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S. Brenet et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 7.52 (dd, J = 8.3, 6.7 Hz, 1 H), 7.41 (d, J =
7.5 Hz, 2 H), 7.37–7.13 (m, 10 H), 2.59 (s, 6 H), 2.31 (s, 6 H), 1.85 (s, 6
H).
13C NMR (100 MHz, CDCl3): δ = 162.92, 149.88, 143.09, 141.85,
138.69, 137.55, 136.74, 134.60, 129.89, 129.49, 128.39, 128.32,
128.14, 127.79, 127.62, 94.26, 26.81, 17.94, 17.19.
13C NMR (100 MHz, CDCl3): δ = 162.94, 149.44, 142.79, 141.22,
140.60, 138.96, 138.60, 137.89, 137.00, 130.08, 129.66, 128.97,
128.75, 127.42, 127.00, 126.58, 125.75, 84.76, 65.23, 28.93, 27.19,
26.90, 22.23.
HRMS (ESI): m/z [M + Na]+ calcd for C44H35I2NNaO6: 950.0451; found:
950.0449.
HRMS (ESI): m/z [M + H]+ calcd for C40H32I2NO4: 844.0421; found:
844.0420.
(aS)-[2′-(2,8-Diiodo-4,6-dioxo-4,6,10,11,12,13,14,15,16,17-decahy-
dro-5H-dinaphtho[1′,2′:7,8;2′′,1′′:5,6][1,4]dioxocino[2,3-c]pyrrol-
5-yl)-1,1′:3′,1′′-terphenyl-3,3′′-diyl]di(methylene) (2S,2′S)-Bis(2-
phenylpropanoate) (8e)
Anal. Calcd for C40H31I2NO4: C, 56.95; H, 3.71; N, 1.66. Found: C, 57.13;
H, 3.94; N, 1.85.
DMF (3 μL) and oxalyl chloride (50 μL, 0.55 mmol) were added to a
solution of (2S)-2-phenylpropanoic acid (82.4 mg, 0.55 mmol) in an-
hyd CH2Cl2 (6 mL), and the mixture was stirred at 0 °C for 5 min and
then at r.t. for 1 h. The mixture was cooled to –20 °C, and a solution of
(aS)-5-[3,3′′-bis(hydroxymethyl)-1,1′:3′,1′′-terphenyl-2′-yl]-2,8-diio-
do-10,11,12,13,14,15,16,17-octahydro-4H-dinaphtho[1′,2′:7,8;2′′,1′′:5,6]
[1,4]dioxocino[2,3-c]pyrrole-4,6(5H)-dione (100 mg, 0.108 mmol) in
anhyd CH2Cl2 (3 mL) was added, followed by a mixture of anhyd Et3N
(82 μL, 0.6 mmol) and DMAP (1.6 mg, 0.013 mmol) in anhyd CH2Cl2 (3
mL). The mixture was stirred at –20 °C for 2 h and then at r.t. for 24 h.
Sat. aq KHSO4 (6 mL) was added and the aqueous phase was extracted
with CH2Cl2 (2 × 6 mL). The organic phase was dried (MgSO4), filtered,
and concentrated in vacuum. The residue was purified by chromatog-
raphy [silica gel (25 g), cyclohexane–toluene (70:30) then toluene–
EtOAc (95: 5 to 90:10)] to give a pale-yellow solid; yield: 100.4 mg
(0.084 mmol, 78%); mp 79 °C; [α]D25 +123 (c 1.02, CHCl3).
(aS)-[2′-(2,8-Diiodo-4,6-dioxo-4,6,10,11,12,13,14,15,16,17-decahy-
dro-5H-dinaphtho[1′,2′:7,8;2′′,1′′:5,6][1,4]dioxocino[2,3-c]pyrrol-
5-yl)-1,1′:3′,1′′-terphenyl-3,3′′-diyl]di(methylene) Diacetate
This intermediate was obtained by following the same procedure at
that used to obtain 1a:7l (aS)-3,3′-diiodo-5,5′,6,6′,7,7′,8,8′-octahydro-
1,1′-binaphthalene-2,2′-diol (1.065 g, 1.9 mmol), [2′-(3,4-dibromo-
2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-1,1′:3′,1′′-terphenyl-3,3′′-di-
yl]di(methylene) diacetate (1.589 g, 1.3 equiv), and KF (1.13 g, 10
equiv) were dissolved in DMF (22 mL), and the mixture was stirred at
80 °C for 16 h. The DMF was evaporated under vacuum (3 Torr), and
the resulting dark-red oil was directly purified by chromatography
[silica gel (25 g), cyclohexane–toluene (3:7 to 0:10)] to give a pale-
25
yellow solid; yield: 846.6 mg (0.837 mmol, 43%); mp 87 °C; [α]D
+134 (c 0.98, CHCl3).
IR (neat): 2923.48, 2850.66, 1729.82, 1672.82, 1448.02, 1416.36,
1375.20, 1315.04, 1299.21, 1216.89, 1128.23, 1026.91, 700.79 cm–1
.
IR (neat): 3059.63, 3024.80, 2929.82, 2869.66, 1808.97, 1729.82,
1672.82, 1489.18, 1448.02, 1416.36, 1375.20, 1311.87, 1299.21,
1H NMR (400 MHz, CDCl3): δ = 7.64 (s, 2 H), 7.58–7.51 (m, 1 H), 7.45–
7.40 (m, 2 H), 7.36–7.10 (m, 8 H), 5.11 (d, J = 12.6 Hz, 2 H), 5.04 (d, J =
12.6 Hz, 2 H), 2.83–2.76 (m, 4 H), 2.33–2.17 (m, 2 H), 2.08 (s, 6 H),
2.15–2.03 (m, 2 H), 1.80–1.58 (m, 8 H).
13C NMR (100 MHz, CDCl3): δ = 170.76, 162.87, 149.50, 142.62,
140.65, 139.11, 138.55, 137.09, 136.20, 130.25, 129.73, 129.70,
128.98, 128.78, 128.06, 127.90, 127.72, 84.85, 66.12, 28.92, 27.20,
26.90, 22.26, 20.91.
1197.89, 1153.56, 1128.23, 1061.74, 783.11, 694.46 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.58 (s, 2 H), 7.56–7.48 (m, 1 H), 7.37–
7.11 (m, 20 H), 5.10 (d, J = 12.8 Hz, 2 H), 4.98 (d, J = 12.8 Hz, 2 H), 3.77
(q, J = 7.2 Hz, 2 H), 2.80–2.67 (m, 4 H), 2.31–2.13 (m, 2 H), 2.13–1.99
(m, 2 H), 1.80–1.56 (m, 8 H), 1.52 (d, J = 7.2 Hz, 6 H).
13C NMR (100 MHz, CDCl3): δ = 174.24, 162.85, 149.48, 142.61,
140.66, 140.37, 139.00, 138.54, 137.81, 136.39, 130.22, 128.97,
128.70, 128.65, 128.61, 127.77, 127.67, 127.62, 127.56, 127.38,
127.21, 127.10, 84.78, 66.20, 45.51, 28.93, 27.18, 22.25, 18.49, 18.22.
HRMS (ESI): m/z [M + Na]+ calcd for C48H39I2NNaO8: 1034.0663;
found: 1034.0631.
HRMS (ESI): m/z [M + H]+ calcd for C62H52I2NO8: 1192.1782; found:
1192.1756.
(aS)-5-[3,3′′-Bis(hydroxymethyl)-1,1′:3′,1′′-terphenyl-2′-yl]-2,8-
diiodo-10,11,12,13,14,15,16,17-octahydro-4H-dinaph-
tho[1′,2′:7,8;2′′,1′′:5,6][1,4]dioxocino[2,3-c]pyrrole-4,6(5H)-dione
[2-(2,8-Diiodo-4,6-dioxo-4,6,10,11,12,13,14,15,16,17-decahydro-
5H-dinaphtho[1′,2′:7,8;2′′,1′′:5,6][1,4]dioxocino[2,3-c]pyrrol-5-yl)-
1,3-phenylene]di(methylene) Diacetate
(aS)-[2′-(2,8-Diiodo-4,6-dioxo-4,6,10,11,12,13,14,15,16,17-decahy-
dro-5H-dinaphtho[1′,2′:7,8;2′′,1′′:5,6][1,4]dioxocino[2,3-c]pyrrol-5-
yl)-1,1′:3′,1′′-terphenyl-3,3′′-diyl]di(methylene) diacetate (688 mg,
0.68 mmol) was placed in a dry 25 mL round-bottomed flask and
purged with argon. Anhyd CH2Cl2 (4 mL), anhyd MeOH (4 mL), and
AcCl (266 mg, 240 μL, 3.39 mmol) were added, and the mixture was
stirred at 40 °C for 16 h then allowed to cool to r.t. The solvent was
evaporated to give a yellow solid; yield: 646.5 mg (0.68 mmol,
quant.); mp 170 °C; [α]D25 +136 (c 1.02, CHCl3). This was used without
further purification in the next step.
This intermediate was obtained by following a procedure similar to
that used to prepare 1a.7l (aS)-3,3′-Diiodo-5,5′,6,6′,7,7′,8,8′-octahy-
dro-1,1′-binaphthalene-2,2′-diol (57.0 mg, 0.104 mmol), [2-(3,4-di-
bromo-2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-1,3-phenylene]di(meth-
ylene) diacetate (64.2 mg, 1.3 equiv), and KF (60.3 mg, 10 equiv) were
dissolved in DMF (1 mL), and the mixture was stirred at 80 °C for 16 h.
The DMF was evaporated under vacuum (3 Torr) and the resulting
dark-red oil was directly purified by chromatography [silica gel (25 g),
cyclohexane–toluene (3:7 to 0:10)] to give a pale-yellow solid; yield:
IR (neat): 3502.90, 2923.48, 2850.66, 1726.65, 1672.82, 1448.02,
1416.36, 1378.36, 1315.04, 1302.37, 1235.88, 1210.55, 1131.40,
25
31.7 mg (0.0369 mmol, 35%); mp 167 °C; [α]D –12.2 (c 0.87,
1061.74, 783.11, 700.79 cm–1
.
CHCl3).
1H NMR (400 MHz, CDCl3): δ = 7.60 (s, 2 H), 7.56–7.48 (m, 1 H), 7.43–
7.36 (m, 2 H), 7.33–7.21 (m, 6 H), 7.21–7.14 (m, 2 H), 4.61 (s, 4 H),
2.79–2.70 (m, 4 H), 2.29–2.16 (m, 2 H), 2.15–2.02 (m, 2 H), 1.78–1.54
(m, 8 H).
IR (neat): 2932.98, 2850.66, 1729.82, 1679.16, 1473.35, 1444.85,
1432.19, 1416.36, 1378.36, 1315.04, 1210.55, 1131.40, 1026.91,
935.09, 792.61, 745.12 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 3859–3873