The Journal of Organic Chemistry
Article
3-{o-[2,2-Bis(phenylsulfonyl)-4-penten-1-yl]phenyl}propanal
(5). To a solution of 4 (1.94 g, 4.00 mmol) in CH2Cl2 (80 mL) at rt
were added molecular sieve 4A powder (2.64 g) and PCC (1.29 g, 5.98
mol). The resulting mixture was stirred at that temperature for 1 h,
and hexane (52 mL) and silica gel (51 g) were added. The resulting
slurry was transferred onto the top of a silica gel column and
chromatographed (3:1 to 2:1 hexane/AcOEt) to afford 1.61 g of 5
(83%) as colorless crystals: 1H NMR (300 MHz, CDCl3) δ 9.76 (t, J =
1.4 Hz, 1H), 7.89 (dd, J = 8.7, 1.2 Hz, 4H), 7.66 (tt, J = 7.4, 1.2 Hz,
2H), 7.50 (dd, J = 8.7, 7.4 Hz, 4H), 7.25 (d, J = 7.5 Hz, 1H), 7.21−
7.14 (m, 2H), 6.99−6.93 (m, 1H), 6.01 (ddt, J = 16.7, 10.4, 6.6 Hz,
1H), 5.16−5.07 (m, 2H), 3.75 (s, 2H), 3.09 (d, J = 6.6 Hz, 2H), 2.99
(t, J = 7.5 Hz, 2H), 2.68 (dt, J = 1.4, 7.5 Hz, 2H); 13C NMR (75 MHz,
CDCl3) δ 201.5, 141.3, 137.7, 134.9, 132.0, 131.98, 131.92, 130.9,
130.1, 129.0, 128.5, 126.8, 120.6, 93.0, 45.3, 35.4, 31.0, 25.8; IR
(reflection) 3081, 1714, 1581, 1448, 1328, 1142, 930, 752, 572 cm−1;
mp 132.9−133.9 °C; HRMS (ESI, positive) [M]+ calcd for
C26H26O5S2 m/z 482.1222, m/z found 482.1217.
4-{o-[2,2-Bis(phenylsulfonyl)-4-penten-1-yl]phenyl}-1-bu-
tene (2a). To a solution of methyltriphenylphosphonium iodide (824
mg, 2.03 mmol) in THF (10 mL) at 0 °C was added n-BuLi (1.4 M in
hexane, 1.36 mL, 1.90 mmol). After the mixture had been stirred at rt
for 1 h, a solution of 5 (655 mg, 1.36 mmol) in THF (15 mL) was
added. After the mixture had been stirred at that temperature for 30
min, the reaction was quenched with saturated aqueous NH4Cl and
the mixture extracted three times with AcOEt. The combined organic
phase was dried over Na2SO4 and filtered, and the solvent was
removed under reduced pressure. The residue was purified by silica gel
chromatography (20:1 to 4:1 hexane/AcOEt) to afford 574 mg of 2a
(88%) as colorless crystals: 1H NMR (300 MHz, CDCl3) δ 7.87 (dd, J
= 8.7, 1.5 Hz, 4H), 7.64 (tt, J = 7.2, 1.5 Hz, 2H), 7.47 (dd, J = 8.7, 7.2
Hz, 4H), 7.23 (d, J = 7.8 Hz, 1H), 7.17−7.15 (m, 2H), 6.96−6.88 (m,
1H), 6.02 (ddt, J = 16.8, 10.2, 6.9 Hz, 1H), 5.81 (ddt, J = 17.3, 10.4,
6.6 Hz, 1H), 5.17−5.00 (m, 4H), 3.72 (s, 2H), 3.10 (d, J = 6.9 Hz,
2H), 2.74 (t, J = 7.8 Hz, 2H), 2.24 (dt, J = 6.6, 7.8 Hz, 2H); 13C NMR
(75 MHz, CDCl3) δ 142.4, 137.7, 137.4, 134.3, 131.5, 131.4, 131.2,
130.6, 130.1, 128.5, 127.8, 126.0, 120.2, 115.2, 92.7, 35.5, 35.0, 32.6,
30.5; IR (reflection) 3069, 1582, 1446, 1310, 1141, 1075, 914, 730,
583, 544 cm−1; mp 100.5−101.5 °C; HRMS (ESI, positive) [M]+
calcd for C27H28O4S2 m/z 480.1429, m/z found 480.1423.
central chirality of carbon in a stereospecific manner. Studies of
further synthetic applications of the planar-chiral orthocyclo-
phene are underway.
EXPERIMENTAL SECTION
■
General Method. All reactions were performed in heat gun-dried
glassware under an argon atmosphere unless otherwise noted. The
dehydrated solvent (THF, CH2Cl2, DMF, benzene, and MeOH) and
the solvent for spectroscopy (CH3CN and pentane) were purchased
and used without further purification. H NMR (300 MHz) and 13C
1
NMR (75 MHz) spectra were recorded at ambient temperature using
CDCl3 as a solvent. Chemical shifts (δ) in parts per million were
referenced to the solvent residual peak as an internal standard: CHCl3
1
for H NMR (δ 7.26) and CDCl3 for 13C NMR (δ 77.1). The peak
multiplicities were given as follows: s, singlet; d, doublet; t, triplet; m,
multiplet; br, broad. Infrared spectra was recorded on an FT-IR
spectrometer as neat liquid on NaCl plates or as crystals by use of a
diffuse reflector. Analytical thin-layer chromatography (TLC) was
conducted on silica gel plates with a fluorescent indicator, and
developed plates were visualized by UV (254 nm) and by heating on a
hot plate after staining with a 4% solution of phosphomolybdic acid in
ethanol or a 2.5% solution of p-anisaldehyde in ethanol. Column
chromatography was performed using neutral and spherical silica gel.
Melting points (mp) were measured on a micro melting point
apparatus. HPLC analyses were performed on an UV detector and a
CD detector. Preparative GPC was performed with an UV detector
and an RI detector. X-ray crystallographic data were recorded using a
CCD diffractometer with graphite-monochromated Mo Kα radiation
(λ = 0.7107 Å) at 123 K. HRMS was performed on a high-resolution
mass spectrometer employing a quadrupole doublet-based lens system.
1,1-Bis(phenylsulfonyl)-3-butene.18 To a solution of bis-
(phenylsulfonyl)methane (500 mg, 1.68 mmol) in DMF (10 mL) at
0 °C was added NaH (55 wt % in mineral oil, 80.2 mg, 1.84 mmol).
After the mixture had been stirred at that temperature for 30 min, allyl
bromide (144 μL, 1.68 mmol) was added. The resulting mixture was
stirred at rt for 4 h. The reaction was quenched with saturated aqueous
NH4Cl and the mixture extracted three times with AcOEt. The
combined organic phase was dried over Na2SO4 and filtered, and the
solvent was removed under reduced pressure. The residue was purified
by silica gel chromatography (2:1 hexane/AcOEt) to afford 534 mg of
1,1-bis(phenylsulfonyl)-3-butene (94%) as colorless crystals: 1H NMR
(300 Hz, CDCl3) δ 7.99−7.95 (m, 4H), 7.71 (tt, J = 7.5, 1.7 Hz, 2H),
7.61−7.56 (m, 4H), 5.81 (ddt, J = 17.0, 10.1, 6.9 Hz, 1H), 5.09−5.00
(m, 2H), 4.46 (t, J = 6.0 Hz, 1H), 2.95−2.90 (m, 2H); 13C NMR (75
MHz, CDCl3) δ 137.8, 134.7, 132.3, 129.7, 129.1, 119.1, 83.6, 29.8; IR
(reflection) 2919, 1643, 1583, 1449, 1311, 1142, 1077, 998, 928, 728,
686, 620, 564, 514 cm−1; mp 116.5−117.0 °C; HRMS (EI, positive)
[M]+ calcd for C16H16O4S2 m/z 336.0490, found m/z 336.0484.
3-{o-[2,2-Bis(phenylsulfonyl)-4-penten-1-yl]phenyl}-1-prop-
anol (4). To a solution of 2-(hydroxymethyl)benzenepropanol (3)
(600 mg, 3.61 mmol), 1,1-bis(phenylsulfonyl)-3-butene (1.46 g, 4.33
mmol), Et3N (1.00 mL, 7.21 mmol), and tri-n-butylphosphine (1.78
mL, 7.12 mmol) in benzene (36 mL) at 0 °C was added TMAD (930
mg, 5.40 mmol). The resulting mixture was stirred at rt for 23 h. The
solvent was removed under reduced pressure. The residue was purified
by silica gel chromatography (3:1 to 2:1 hexane/AcOEt) to afford 1.80
(Z)-6,6-Bis(phenylsulfonyl)-6,7,10,11-tetrahydro-5H-benzo-
cyclononene (6). To a refluxed solution of 2a (179 mg, 0.373 mmol)
in CH2Cl2 (35 mL) was added a solution of Grubbs’ first-generation
catalyst (15.4 mg, 0.0187 mmol) in CH2Cl2 (7 mL) over an 8 h
period. The resulting mixture was stirred for 22 h, and the solvent was
removed under reduced pressure. To the residue in CH2Cl2 (15 mL)
was added active charcoal (770 mg). After being stirred for 12 h, the
resulting mixture was filtered, and the solvent was removed under
reduced pressure. The residue was purified by silica gel chromatog-
raphy (3:1 hexane/AcOEt) to afford 168 mg of 6 (quant.) as colorless
1
crystals. H NMR analysis of 6 shows broadening peaks, and the 13C
NMR signal of the sulfonyl α-carbon was not detected probably
because of the very low intensity of the peak under standard
measurement conditions. These observations would be caused by the
interconversion of the conformers on the measurement time scale: 1H
NMR (300 MHz, CDCl3) δ 8.05 (dd, J = 9.0, 1.5 Hz, 4H), 7.76−7.68
(m, 3H), 7.60 (dd, J = 9.0, 7.5 Hz, 4H), 7.22−7.11 (m, 2H), 7.01 (dd,
J = 7.4, 2.0 Hz, 1H), 5.76 (dt, J = 10.5, 8.4 Hz, 1H), 5.48 (br, 1H),
3.69 (s, 2H), 3.05 (d, J = 8.4 Hz, 2H), 2.57 (br, 2H), 2.39−2.32 (br,
2H); 13C NMR (75 MHz, CDCl3) δ 141.8, 137.4, 134.6, 134.5, 133.0
(br), 131.9, 131.4, 128.7, 128.0, 125.4, 123.8, 33.9, 32.0 (br), 28.7,
26.8; IR (reflection) 3064, 1582, 1447, 1309, 1142, 1076, 910, 733,
686, 629, 585 cm−1; mp 90.5−91.0 °C; HRMS (ESI, positive) [M]+
calcd for C25H24O4S2 m/z 452.1116, m/z found 452.1112.
(Z)-6,7,10,11-Tetrahydro-5H-benzocyclononene [(Z)-1]. To a
suspension of 6 (307 mg, 0.678 mmol) in MeOH (23 mL) at rt were
added Mg turnings (569 mg, 23.7 mmol). The resulting mixture was
stirred for 1 h. The reaction was quenched with aqueous HCl (1.0 M,
35 mL) and the mixture extracted twice with pentane. The combined
organic phase was dried over Na2SO4 and filtered, and the solvent was
1
g of 4 (quant.) as colorless crystals: H NMR (300 MHz, CDCl3) δ
7.92 (dd, J = 8.7, 1.2 Hz, 4H), 7.65 (tt, J = 7.5, 1.2 Hz, 2H), 7.50 (dd, J
= 8.7, 7.5 Hz, 4H), 7.27 (d, J = 8.1 Hz, 1H), 7.22−7.14 (m, 2H),
6.99−6.91 (m, 1H), 5.97 (ddt, J = 17.1, 10.2, 6.3 Hz, 1H), 5.13−5.05
(m, 2H), 3.75 (s, 2H), 3.64 (dt, J = 5.7, 6.0 Hz, 2H), 3.09 (d, J = 6.6
Hz, 2H), 2.78 (t, J = 7.8 Hz, 2H), 1.78 (tt, J = 7.8, 6.0 Hz, 2H), 1.41 (t,
J = 5.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 142.3, 137.2, 134.3,
131.5, 131.4, 131.2, 130.4, 129.9, 128.4, 127.8, 125.9, 120.0, 92.6, 62.1,
34.8, 34.0, 30.4, 29.3; IR (reflection) 3543, 2924, 1582, 1446, 1143,
1076, 911, 730, 686, 615, 586, 538 cm−1; mp 139.0−139.8 °C; HRMS
(FAB, positive, matrix of 3-nitrobenzyl alcohol) [M + H]+ calcd for
C26H29O5S2 m/z 485.1456, found m/z 485.1454.
E
J. Org. Chem. XXXX, XXX, XXX−XXX