10.1002/chem.201800322
Chemistry - A European Journal
FULL PAPER
134.0, 132.9, 131.5, 128.2, 127.2, 123.5, 117.0, 68.3, 53.3, 29.7, 27.8,
25.6; HRMS (pos. APCI): m/z calcd for C36H33O4 529.2373 [M+H]+, found
529.2372.
20,25-dimesityl-20,25-dihydroxy-1,10-
dioxa[10]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
a]indeno[0]paracyclophane (6[8]). Following general procedure B using
diketone 4[8] (100 mg, 189 µmol, 1.0 eq.), anhydrous CeCl3 (145 mg,
588 µmol, 3.1 eq.), mesityl magnesium bromide (0.90 M in THF, 0.63 mL,
57 µmol, 3.0 eq.) and THF (3.8 mL), 6[8] was obtained as a white solid
(129 mg, 168 µmol, 89%). Rf 0.21 (cyclohexane/EtOAc: 10/1); m.p.
236 °C (decomposition); 1H NMR (500 MHz, CDCl3, 243 K): δ 7.89 (d, J =
8.1 Hz, 2H), 7.65 (dd, J = 8.1, 1.7 Hz, 2H), 7.53 (d, J = 1.7 Hz, 2H), 7.50–
7.46 (m, 4H), 7.03 (s, 2H), 6.90–6.85 (m, 4H), 6.61 (s, 2H), 4.37 (s, 2H),
4.22–4.08 (m, 4H), 2.86 (s, 6H), 2.51 (s, 2H), 2.22 (s, 6H), 1.68–1.55 (m,
2H), 1.42 (s, 6H), 1.38–1.15 (m, 6H), 1.12–0.90 (m, 4H); 13C NMR
(126 MHz, CDCl3, 243 K): δ 156.1, 150.3, 139.2, 139.2, 138.3, 136.9,
136.7, 135.0, 132.5, 132.0, 131.5, 128.2, 127.4, 126.4, 123.5, 116.0, 87.0,
67.4, 58.9, 29.4, 27.0, 25.1, 23.9, 23.0, 20.6; HRMS (pos. APCI): m/z calcd
for C54H60NO4 786.4517 [M+NH4]+, found 786.4515; m/z calcd for
C54H55O3 751.4146 [M−OH]+, found 751.4144.
21,26-dioxo-1,11-dioxa[11]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
a]indeno[0]paracyclophane (4[9]). Following general procedure A using
diketone 2 (400 mg, 1.02 mmol, 1.0 eq.), diborylated bisether 3[9] (576 mg,
1.02 mmol, 1.0 eq.), K3PO4 (1.73 g, 8.16 mmol, 8.0 eq.), Pd(OAc)2
(11.6 mg, 51.7 µmol, 5.0 mol%) and SPhos (42.0 mg, 102 µmol, 10 mol%)
in a mixture of toluene (1.22 L) and H2O (122 mL), 4[9] was obtained as
an
off-white
solid
(164 mg,
0.302 mmol,
30%).
Rf
0.21
(cyclohexane/EtOAc: 6/1); m.p. 233 °C; 1H NMR (400 MHz, CDCl3): δ
7.78 (dd, J = 8.2, 1.9 Hz, 2H), 7.73 (dd, J = 8.2, 0.6 Hz, 2H), 7.65 (dd, J =
1.9, 0.7 Hz, 2H), 7.44–7.39 (m, 4H), 6.89–6.84 (m, 4H), 4.52 (s, 2H), 4.19–
4.04 (m, 4H), 1.55–1.44 (m, 4H), 1.20–0.93 (m, 10H); 13C NMR (101 MHz,
CDCl3): δ 202.9, 158.5, 147.7, 141.8, 134.0, 133.1, 131.1, 128.0, 127.0,
122.8, 116.4, 68.5, 53.2, 30.7, 29.8, 29.3, 26.5; HRMS (pos. APCI): m/z
calcd for C37H35O4 543.2530 [M+H]+ found 543.2527.
21,26-dimesityl-21,26-dihydroxy-1,11-
dioxa[11]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
22,27-dioxo-1,12-dioxa[12]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
a]indeno[0]paracyclophane (4[10]). Following general procedure A
using diketone 2 (400 mg, 1.02 mmol, 1.0 eq.), diborylated bisether 3[10]
(590 mg, 1.02 mmol, 1.0 eq.), K3PO4 (1.73 g, 8.16 mmol, 8.0 eq.),
Pd(OAc)2 (11.5 mg, 51.2 µmol, 5.0 mol%) and SPhos (42.1 mg, 103 µmol,
10 mol%) in a mixture of toluene (1.22 L) and H2O (122 mL), 4[10] was
obtained as an off-white solid (247 mg, 0.444 mmol, 43%). Rf 0.28
(cyclohexane/EtOAc: 6/1); Rf 0.18(cyclohexane/CH2Cl2/EtOAc: 10/1/1);
m.p. 222 °C; 1H NMR (400 MHz, CDCl3): δ 7.80 (dd, J = 8.2, 1.9 Hz, 2H),
7.76 (dd, J = 8.2, 0.6 Hz, 2H), 7.67 (dd, J = 1.9, 0.7 Hz, 2H), 7.47–7.39 (m,
4H), 6.93–6.84 (m, 4H), 4.52 (s, 2H), 4.14–4.04 (m, 4H), 1.51–1.38 (m,
4H), 1.22–0.98 (m, 12H); 13C NMR (101 MHz, CDCl3): δ 202.9, 158.1,
148.1, 142.1, 134.2, 133.3, 131.6, 128.1, 127.1, 123.1, 117.3, 68.6, 53.3,
30.3, 30.2, 28.4, 25.7; HRMS (pos. APCI): m/z calcd for C38H37O4
557.2686 [M+H]+, found 557.2688.
a]indeno[0]paracyclophane (6[9]). Following general procedure B using
diketone 4[9] (119 mg, 220 µmol, 1.0 eq.), anhydrous CeCl3 (169 mg,
686 µmol, 3.1 eq.), mesityl magnesium bromide (0.90 M in THF, 0.74 mL,
67 µmol, 3.0 eq.) and THF (2.2 mL), 6[9] was obtained as a white solid
(159 mg, 203 µmol, 92%). Rf 0.08 (cyclohexane/EtOAc: 20/1); m.p.
253 °C (decomposition); 1H NMR (500 MHz, CDCl3, 243 K): δ 7.89 (d, J =
8.6 Hz, 2H), 7.60–7.56 (m, 4H), 7.49–7.44 (m, 4H), 7.02 (br. s, 2H), 6.90–
6.86 (m, 4H), 6.59 (br. s, 2H), 4.35 (s, 2H), 4.21–4.10 (m, 4H), 2.85 (s, 6H),
2.52 (s, 2H), 2.20 (s, 6H), 1.60–1.44 (m, 4H), 1.40 (s, 6H), 1.21–1.08 (m,
8H), 1.02–0.91 (m, 2H); 13C NMR (126 MHz, CDCl3, 243 K): δ 157.4, 150.6,
139.3, 139.2, 138.3, 136.9, 136.8, 135.0, 132.5, 131.8, 131.5, 127.9, 127.3,
127.0, 122.9, 115.5, 87.0, 67.9, 58.8, 30.4, 29.3, 28.6, 26.3, 23.9, 23.0,
20.6; HRMS (pos. ESI): m/z calcd for C55H58O4 782.4330 [M]●+, found
782.4329; m/z calcd for C55H56O3 764.4224 [M−OH2]●+, found 764.4224.
22,27-dimesityl-22,27-dihydroxy-1,12-
dioxa[12]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
24,29-dioxo-1,14-dioxa[14]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
a]indeno[0]paracyclophane (4[12]). Following general procedure A
using diketone 2 (400 mg, 1.02 mmol, 1.0 eq.), diborylated bisether 3[12]
(619 mg, 1.02 mmol, 1.0 eq.),K3PO4 (1.73 g, 8.16 mmol, 8.0 eq.),
Pd(OAc)2 (11.5 mg, 51.2 µmol, 5.0 mol%) and SPhos (41.9 mg, 102 µmol,
10 mol%) in a mixture of toluene (1.22 L) and H2O (122 mL), 4[12] was
obtained as an off-white solid (321 mg, 0.549 mmol, 54%). Rf 0.20
(cyclohexane/CH2Cl2/EtOAc: 10/1/1); m.p. 202 °C; 1H NMR (400 MHz,
CDCl3): 7.82–7.80 (m, 4H), 7.73–7.72 (m, 2H), 7.47–7.41 (m, 4H), 6.93–
6.88 (m, 4H), 4.52 (s, 2H), 4.12 (t, J = 6.7 Hz, 4H), 1.61–1.47 (m, 4H),
1.38–0.96 (m, 16H); 13C NMR (101 MHz, CDCl3): δ 202.7, 158.4, 148.1,
142.1, 134.2, 133.5, 131.5, 128.0, 126.9, 122.8, 116.9, 68.4, 53.2, 30.6,
30.2, 30.2, 28.6, 25.8; HRMS (pos. APCI): m/z calcd for C40H41O4
585.2999 [M+H]+, found 585.2994.
a]indeno[0]paracyclophane (6[10]). Following general procedure B
using diketone 4[10] (140 mg, 251 µmol, 1.0 eq.), anhydrous CeCl3
(193 mg, 783 µmol, 3.1 eq.), mesityl magnesium bromide (0.90 M in THF,
0.84 mL, 0.76 mmol, 3.0 eq.) and THF (5.0 mL), 6[10] was obtained as a
white solid (188 mg, 236 µmol, 94%). Rf 0.24 (cyclohexane/EtOAc: 10/1);
Rf 0.10 (cyclohexane/EtOAc: 20/1); m.p. 242 °C (decomposition); 1H NMR
(500 MHz, [D6]DMSO, 373 K): δ 7.94 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 1.8
Hz, 2H), 7.56–7.52 (m, 4H), 7.50 (dd, J = 8.1, 1.8 Hz, 2H), 6.94–6.90 (m,
4H), 6.71 (s, 4H), 5.34 (s, 2H), 4.14–4.03 (m, 4H), 3.97 (s, 2H), 2.13 (s,
6H), 2.10 (br. s, 12H), 1.48–1.40 (m, 4H), 1.21–1.09 (m, 4H), 1.09–0.96
(m, 8H); 13C NMR (126 MHz, [D6]DMSO, 373 K): δ 156.7, 150.6, 139.7,
139.5, 136.7, 135.7, 134.6, 131.9, 130.9, 127.9, 126.5, 124.8, 121.6, 116.6,
85.4, 67.7, 58.7, 29.0, 28.8, 27.5, 24.6, 22.1, 19.3; HRMS (pos. ESI): m/z
calcd for C56H60O4Na 819.4384 [M+Na]+, found 819.4382, m/z calcd for
C56H59O3 779.4459 [M−OH]+, found 779.4457.
General procedure B for the synthesis of cyclic diols 6[n] and 14[n].
In an oven-dried Schlenk tube anhydrous CeCl3 (3.1 eq.) was dried at
135 °C at 1∙10−3 mbar for 2 h. The tube was purged with argon, cooled to
rt, and anh. THF was added. The resulting white suspension was stirred
at rt overnight. The mixture was cooled to 0 °C, and a solution of mesityl
magnesium bromide or 3,5-bis(trifluoromethyl)phenyl magnesium bromide
(~0.90 M in THF, 3.0 eq.) was added dropwise. The grey suspension was
stirred at 0 °C for 1.5 h. Diketone 4[n] (1.0 eq.) was added in one portion,
and the resulting yellow mixture was stirred at 0 °C for 4 h. The reaction
mixture was quenched with 10% aq. HOAc, warmed to rt and extracted
with CH2Cl2 (2 times). The organic layer was washed with sat. aq. NaHCO3,
dried over Na2SO4, and the solvent was removed under reduced pressure.
Automated flash column chromatography (SiO2, cyclohexane/EtOAc 20/1
to 10/1) yielded diol 6[n].
24,29-dimesityl-24,29-dihydroxy-1,14-
dioxa[14]paracyclo[0](2,7)4b,9b-dihydroindeno[2,1-
a]indeno[0]paracyclophane (6[12]). Following general procedure B
using diketone 4[12] (234 mg, 0.400 mmol, 1.0 eq.), anhydrous CeCl3
(306 mg, 1.24 mmol, 3.1 eq.), mesityl magnesium bromide (0.90 M in THF,
1.30 mL, 1.17 mmol, 2.9 eq.) and THF (4.0 mL), 6[12] was obtained as a
white solid (305 mg, 0.370 mmol, 92%). Rf 0.27 (cyclohexane/EtOAc:
10/1); Rf 0.13 (cyclohexane/EtOAc: 20/1); m.p. 253 °C (decomposition);
1H NMR (500 MHz, CDCl3, 254 K): δ 7.93 (d, J = 8.1 Hz, 2H), 7.66 (d, J =
1.8 Hz, 2H), 7.58 (dd, J = 8.1, 1.8 Hz, 2H), 7.51–7.44 (m, 4H), 7.02 (s, 2H),
6.95–6.88 (m, 4H), 6.59 (s, 2H), 4.34 (s, 2H), 4.20–4.06 (m, 4H), 2.86 (s,
This article is protected by copyright. All rights reserved.