Beilstein J. Org. Chem. 2018, 14, 3018–3024.
3
3
J = 4.6 Hz, 1H, exchangeable with D2O, OH), 4.35 (dd, α-(9´-Hydroxyfluoren-9´-yl)-α-(1,1,3,3-tetramethylindan-2-
J = 7.7 and 4.6 Hz, 1H, H–CO), 7.14 and 7.18 (2 m, 2 × 1H, ylidene)acetonitrile (18). Using the GP protocol, the solid
4
-/7-H), 7.27 (m, 2H, 5-/6-H) ppm, assigned through compari- acrylonitrile derivative 1 (200 mg, 0.95 mmol) was added to a
son with 7; 13C NMR (CDCl3, 100.6 MHz) δ 2.8 and 3.8 (2 t, solution of LDA (1.05 mmol) in dry Et2O, followed by fluoren-
diastereotopic cylopropyl-CH2), 16.4 (d, tert-C of cyclo- 9-one (15, 223 mg, 1.24 mmol) which changed the color of the
propyl), 28.83 and 28.88 (2 q, 2 × 1-CH3), 30.3 and 32.0 (2 q, mixture from yellow to dark green. The crude material
× 3-CH3), 49.11 and 49.16 (2 quat, C-3 and C-1), 71.2 (d, (406 mg) obtained after work-up (GP) was recrystallized from
HCO), 112.3 (quat, C-α), 117.4 (quat, C≡N), 122.1 (d, C-4), toluene (9 mL) to afford colorless 18 (147 mg, 40%) with mp
22.5 (d, C-7), 127.76 and 127.87 (2 d, C-5/-6), 147.71 (quat, 243–245 °C. 1H NMR (CDCl3, 400 MHz, 25 °C) δ 1.66 (sharp
2
2
1
C-7a), 147.92 (quat, C-3a), 178.6 (quat, C-2) ppm, assigned as s, 6H, 2 × 1-CH3), 1.98 (broadened s, 6H, 2 × 3-CH3), 2.35 (s,
above; IR (KBr): 3471 (O–H), 2993, 2961, 2928, 2214 (s, 1H, OH), 7.15 (dm, 1H, 7-H), 7.22 (broadened d, 1H, 4-H,
C≡N), 1629, 1487, 1461, 1039, 759 cm−1; anal. calcd for narrowed at −45 °C), 7.25 (td, 1H, 5-H), 7.28 (td, 1H, 6-H),
C19H23NO (281.4): C, 81.10; H, 8.24; N, 4.98; found: C, 80.92; 7.33 (td, 3J = 7.5 Hz, 2H, 2´-/7´-H), 7.42 (td, 3J = 7.0 Hz, 2H,
H, 8.11; N, 4.97.
3´-/6´-H), 7.48 (d, 3J = 7.6 Hz, 2H, 1´-/8´-H), 7.69 (d,
J = 7.5 Hz, 2H, 4´-/5´-H) ppm, assigned through comparison
3
α-(2´-Hydroxyadamantan-2´-yl)-α-(1,1,3,3-tetramethyl- with 13 and the NOESY correlations 3-CH3 ↔ 1´-/8´-H ↔
indan-2-ylidene)acetonitrile (13). The technique of the GP 1-CH3 (weaker) ↔ 7-H ↔ 6-H, and 1´-/8´-H ↔ 2´-/7´-H ↔
was used to generate 2Li in Et2O from LDA (1.05 mmol) and 3´-/6´-H ↔ 4´-/5´-H; 1H NMR (CDCl3, 400 MHz, −45 °C)
acrylonitrile derivative 1 (200 mg, 0.95 mmol). After continued δ 1.65, 1.98, 2.39, 7.20, 7.27, 7.30, 7.33, 7.37, 7.46, 7.49,
stirring till 1 was completely dissolved, a solution of 7.69 ppm; 13C NMR (CDCl3, 100.6 MHz) δ 29.1 (qq,
adamantan-2-one (11, 186 mg, 1.24 mmol) in dry Et2O (4 mL) 1J = 128 Hz, 3J = 4.5 Hz, 2 × 1-CH3), 31.7 (broadened qq,
was added slowly (1 drop per s) at rt, whereupon the mixture sharp at −45 °C, 1J = 128 Hz, 3J = ca. 4.5 Hz, 2 × 3-CH3), 50.1
was stirred for 30 min and then worked up (GP). The crude ma- (unresolved m, C-3), 51.0 (unresolved m, C-1), 85.7 (m, C-9´),
terial (321 mg after drying in presence of solid KOH) was re- 111.1 (very weak d, stronger at −45 °C, 3J = 8.5 Hz to OH,
crystallized from CCl4 (5 mL) to give colorless platelets 13 C-α), 117.9 (sharp s, C≡N), 120.6 (dd, 1J = 160 Hz, 3J = 8 Hz,
(
141 mg, 41%) with mp 179–180.5 °C. 1H NMR (CDCl3, CH-4´/-5´), 122.3 and 122.4 (2 dd, 1J = 159 Hz, 3J = 8 Hz,
00 MHz, 25 °C) δ 1.64 (s, 6H, 2 × 3-CH3), 1.68 (dm. CH-7/-4), 124.1 (dd, 1J = 160 Hz, 3J = 8 Hz, CH-1´/-8´), 127.2
4
2
3
J = 12.5 Hz, 2H, 1 × 4´-H and 1 × 9´-H), 1.74 (broadened t, and 127.5 (2 dd, 1J = 160 Hz, 3J = 7.5 Hz, CH-5/-6), 128.8 (dd,
J ≈ 2 Hz, 2H, 2 × enantiotopic 6´-H), 1.79 (s, 6H, 2 × 1-CH3), 1J = 162 Hz, 3J = 7.3 Hz, CH-2´/-7´), 130.1 (dd, 1J = 159 Hz,
1
1
–
.83 (m, 3J ≈ 2.5 Hz, 1H, 5´-H), 1.85 (dm, 2J obscured, 2H, 3J = 7.2 Hz, CH-3´/-6´), 139.9 (broadened t, 3J = 7 Hz,
× 8´-H and 1 × 10´-H), 1.86 (s, 1H, OH, δ = 2.30 ppm at C-4a´/4b´), 147.4 (m, C-7a), 147.9 (t, 3J = 7.2 Hz, C-8a´/9a´),
60 °C), 1.89 (m, 3J = 2.8 Hz, 1H, 7´-H), 1.96 (broadened d, 149.6 (unresolved m, C-3a), 179.4 (m, C-2) ppm, assigned
2
2
J = 13 Hz, 2H, 1 × 8´-H and 1 × 10´-H), 2.33 (broadened d, through comparison with 7, 8, 9, and fluoren-9-one →
J = 12.5 Hz, 2H, 1 × 4´-H and 1 × 9´-H), 2.70 (broad, 2H, HETCOR → COLOCS(7 Hz); COLOCS cross-peaks of
1
6
4
2
7
´-/3´-H), 7.12 (m, 1H, 4-H), 7.17 (m, 1H, 7-H), 7.26 (m, 2H, 3J: 1-CH3 → C-2 and C-7a, 3-CH3 → C-2 and C-3a, OH →
-/5-H) ppm, assigned through the NOESY correlations C-α, 4-H → C-6, 5-H → C-7, 6-H → C-4, 7-H → C-5, 1´-H →
-H ↔ 3-CH3 ↔ 1´-/3´-H ↔ all four 4´-/9´-H ↔ 5´-H ↔ C-3´ and C-4a´, 2´-H → C-4´ and C-9a´, 3´-H → C-1´ and
× 6´-H ↔ 7´-H ↔ 8´-/10´-H ↔ 1´-/3´-H ↔ OH, and C-4a´, 4´-H → C-2´ and C-9a´; IR (KBr): 3525 (w). 3417 (s),
-H ↔ 1-CH3 (this without any cross-peaks to the adamantane 3022, 2959, 2925, 2215 (sharp, C≡N), 1607, 1488, 1451, 1366,
protons); 13C NMR (CDCl3, 100.6 MHz) δ 25.9 (d, CH-5´), 1207, 771, 761, 754, 735 cm−1; anal. calcd for C28H25NO
6.5 (d, CH-7´), 28.8 (q, 2 × 1-CH3), 30.0 (q, 2 × 3-CH3), 32.9 (391.5): C, 85.90; H, 6.44; N, 3.58; found: C, 86.13; H, 6.04; N,
t, CH2-4´-/9´), 35.6 (t, CH2-8´-/10´), 37.0 (t, CH2-6´), 37.4 (d, 3.60.
CH-1´-/3´), 50.5 (quat, C-3), 51.5 (quat, C-1), 77.1 (quat, C-2´),
d, C-7), 127.45 and 127.57 (2 d, C-5/-6), 147.4 (quat, C-7a), propyl ketone (21) [9]. 1H NMR (CDCl3, 400 MHz) δ 0.27 (m,
49.2 (quat, C-3a), 182.6 (quat, C-2) ppm, assigned through 4H), 0.49 (m, 4H), 0.80 (m, 2H), 0.86 (m, 4H), 0.98 (m, 2H),
2
(
1
(
1
DEPT, HSQC, and comparison with 7–9, no other significant 1.27 (m, 2H), 1.46 (m, 1 tert-H), 4.3 (broadened s, 1H, OH)
changes at −60 °C; IR (KBr): 3471 (sharp, O–H), 2855, 2201 ppm; 13C NMR (CDCl3, 100.6 MHz) δ 0.28 (2 × CH2), 0.39
(
sharp, C≡N), 1602 (w), 1488, 1453, 1353, 1020, 760 (s) cm−1; (2 × CH2), 11.1 (2 × CH2), 11.3 (2 × CH2), 15.7 (1 × CH), 17.6
anal. calcd for C25H31NO (361.53): C, 83.06; H, 8.64; N, 3.87; (2 × CH), 39.8 (1 × quat C), 70.7 (1 × quat, C–O), 212.9
found: C, 82.90; H, 8.50; N, 3.61. (1 × quat, C=O) ppm.
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