Huang et al.
1
,16-Dihydroxy-6,11-dimethyltetraphenylene (19). To a sus-
pension of 1,16-dimethoxy-6,11-dimethyltetraphenylene (18) (182
mg, 0.5 mmol) in CH Cl (20 mL) was added dropwise BBr (4
mL, 1 M solution in CH Cl2, 4 mmol) at 0 °C. The mixture was
(20 mL) was added aqueous solution of KOH (2M, 5 mL, 10
mmol). The resulting mixture was warmed to 60 °C until a clear
yellow solution was obtained and TLC indicated the completion
of reaction. After the solution was cooled to room temperature, it
was acidified with 3N HCl (10 mL), and excess methanol was
removed from the mixture by evaporation. The residual aqueous
layer was extracted with ethyl acetate (30 mL × 4). The combined
organic phase was washed with sodium bicarbonate (20 mL × 2)
2
2
3
2
stirred overnight at room temperature and a clear brownish red
solution was obtained. The reaction mixture was quenched with
ice water (10 mL), and a white solid precipitated which was
dissolved by the addition of ethyl acetate (25 mL). The organic
layer was separated and the residual aqueous layer was extracted
with ethyl acetate (30 mL × 4). The combined organic phase was
and brine (30 mL × 4), dried over Na
2 4
SO , filtered and concentrated
under reduced pressure. The resulting residue was purified by
column chromatography on silica gel (ethyl acetate/hexane 1:2),
giving (R,S)-19 or (S,R)-19 (70.6 mg, 97%) as a white solid, with
a purity of >99% ee as determined by chiral HPLC. The
spectroscopic data of (R,S)-19 or (S,R)-19 were identical to those
washed with NaHCO
3
(2M, 30 mL), brine (20 mL × 4), dried over
Na SO , filtered and concentrated under reduced pressure. The
2
4
resulting residue was purified by column chromatography on silica
gel (ethyl acetate/hexane 1:3) to give 1,16-dihydroxy-6,11-dimeth-
yltetraphenylene (19) (164 mg, 97%) as a white solid, mp 222-223
C. H NMR (300 MHz, CD
2
0
of (()-19. (R,S)- 19 [R]
D
: -57.4 (CH
2 2
Cl , c ) 0.50), or (S,R)-19
1
20
°
3
COCD
3
) δ 7.24 (dd, J ) 4.8, 1.2 Hz,
[R]
D
: +55.1 (CH Cl , c ) 0.50).
2 2
2
2
1
2
8
H), 7.06-6.95 (m, 4H), 6.85 (dd, J ) 15.6, 7.5 Hz, 4H), 4.97 (s,
6,11-Dimethyl-1,16-bis(trifluoromethanesulfonyloxy)tetraphe-
nylene (22). To a suspension of (()-1,16-dihydroxy-6,11-dimeth-
yltetraphenylene (19) (36 mg, 0.099 mmol) in dry CH Cl (5 mL)
H), 2.31 (s, 6H); 13C NMR (75 MHz, CD
COCD ) δ 154.6, 144.6,
3
3
42.6, 139.2, 136.8, 129.3, 129.2, 128.5, 128.2, 124.2, 120.9, 114.6,
0.6; IR (KBr) 3499, 3921, 1573, 1442, 1305, 1279, 1208, 1180,
41, 796 cm ; MS (EI) m/z (relative intensity) 364 (M , 100);
HRMS calcd for C26
calcd for C26
H, 6.08.
2
2
was added pyridine (0.1 mL, 1.2 mmol) and then trifluoromethane-
sulfonic anhydride (0.11 mL, 0.67 mmol) at 0 °C. After the addition,
the reaction mixture was stirred for 24 h at ambient temperature
until TLC indicated complete consumption of the starting material.
The reaction was quenched with ice water (5 mL), and the residual
-
1
+
+
H
20
O
2
Na 387.1354; found 387.1355; Anal.
20 2
H O +1/2EtOAc C, 82.33; H, 5.92; found C, 82.39;
(
R)-(+)-6,11-Dimethyl-1,16-bis[(S)-camphorsulfonyloxy]te-
aqueous layer was extracted with CH
combined organic layer was washed with HCl (1M, 10 mL) and
brine (20 mL × 2), dried over Na SO , filtered and concentrated
under reduced pressure. The resulting residue was purified by
column chromatography on silica gel (CH Cl /hexane 1:3) to give
22 as a white solid, mp 147-148 °C. H NMR (300 MHz, CDCl
δ 7.43 (t, J ) 7.8 Hz, 2H), 7.26 (t, J ) 7.8 Hz, 4H), 7.12 (d, J )
2
Cl
2
(15 mL × 3). The
traphenylene (20) and (S)-(+)- 6,11-Dimethyl-1,16-bis[(S)-cam-
phorsulfonyloxy]tetraphenylene (21). To a solution of (()-1,16-
dihydroxy-6,11-dimethyltetraphenylene (19) (75 mg 0.225 mmol)
and (S)-(+)-camphorsulfonyl chloride (0.6 g, 2.3 mmol) in THF
8 mL) was added dropwise triethylamine (0.4 mL, 2.86 mmol) at
°C. The resulting mixture was stirred for 24 h at room temperature
until TLC indicated complete consumption of the starting material.
The reaction was quenched with ice water (5 mL), and then THF
was evaporated. The residual aqueous layer was extracted with
2
4
2
2
1
(
0
3
)
13
7.8 Hz, 2H), 7.05-7.01 (m, 4H), 2.34 (s, 6H); C NMR (75 MHz,
CDCl ) δ 146.0, 138.8, 137.8, 137.0, 130.2, 129.8, 129.0, 127.8,
120.0, 21.0; IR (KBr) 1556, 1459, 1427, 1407, 1212, 1138, 1011,
3
-1
+
CH
2
Cl
2
(50 mL × 3). The combined organic phase was washed
2
953, 888, 825, 761, 610, 516 cm ; MS (ESI) m/z 646 (M + H O ).
with brine (20 mL × 4), dried over Na
2
SO , filtered and concen-
4
The (S,R)-22 or (R,S)-22 was synthesized through a similar
method as that for (S,R)-19 or (R,S)-19 respectively, the spectro-
scopic data of (S,R)-22 or (R,S)-22 were identical to those of (()-
trated under reduced pressure. The residue was purified by column
chromatography on silica gel (ethyl acetate/hexane 1:8) to give the
two diastereomers 20 and 21. Single crystal of the more polar
bissulfonate 20 was grown from ethyl acetate and its absolute
configuration was determined on the basis of an X-ray diffraction
analysis.
2
0
20
22. (S,R)-22 [R] : +43.3 (CH Cl , c ) 0.47), (R,S)-22 [R]
D
2
2
D
:
-48.1 (CH Cl , c ) 0.42).
2
2
2,7-Dimethyltetraphenylene (15). To a mixture of (()-22 (189
mg, 0.3 mmol), Pd(OAc) (100 mg, 0.44 mmol), and dppb (70 mg,
2
The more polar diasteromer was 20 (124 mg, 36%), mp
0.16 mmol), dppp (100 mg, 0.24 mmol) were added dry DMSO
(20 mL) and Et N (0.4 mL). The mixture was stirred at 0 °C for
3
0.5 h before anhydrous formic acid (0.4 mL) was injected in. After
being stirred at 60 °C for 24 h, the reaction was quenched with ice
water (15 mL), and the residual aqueous layer was extracted with
2
0
1
2
35-235.5 °C. [R]
D
: + 7.4 (CH
2
Cl
2
, c ) 1.265); H NMR (300
MHz, CDCl
3
) δ 7.43-7.12 (m, 12H), 3.53 (d, J ) 15 Hz, 2H),
2
.80 (d, J ) 15.1 Hz, 2H), 2.42-2.33 (m, 2H), 2.21-1.89(m, 6H),
1
.65-1.55 (m, 8H), 1.45-1.36 (m, 2H), 0.98 (s, 6H), 0.79 (s, 6H);
1
3
C NMR (75 MHz, CDCl
3
) δ 213.6, 145.9, 145.1, 139.5, 137.9,
CH
2
Cl
2
(30 mL × 3). The combined organic phase was washed
1
4
2
36.6, 129.5, 129.0, 128.9, 128.5, 127.7, 127.6, 119.6, 57.7, 48.7,
7.7, 42.7, 42.2, 29.6, 26.7, 24.6, 21.0, 19.6, 19.4; IR (KBr) 2958,
with brine (20 mL × 4), dried over Na
2
SO , filtered and concen-
4
trated under reduced pressure. The resulting residue was purified
by column chromatography on silica gel (hexane) to give 2,7-
-
1
924, 1747, 1571, 1438, 1365, 1224, 1166, 945, 837, 502 cm ;
+
MS (ESI) m/z (relative intensity) 793 (MH ); HRMS calcd for
dimethyltetraphenylene (15) (10.8 mg, 72%) as a white solid. mp
+
1
C
C
46
H
H
48
O
8
S
2
Na 815.2682; found 815.2682; Anal. calcd for
C, 61.80; H, 5.52; found C, 61.53; H, 5.88.
228 °C (sublimed). H NMR (300 MHz, CDCl
3
) δ 7.29-7.24 (m,
46
48
O
8
S
2
4H), 7.15 (dd, J ) 7.2, 2.4 Hz, 4H), 7.04 (t, J ) 7.5 Hz, 4H), 6.97
(s, 2H), 2.31 (s, 6H); C NMR (75 MHz, CDCl ) δ 141.7, 141.6,
3
13
The less polar diastereomer was 21 (126.7 mg 37%), mp 109-111
2
0
1
°
C. [R]
D
: + 35.6 (CH
2
Cl
2
, c ) 0.675); H NMR (300 MHz, CDCl
3
)
141.4, 138.6, 136.6, 129.8, 129.1, 129.0, 128.0, 127.1, 127.0, 21.0;
IR (KBr) 3011, 2921, 2851, 1612, 1471, 1435, 1045, 815, 776,
δ 7.31-7.26 (m, 4H), 7.16-7.07 (m, 6H), 6.99 (d, J ) 8.1 Hz, 2H),
-
1
3
1
6
1
4
2
.22 (d, J ) 15.3 Hz, 2H), 2.99 (d, J ) 15.0 Hz, 2H), 2.41-2.31 (m,
761, 744, 562, 467 cm ; MS (EI) m/z (relative intensity) 332
+
0H), 2.10-1.90 (m, 6H), 1.61-1.38 (m, 4H), 1.09 (s, 6H), 0.84 (s,
(M ,100); Anal. Calcd for C26
H20 C, 93.94; H, 6.06; found C, 93.81;
H); 13C NMR (75 MHz, CDCl
) δ 213.7, 145.8, 145.1, 142.1, 139.4,
H, 6.19.
3
37.8, 136.6, 129.8, 128.9, 128.6, 128.4, 128.0, 127.9, 120.3, 57.8,
8.5, 47.7, 42.6, 42.2, 26.7, 24.8, 20.9, 19.6, 19.4; IR (KBr) 2961,
Compounds (R)-15 or (S)-15 were synthesized through a similar
method as that for (S,R)-22 or (R,S)-22 respectively, the spectro-
scopic data of (R)-15 or (S)-15 were identical to those of (()-15.
-1
924, 1750, 1364, 1176, 1162, 946, 859, 839, 741, 577, 521 cm ;
+
+
20
20
MS (ESI) m/z 793 (MH ); HRMS calcd for C46
found 815.2673; Anal. calcd for C46 +1/2EtOAc C, 68.87; H,
.26; found C, 68.87; H, 5.86.
R,S)-1,16-Dihydroxy-6,11-dimethyltetraphenylene, (R,S)-19,
and (S,R)-1,16-Dihydroxy-6,11-dimethyltetraphenylene, (S,R)-
H
48
O
8
S
2
Na 815.2682;
(R)-15 [R]
D
: +22 (CH
2
Cl
2
, c ) 0.125), (S)-15 [R]
D
: -23
H O S
48 8 2
(CH Cl , c ) 0.125).
2
2
6
General Procedure for the Racemization and Decomposi-
tion Experiments on the Tetraphenylenes. Tetraphenylene samples
(∼50 mg) were placed in short quartz capillaries, which were flame-
sealed under argon and then heated for 2 h at 300, 400, 500 or 550
(
1
9. To a suspension of 20 or 21 (160 mg, 0.2 mmol) in methanol
3
68 J. Org. Chem. Vol. 74, No. 1, 2009