The Journal of Organic Chemistry
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room temperature for 30 min, diluted with dichloromethane, and then
washed with water. The organic layer was dried over MgSO4,
concentrated, and then purified by column chromatography on Al2O3
(dichloromethane) to give a mixture (103 mg) containing 8c (n = 2)
and 8d (n = 3) as a yellow solid, which was immediately subjected to
the following reaction without further purification.
93.8, 88.7, 78.1, 77.3, 67.1, 60.2, 41.8, 30.6, 26.3, 26.1, 26.0, 16.7. IR
(KBr): 3064, 2926, 2855, 2216, 2190, 2174, 1649, 1511 cm−1. FD-
LRMS m/z (%): 809.5 (5) [M + 3]+, 808.5 (23) [M + 2]+, 807.5 (66)
[M + 1]+, 806.5 (100) [M]+. UV (CH2Cl2): λmax (log ε) 394 (3.98),
361 (4.26), 344 (4.44), 335 (4.48), 316 (4.72), 304 (4.76), 269 (5.00),
256 (sh, 4.83) nm. CD (CH2Cl2): λ 391 (Δε −12), 387 (−11), 384
(−12), 370 (−6), 355 (−18), 346 (+9), 340 (+0), 335 (+10), 329
(−7), 315 (+41), 310 (+19), 305 (+44), 278 (−104), 253 (+42) nm.
FD-HRMS (m/z):31 [M]+ calcd for C58H50N2O2: 806.38723; found,
806.38857.
To a solution of the above mixture (103 mg) containing 8c (n = 2)
and 8d (n = 3) in toluene (70 mL) and Et3N (0.52 mL) was added
terephthaloyl chloride (42 mg, 0.21 mmol), and the reaction mixture
was stirred at 85 °C for 60 min, diluted with dichloromethane, and
then washed with water. The organic layer was dried over MgSO4,
concentrated, and then purified by column chromatography on SiO2
(1:4 ethyl acetate/dichloromethane) to give a mixture (116 mg) of 1c
(n = 2) and 1d (n = 3) as a white solid. Further purification with
HPLC gave pure 1d (n = 3) (28 mg) as a white solid. A single crystal
was obtained by recrystallization from chloroform. 1d: mp 214.0−
216.0 °C (dec). 1H NMR (400 MHz, CDCl3, TMS): δ 7.56 (2H × 2,
dd, J = 1.2, 7.6), 7.46 (4H, d, J = 8.8 Hz), 7.39 (2H, dt, J = 1.2, 7.6
Hz), 7.31 (2H, dt, J = 1.2, 7.6 Hz), 7.08 (4H, s), 7.00 (4H, br.d), 3.93
(4H, br.s), 1.56 (4H, quin, J = 7.2 Hz), 1.33 (4H, sext, J = 7.2 Hz),
0.88 (6H, t, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ 168.3, 143.8,
136.6, 133.1, 132.5, 131.6, 129.5, 128.6, 128.2, 127.7, 127.4, 123.6,
121.2, 93.8, 88.7, 78.1, 77.4, 67.1, 50.1, 29.7, 20.1, 13.8. IR (KBr):
3058, 2959, 2932, 2871, 2216, 2190, 2173, 1649, 1511 cm−1. FD-
LRMS m/z (%): 701.4 (4) [M + 3]+, 700.4 (17) [M + 2]+, 699.4 (57)
[M + 1]+, 698.4 (100) [M]+. UV (CH2Cl2): λmax (log ε) 394 (4.00),
361 (4.29), 344 (4.49), 334 (4.52), 316 (4.75), 304 (4.80), 270 (5.02)
nm. FD-HRMS (m/z):31 [M]+ calcd for C50H38N2O2: 698.29333;
found, 698.29556.
Preparation of (R,R)-2d [X = (R)-CHMe(cHex), n = 3]. To a
solution of a mixture (214 mg) of 5c (n = 2), 5d (n = 3), and (R)-11
(916 mg, 2.16 mmol) in Et3N/THF (8 mL/8 mL) under an argon
atmosphere were added Pd(PPh3)4 (192 mg, 0.166 mmol) and CuI
(32 mg, 0.17 mmol), and the reaction mixture was stirred at 55 °C for
12 h, diluted with dichloromethane, and then washed with water. The
organic layer was dried over MgSO4, concentrated, and then purified
by column chromatography on SiO2 (3:2 dichloromethane/hexane) to
give a mixture (661 mg) containing (R,R)-7c (n = 2) and (R,R)-7d (n
= 3) as a pale yellow amorphous solid, which was subjected to the
following reaction without further purification.
To an ice-cooled solution of a mixture (285 mg) of (R,R)-7c (n =
2) and (R,R)-7d (n = 3) in THF (13 mL) were added 60% NaH in oil
(529 mg, 13.2 mmol) and MeOH (13 mL), and the reaction mixture
was stirred at room temperature for 60 min, diluted with dichloro-
methane, and then washed with water. The organic layer was dried
over MgSO4, concentrated, and then purified by column chromatog-
raphy on Al2O3 (1:1 dichloromethane/hexane) to give a mixture (190
mg) containing (R,R)-9c (n = 2) and (R,R)-9d (n = 3) as a yellow
solid, which was immediately subjected to the following reaction
without further purification.
To a solution of the above mixture (190 mg) containing (R,R)-9c
(n = 2) and (R,R)-9d (n = 3) in toluene (96 mL) and Et3N (0.80 mL)
was added terephthaloyl chloride (65 mg, 0.32 mmol), and the
reaction mixture was stirred at 100 °C for 10 min. To the reaction
mixture were added several portions of terephthaloyl chloride [(98 mg,
0.48 mmol), (101 mg, 0.498 mmol), and (101 mg, 0.498 mmol)]
every 1 h period at 100 °C. The reaction mixture was diluted with
dichloromethane and then washed with water. The organic layer was
dried over MgSO4, concentrated, and then purified by column
chromatography on SiO2, followed by Al2O3 (1:9 ethyl acetate/
dichloromethane), to give a mixture (139 mg) of (R,R)-2c (n = 2) and
(R,R)-2d (n = 3) as a white solid. A further purification with HPLC
gave pure (R,R)-2d (n = 3) (30 mg) as a white solid. (R,R)-2d: mp
178.0−180.0 °C (dec). [α]D22 −310 (c 1.0 in CHCl3). 1H NMR (400
MHz, CDCl3, TMS): δ 7.58−7.55 (2H × 2, m), 7.44 (4H, br.s), 7.39
(2H, dt, J = 1.2, 7.6 Hz), 7.31 (2H, dt, J = 1.2, 7.6 Hz), 7.05 (4H, s),
7.00 (4H, br.s), 4.43 (2H, br.s), 2.06 (2H, br.d), 1.84−1.70 (8H,
br.m), 1.70−1.61 (2H, br.m), 1.33−1.07 (8H, br.m), 1.18 (6H, br.d),
1.05−0.90 (2H, br.m). 13C NMR (100 MHz, CDCl3): δ 168.6, 142.8,
137.1, 133.0, 132.2, 131.6, 129.5, 128.5, 128.2, 127.4, 123.5, 121.5,
Preparation of (R,R)-12a (n = 0). To a solution of 5a (114 mg,
0.564 mmol) and (R)-209g (615 mg, 1.42 mmol) in Et3N/THF (8
mL/8 mL) were added Pd(PPh3)4 (135 mg, 0.117 mmol) and CuI (25
mg, 0.13 mmol) under an argon atmosphere, and the mixture was
stirred at 55 °C for 15 h. The reaction mixture was diluted with
dichloromethane and then washed with water. The organic layer was
dried over MgSO4, concentrated, and then purified by column
chromatography on SiO2 (1:19 ethyl acetate/dichloromethane) to give
(R,R)-12a (426 mg) as a reddish solid in 93% yield. An analytical
sample was obtained as a white solid by further purification with GPC
22
(chloroform). (R,R)-12a: mp 161.0−162.0 °C. [α]D −113 (c 1.0 in
1
CHCl3). H NMR (400 MHz, CDCl3, TMS): δ 7.62−7.59 (2H, m),
7.51−7.49 (2H, m), 7.40 (2H, dt, J = 1.6, 7.6 Hz), 7.36 (2H, dt, J =
1.6, 7.6 Hz), 7.22 (4H, br.d), 7.18−7.09 (6H, br.m), 7.01 (4H, d, J =
8.0 Hz), 6.87 (4H, d, J = 8.0 Hz), 4.43 (2H, br.s), 2.12 (2H, br.d),
1.86−1.57 (10H, br.m), 1.35−0.91 (10H, br.m), 1.15 (6H, d, J = 6.8
Hz). 13C NMR (100 MHz, CDCl3): δ 170.8, 143.0, 141.7, 137.1,
132.0, 131.6, 130.3, 129.3, 129.2, 128.3, 127.8, 127.7, 127.5, 122.4,
121.8, 91.6, 89.9, 59.3, 41.4, 30.8, 30.4, 26.3, 26.1, 26.0, 16.8. IR (KBr):
3064, 2976, 2932, 2849, 2216, 1644, 1506 cm−1. FD-LRMS m/z (%):
815.5 (6) [M + 3]+, 814.5 (22) [M + 2]+, 813.5 (66) [M + 1]+, 812.5
(100) [M]+. UV (CH2Cl2): λmax (log ε) 313 (4.70), 303 (4.69), 266
(4.46) nm. CD (CH2Cl2): λ 313 (Δε −5.4), 308 (−4.7), 299 (−6.1),
282 (−4.8), 274 (−5.4) nm. FD-HRMS (m/z):31 [M]+ calcd for
C58H56N2O2: 812.43418; found, 812.43454.
Preparation of (R,R)-12b9c (n = 1). To a solution of 5b (97 mg,
0.43 mmol) and (R)-20 (467 mg, 1.08 mmol) in Et3N/THF (5 mL/5
mL) were added Pd(PPh3)4 (105 mg, 0.0910 mmol) and CuI (18 mg,
0.095 mmol) under an argon atmosphere, and the mixture was stirred
at 55 °C for 15 h. The reaction mixture was diluted with
dichloromethane and then washed with water. The organic layer was
dried over MgSO4, concentrated, and then purified by column
chromatography on SiO2 (1:24 ethyl acetate/dichloromethane) to give
(R,R)-12b (327 mg) as a yellow amorphous solid in 91% yield.
Preparation of (R,R)-12c (n = 2). To a solution of 5c (22 mg,
0.088 mmol) and (R)-20 (98 mg, 0.23 mmol) in Et3N/THF (1 mL/1
mL) were added Pd(PPh3)4 (22 mg, 0.019 mmol) and CuI (4 mg,
0.02 mmol) under an argon atmosphere, and the mixture was stirred at
55 °C for 20 h. The reaction mixture was diluted with dichloro-
methane and then washed with water. The organic layer was dried over
MgSO4, concentrated, and then purified by column chromatography
on SiO2 (1:24 ethyl acetate/dichloromethane) to give (R,R)-12c (52
mg) as a reddish solid in 68% yield. An analytical sample was obtained
as a white solid by further purification with GPC (chloroform),
23
followed by preparative TLC. (R,R)-12c: mp 156.0−157.0 °C. [α]D
−213 (c 1.0 in CHCl3). 1H NMR (400 MHz, CDCl3, TMS): δ 7.55−
7.51 (2H × 2, m), 7.40 (4H, d, J = 8.4 Hz), 7.37 (2H, dt, J = 1.6, 7.6
Hz), 7.33 (2H, dt, J = 1.6, 7.6 Hz), 7.23−7.21 (4H, br.m), 7.16−7.07
(6H, br.m), 6.92 (4H, d, J = 8.4 Hz), 4.43 (2H, br.s), 2.12 (2H, br.d),
1.84−1.57 (10H, br.m), 1.33−0.91 (10H, br.m), 1.10 (6H, d, J = 7.2
Hz). 13C NMR (100 MHz, CDCl3): δ 170.8, 142.1, 137.0, 132.6,
132.3, 131.5, 129.4, 129.3, 129.1, 128.3, 128.2, 127.7, 127.0, 124.5,
121.3, 93.7, 88.8, 81.5, 77.9, 59.2, 41.5, 30.8, 30.5, 26.3, 26.1, 26.0,
16.7. IR (KBr): 3058, 2928, 2849, 2213, 1650, 1510 cm−1. FD-LRMS
m/z (%): 863.5 (6) [M + 3]+, 862.5 (26) [M + 2]+, 861.5 (70) [M +
1]+, 860.5 (100) [M]+. UV (CH2Cl2): λmax (log ε) 371 (sh, 3.97), 343
(sh, 4.39), 316 (sh, 4.58), 300 (4.70), 290 (4.70), 256 (4.77) nm. CD
(CH2Cl2): λ 368 (Δε −15.8), 357 (−12.6), 346 (−14.9), 315 (+15.9),
307 (+7.5), 304 (+8.5), 290 (−6.9), 277 (+1.2), 274 (+1.0), 262
7623
J. Org. Chem. 2015, 80, 7613−7625