The Journal of Organic Chemistry
Article
7.02 (t, J = 8.2 Hz, 2 H), 7.06−7.27 (m, 4 H); 13C NMR (100 MHz,
CD2Cl2) δ 29.7, 55.7, 68.9, 69.4, 95.2, 111.2, 113.0, 114.1, 114.1,
121.3, 121.9, 122.1, 122.2, 122.2, 126.6, 127.0, 127.3, 128.2, 128.3,
128.5, 143.1, 143.3, 143.5, 143.6, 154.3, 154.4, 155.3, 156.2. (S,S,S,S)-
19: [α]2D0 = −20.7 (c = 0.78, CH2Cl2); HRMS (ESI) m/z calcd for
C62H56Br2O12 [M + Na]+ 1175.2011, found 1175.2011. (R,R,R,R)-19:
[α]2D0 = +19.5 (c = 0.86, CH2Cl2); HRMS (ESI) m/z calcd for
C62H56Br2O12 [M + Na]+ 1175.2011, found 1175.2010.
128.5, 128.6, 129.3, 143.1, 143.2, 143.5, 143.6, 144.3, 152.6, 154.3,
154.4, 154.4, 155.5, 155.8; IR νmax (film) cm−1 3118.1, 2992.5, 1615.2,
1591.1, 1516.9, 1485.5, 1378.9, 1323.1, 1059.7, 857.6, 767.7.
(S,S,S,S,S,S)-22: [α]D20 = −27.6 (c = 0.32, CH2Cl2); HRMS (ESI)
m/z calcd for C88H76O18[M + Na]+ 1443.4924, found 1443.4923.
(R,R,R,R,R,R)-22: [α]D20 = +26.5 (c = 0.34, CH2Cl2); HRMS (ESI) m/
z calcd for C88H76O18[M + Na]+ 1443.4924, found 1443.4934.
(S,S,S,S,S,S)-16,16′-((((8,9-Bis(methoxymethoxy)-
tetraphenylene-1,16-diyl)bis(oxy))bis(ethane-2,1-diyl))bis-
(oxy))bis(1-(2-bromoethoxy)-8,9-bis(methoxymethoxy)-
tetraphenylene) [(S,S,S,S,S,S)-23] and (R,R,R,R,R,R)-23. Com-
pound (S,S,S,S,S,S)-23 was prepared from (S,S,S,S,S,S)-22 (38.0 mg,
26.7 μmol) by using the same preparative method as that for
compound (S,S)-19. Column chromatography on silica gel (EtOAc/
CH2Cl2/hexanes, 1:1:8) gave pure (S,S,S,S,S,S)-23 (27.3 mg, 62%) as
Tetramer (S,S,S,S,S,S,S,S)-20 and (R,R,R,R,R,R,R,R)-20. To a
stirring solution of compounds (S,S,S,S)-18 (25.0 mg, 25.0 μmol) and
(S,S,S,S)-19 (17.0 mg, 15.0 μmol) in acetone (1.0 mL), K2CO3 (80.0
mg, 0.6 mmol) was added. The mixture was heated to reflux overnight.
The solution was cooled and was diluted with water (15 mL). After
that, the mixture was partitioned between water and CH2Cl2 (15 mL ×
3). The combined organic layer was dried over anhydrous Na2SO4 and
filtered. After removal of solvent, the residue was purified by column
chromatography on silica gel (EtOAc/CH2Cl2/hexanes, 1:1:3−1:1:1)
to give pure (S,S,S,S,S,S,S,S)-20 (11.5 mg, 40%) as colorless waxy
solids: 1H NMR (400 MHz, CD2Cl2) δ 3.24 (s, 3 H), 3.76−3.84 (m, 2
H), 4.88 (d, J = 6.4 Hz, 2 H), 4.99 (d, J = 6.8 Hz, 2 H), 6.50 (d, J = 8.4
Hz, 1 H), 6.75 (d, J = 7.8 Hz, 1 H), 6.87 (d, J = 7.8 Hz, 1 H), 7.01 (d, J
= 8.4 Hz, 1 H), 7.14 (t, J = 8.0 Hz, 2 H); 13C NMR (100 MHz,
CD2Cl2) δ 55.7, 69.5, 95.2, 113.5, 114.1, 121.7, 122.2, 127.2, 128.3,
128.6, 143.3, 143.4, 154.3, 156.3; IR νmax (film) cm−1 3118.5, 2992.3,
2882.6, 1591.1, 1516.2, 1484.8, 1159.4, 1109.3, 1059.7, 857.5, 767.5,
745.6, 710.5. (S,S,S,S,S,S,S,S)-20: [α]2D0 = −18.1 (c = 0.92, CH2Cl2);
HRMS (ESI) m/z calcd for C120H104O24 [M + Na]+ 1952.6844, found
1952.6846. (R,R,R,R,R,R,R,R)-20: [α]2D0 = +21.1 (c = 0.78, CH2Cl2);
HRMS (ESI) m/z calcd for C120H104O24 [M + Na]+ 1952.6844, found
1952.6853.
1
colorless waxy solids: H NMR (400 MHz, CD2Cl2) δ 3.22−3.26 (m,
22 H), 3.78−3.86 (m, 8 H), 4.96−4.01 (m, 4 H), 5.00 (m, 6 H), 4.87
(d, J = 6.4, 6 H), 4.98−5.00 (m, 6 H), 6.60 (q, J = 8.0 Hz, 4 H), 6.75
(d, J = 7.6 Hz, 4 H), 6.82−6.90 (m, 10 H), 7.01 (d, J = 8.4 Hz, 6 H),
7.10−7.27 (m, 12 H); 13C NMR (100 MHz, CD2Cl2) δ 29.8, 55.7,
68.8, 68.9, 69.1, 69.6, 69.7, 95.4, 112.5, 113.0, 113.0, 113.2, 113.3,
113.4, 114.3, 121.4, 121.6, 122.1, 122.2, 122.3, 122.3, 126.7, 127.2,
127.2, 127.3, 127.6, 128.3, 128.4, 124.5, 128.5, 143.3, 143.5, 143.6,
143.7, 143.8, 154.4, 154.5, 155.4, 156.2, 156.3. 156.4; IR νmax (film)
cm−1 3117.4, 2993.2, 2882.1, 1615.0, 1590.7, 1520.9, 1487.6, 1181.0,
1160.8, 886.6, 858.2, 768.2, 749.0. (S,S,S,S,S,S)-23: [α]2D0 = −16.8 (c =
0.29, CH2Cl2); HRMS (ESI) m/z calcd for C92H82Br2O18 [M + Na]+
1657.3759, found 1657.3760. (R,R,R,R,R,R)-23: [α]2D0 = +12.6 (c =
0.21, CH2Cl2); HRMS (ESI) m/z calcd for C92H82Br2O18 [M +
Na]+1657.3759, found 1657.3763.
Pentamer (S,S,S,S,S,S,S,S,S,S)-24 and (R,R,R,R,R,R,R,R,R,R)-24.
To a stirring solution of compounds (S,S,S,S,S,S)-23 (30.0 mg, 18.0
μmol) and (S,S,S,S)-18 (17.0 mg, 18.0 μmol) in acetone (3.0 mL),
K2CO3 (50.0 mg, 360.0 μmol) was added. The mixture was heated to
reflux overnight. The mixture was cooled and was diluted with water
(15 mL). After that, the mixture was partitioned between water and
CH2Cl2 (15 mL × 3). The combined organic layer was dried over
anhydrous Na2SO4 and filtered. After removal of solvent, the residue
was purified by column chromatography on silica gel (EtOAc/
CH2Cl2/hexanes, 1:1:3−1:1:1) to give pure (S,S,S,S,S,S,S,S,S,S)-24
(17.4 mg, 40%) as colorless waxy solids: 1H NMR (400 MHz,
CD2Cl2) δ 3.24 (s, 6 H), 3.78 (s, 4 H), 4.88 (d, J = 6.5 Hz, 2 H), 4.99
(d, J = 6.5 Hz, 2 H), 6.53 (d, J = 8.0 Hz, 2 H), 6.75 (d, J = 8.0 Hz, 2
H), 6.85 (d, J = 7.6 Hz, 2 H), 7.01 (d, J = 7.6 Hz, 2 H), 7.11−7.16 (m,
4 H); 13C NMR (100 MHz, CD2Cl2) δ 55.7, 69.3, 95.3, 113.5, 114.2,
121.6, 122.2, 127.1, 127.2, 128.3, 128.5, 143.4, 143.5, 154.4, 156.2; IR
νmax (film) cm−1 3118.1, 2991.7, 2882.8, 1615.5, 1566.0, 1513.2,
1484.1, 1060.8, 854.8, 767.5. (S,S,S,S,S,S,S,S,S,S)-24: [α]2D0 = −7.6 (c =
0.12, CH2Cl2); HRMS (ESI) m/z calcd for C150H130O30 [M + Na]+
2434.8573, found 2434.8545. (R,R,R,R,R,R,R,R,R,R)-24: [α]2D0 = +6.8
(c = 0.09, CH2Cl2); HRMS (ESI) m/z calcd for C150H130O30 [M +
Na]+ 2434.8573, found 2434.8556.
(S,S,S,S,S,S)-16,16′-((((8,9-Bis(methoxymethoxy)-
tetraphenylene-1,16-diyl)bis(oxy))bis(ethane-2,1-diyl))bis-
(oxy))bis(1-(benzyloxy)-8,9-bis(methoxymethoxy)-
tetraphenylene) [(S,S,S,S,S,S)-21] and (R,R,R,R,R,R)-21. To a
stirring solution of compounds (S,S)-14 (45.0 mg, 0.1 mmol) and
(S,S)-16 (130.0 mg, 0.2 mmol) in acetone (4 mL) was added Cs2CO3
(130.3 mg, 0.4 mmol). The mixture was heated to reflux 24 h. The
mixture was cooled and was diluted with water (15 mL). The mixture
was extracted with CH2Cl2 (15 mL × 3) successively. After removal of
solvent, the residue was purified by column chromatography on silica
gel (EtOAc/CH2Cl2/hexanes, 1:1:6) to give pure (S,S,S,S,S,S)-21
(86.4 mg, 54%) as colorless waxy solids. 1H NMR (400 MHz,
CD2Cl2) δ 3.25 (d, J = 2.0 Hz, 18 H), 3.68 (t, J = 8.0 Hz, 8 H), 4.80 (s,
4 H), 4.89 (dd, J = 3.6, 6.4 Hz, 6 H), 4.89 (dd, J = 3.6, 6.4 Hz, 6 H),
6.50 (dd, J = 8.4, 10.4 Hz, 4 H), 6.72−6.91 (m, 14 H), 6.97−7.12 (m,
10 H), 7.13−7.23 (m, 18 H); 13C NMR (100 MHz, CD2Cl2) δ 55.7,
68.4, 68.6, 70.4, 95.2, 112.0, 112.8, 113.1, 114.1, 121.1, 121.3, 121.4,
122.1, 122.2, 126.5, 126.8, 126.8, 127.0, 127.0, 127.4, 128.2, 128.2,
128.2, 128.3, 128.3, 128.4, 137.6, 143.2, 143.2, 143.4, 143.5, 143.4,
143.5,143.6, 154.3, 154.3, 155.6, 156.0, 156.2; IR νmax (film) cm−1
3117.4, 2993.2, 2882.1, 1615.0, 1590.7, 1520.9, 1487.6, 1160.8, 1059.4,
886.6, 858.2, 768.2, 624.5. (S,S,S,S,S,S)-21: [α]2D0 = −42.3 (c = 0.48,
CH2Cl2); HRMS (ESI) m/z calcd for C102H88O18[M + Na]+
1624.5897, found 1624.5879. (R,R,R,R,R,R)-21: [α]2D0 = +39.1 (c =
0.52, CH2Cl2); HRMS (ESI) m/z calcd for C102H88O18[M + Na]+
1624.5897, found 1624.5890.
(S,S,S,S,S,S)-16,16′-((((8,9-Bis(methoxymethoxy)-
tetraphenylene-1,16-diyl)bis(oxy))bis(ethane-2,1-diyl))bis-
(oxy))bis(8,9-bis(methoxymethoxy)tetraphenylen-1-ol)
[(S,S,S,S,S,S)-22] and (R,R,R,R,R,R)-22. Compound (S,S,S,S,S,S)-22
was prepared from (S,S,S,S,S,S)-21 (42.0 mg, 26.0 μmol) by using the
same preparative method as that for compound (S,S)-18. Column
chromatography on silica gel (EtOAc/CH2Cl2/hexanes, 1:1:1) gave
pure (S,S,S,S,S,S)-22 (26.1 mg, 70%) as colorless waxy solids: 1H
NMR (400 MHz, CD2Cl2) δ 3.25 (s, 18 H), 3.74−3.81 (m, 8 H), 4.89
(dd, J = 2.8, 6.4 Hz, 6 H), 5.00 (m, 6 H), 6.59 (dd, J = 8.0, 20 Hz, 5
H), 6.76−6.79 (m, 6 H), 6.83−6.90 (m, 6 H), 7.01−7.04 (m, 6 H),
7.10−7.22 (m, 13 H); 13C NMR (100 MHz, CD2Cl2) δ 55.7, 55.7,
68.6, 68.8, 95.2, 113.4, 113.5, 114.0, 114.1, 114.3, 114.7, 120.6, 121.7,
122.1, 122.2, 122.2, 123.9, 124.8, 126.8, 126.9, 127.0, 127.1, 128.3,
Hexamer (S,S,S,S,S,S,S,S,S,S,S,S)-25 and (R,R,R,R,R,R,R,R,R,-
R,R,R)-25. Compound (S,S,S,S,S,S,S,S,S,S,S,S)-25 was prepared from
(S,S,S,S,S,S)-23 (18.0 mg, 11.0 μmol) and (S,S,S,S,S,S)-22 (10.0 mg,
7.0 μmol) by using the same preparative method as that for compound
(S,S,S,S,S,S,S,S,S,S)-24. Column chromatography on silica gel (EtOAc/
CH2Cl2/hexanes, 1:1:6) gave pure (S,S,S,S,S,S,S,S,S,S,S,S)-25 (8.1 mg,
40%) as colorless waxy solids: 1H NMR (400 MHz, CD2Cl2) δ 3.24 (s,
6 H), 3.61−3.80 (m, 4 H), 4.88 (d, J = 6.4 Hz, 2 H), 4.99 (d, J = 6.4
Hz, 2 H), 6.43 (d, J = 8.0 Hz, 1 H), 6.55 (d, J = 8.0 Hz, 2 H), 6.67−
6.85 (m, 2 H), 6.91 (d, J = 8.0 Hz, 3 H), 6.97−7.16 (m, 3 H); 13C
NMR (100 MHz, CD2Cl2) δ 56.0, 95.5, 113.8, 114.4, 121.9, 122.4,
127.3, 127.4, 128.6, 128.8, 143.6, 143.7, 154.6, 156.4; IR νmax (film)
cm−1 3118.3, 3043.5, 2990.4, 2882.0, 1591.2, 1516.6, 1483.48, 1378.6,
1060.7, 858.1, 767.5, 710.4. (S,S,S,S,S,S,S,S,S,S,S,S)-25: [α]2D0 = −8.5 (c
= 0.10, CH2Cl2); HRMS (ESI) m/z calcd for C180H156O36 [M + Na]+
1470.5114, found 1470.5122. (R,R,R,R,R,R,R,R,R,R,R,R)-25: [α]D20
=
+7.2 (c = 0.08, CH2Cl2); HRMS (ESI) m/z calcd for C180H156O36 [M
+ Na]+ 1470.5114, found 1470.5122.
8571
dx.doi.org/10.1021/jo401240k | J. Org. Chem. 2013, 78, 8562−8573