd for [C29H30NO ]+: 440.2220; found:
3
+
+
HRMS (ESI): m/z [M + NH ] calcd for [C25H32NO ] : 394.2377; found:
440.2217.
4
3
394.2374.
Minor Diastereomer
tert-Butyl 2-Benzoyl-3′,4′-dihydro-2′H-spiro[cyclopentane-1,1′-
naphthalene]-4-carboxylate (18)
Colorless oil.
IR (ATR): 2977, 1722, 1681, 1597, 1484, 1453, 1367, 1337, 1221, 1151,
Yield: 66.6 mg (84%, 2:1 dr); R = 0.3 (acetone/pentanes, 1:49).
–1
f
750, 724, 699 cm
.
1
H NMR (CDCl , 400 MHz): δ = 8.05 (d, J = 7.7 Hz, 2 H), 7.71 (d, J = 7.2
3
Major Diastereomer
Hz, 2 H), 7.64 (d, J = 7.0 Hz, 2 Hz), 7.49–7.35 (m, 3 H), 7.28–7.17 (m, 5
H), 5.81 (dt, J = 11.0, 8.5 Hz, 1 H), 4.85–4.74 (m, 1 H), 3.09 (dt, J = 15.9,
7.8 Hz, 1 H), 2.97–2.84 (m, 1 H), 2.76 (ddd, J = 13.5, 9.9, 7.7 Hz, 1 H),
2.51 (dt, J = 13.3, 8.1 Hz, 1 H), 2.30 (dt, J = 14.0, 7.6 Hz, 1 H), 1.52 (s, 9
H).
White solid; mp 104.0–106.8 °C.
IR (ATR): 2974, 2936, 1724, 1673, 1447, 1366, 1254, 1230, 1152, 754,
–1
7
20, 691 cm .
1
H NMR (CDCl , 400 MHz): δ = 7.52 (d, J = 7.9 Hz, 1 H), 7.44 (d, J = 8.4
3
13
Hz, 2 H), 7.35 (t, J = 7.4 Hz, 1 H), 7.27 (d, J = 6.2 Hz, 1 H), 7.14 (t, J = 7.8
Hz, 2 H), 7.10 (t, J = 7.7 Hz, 1 H), 6.90 (d, J = 7.6 Hz, 1 H), 4.16 (dd, J =
C NMR (CDCl , 101 MHz): δ = 200.20, 174.24, 139.40, 135.75,
3
133.31, 128.49, 128.47, 125.71, 123.40, 120.34, 119.11, 109.90, 81.07,
56.75, 47.76, 42.78, 33.31, 32.53, 28.15.
11.6, 6.4 Hz, 1 H), 3.10 (dtd, J = 11.6, 9.3, 7.2 Hz, 1 H), 2.72 (q, J = 11.8
Hz, 1 H), 2.57 (dt, J = 16.5, 5.5 Hz, 1 H), 2.36 (qd, J = 11.7, 10.4, 4.5 Hz,
HRMS (ESI): m/z [M + H]+ calcd for [C29H30NO ]+: 440.2220; found:
3
2
1
H), 2.23 (ddd, J = 13.5, 7.9, 5.5 Hz, 2 H), 1.81–1.64 (m, 2 H), 1.66–
.50 (m, 2 H), 1.47 (s, 9 H).
440.2217.
1
3
C NMR (CDCl , 101 MHz): δ = 201.38, 174.27, 143.94, 137.78,
3
Ethyl 4-Benzoyl-3-[(tert-butyldimethylsilyl)oxy]-3-phenylcyclo-
pentanecarboxylate (20)
1
5
37.47, 132.45, 129.28, 128.34, 128.08, 126.70, 126.46, 125.88, 80.39,
8.96, 49.24, 48.71, 43.93, 34.36, 33.26, 29.98, 28.13, 20.23.
Colorless oil; yield: 80.8 mg (94%, 11:1 dr); R = 0.3 (Et O/pentanes,
f
2
HRMS (ESI): m/z [M + H]+ calcd for [C26H31O ] : 391.2273; found:
+
3
1:5).
391.2263.
IR (ATR): 2960, 1722, 1667, 1369, 1153 cm–1
.
1
H NMR (CDCl , 400 MHz): δ = 7.76 (d, J = 7.76 Hz, 2 H), 7.5 (t, J = 7.8
3
Minor Diastereomer
Hz, 1 H), 7.4 (t, J = 7.8 Hz, 2 H), 7.35–7.3 (m, 2 H), 7.2–7.1 (m, 3 H), 4.4
Colorless oil.
(ddd, J = 8.6, 3.6, 1.3 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2 H), 3.43 (tt, J = 10.8,
IR (ATR): 2976, 2937, 1723, 1674, 1447, 1366, 1218, 1151, 733 cm–1
.
7.4 Hz, 1 H), 3.15 (dd, J = 13.1, 10.9 Hz, 1 H), 2.7 (dt, J = 13.1, 9.8 Hz, 1
H), 2.57 (dd, J = 13.1, 7.4 Hz, 1 H), 2.41 (ddd, J = 13.1, 6.7, 4.1 Hz, 1 H),
1
H NMR (CDCl , 400 MHz): δ = 7.67 (d, J = 8.0 Hz, 1 H), 7.46 (d, J = 8.2
3
1.34 (t, J = 7.1 H, 3 H), 0.97 (s, 9 H), –0.07 (s, 3 H), –0.45 (s, 3 H).
Hz, 2 H), 7.32 (t, J = 7.4 Hz, 1 H), 7.30–7.21 (m, 1 H), 7.13 (t, J = 7.8 Hz,
2
H), 7.04 (t, J = 7.3 Hz, 1 H), 6.85 (d, J = 7.6 Hz, 1 H), 4.32 (t, J = 8.3 Hz,
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I