Stereocontrolled synthesis of anthracene β-C-ribosides: Fluorescent probes for photophysical studies of DNA

Article abstract of DOI:10.1016/S0040-4039(02)02791-0

Effective, stereocontrolled syntheses of the 1-anthracenyl and 2-anthrancenyl β-C-2′-deoxyribosides are reported and were based on a diastereofacialselective, palladium-catalyzed glycosidation of the corresponding protected (4S,5R)-4-hydroxy-5-(hydroxymethyl)dihydrofuran.

Full text of DOI:10.1016/S0040-4039(02)02791-0

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 1215–1219
Stereocontrolled synthesis of anthracene b-C-ribosides:
fluorescent probes for photophysical studies of DNA
Robert S. Coleman* and Mark A. Mortensen
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH 43210, USA
Received 13 September 2002; revised 6 December 2002; accepted 9 December 2002
Abstract—Effective, stereocontrolled syntheses of the 1-anthracenyl and 2-anthrancenyl b-C-2%-deoxyribosides are reported and
were based on a diastereofacialselective, palladium-catalyzed glycosidation of the corresponding protected (4S,5R)-4-hydroxy-5-
(hydroxymethyl)dihydrofuran. © 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
In studying the dynamic properties of DNA using
ultrafast photophysical techniques,1 it is necessary to
appropriately localize a reporter molecule within the
double helix. The native purine and pyrimidine bases
have excited state lifetimes on the sub-picosecond time
scale, which makes them unsuitable for studying
dynamic events that occur on the picosecond or slower
We propose that anthracene b-C-2%-deoxyribosides10
will function as van der Waals probes. There will be a
time-scale.2 In our collaborative effort to understand
molecular origins of the unique dynamics of DNA, we
use an adaptation of the time-resolved Stokes shift
technique3 for measurement of the local structural
relaxation in response to the instantaneously altered
dipole moment in the excited state. As the nearby
components of the DNA molecule relax, the electric
field at the dipole is increased, resulting in a lowered
energy of the probe molecule and an accompanying
red-shift of the fluorescence.4 The time dependence of
the shift in the fluorescence can be related with the
time-dependent relaxation the surrounding charged
groups (i.e., the bases and sugar-phosphate backbone
of DNA).
change in polarizability11 upon excitation of these
molecules12 to the p* state, thereby altering van der
Waals attractions for nearby groups. This change will
affect the nearby components of the DNA by what can
best be described as a ‘mechanical’ effect. Modeling
studies were ambiguous with respect to the site of
covalent attachment of anthracene to the deoxyribose
C1%, as it appeared that both C1 and C2 of anthracene
could provide appropriate localization of the probe
within the DNA double helix. We now report full
synthetic details for the preparation of C-ribosides 2
and 3, and improved syntheses of 1- and 2-
hydroxyanthracene.
Our previous studies relied on coumarin C-riboside 15
that is incorporated synthetically into DNA oligomers.
This molecule is placed in the complementary position
to a tetrahydrofuran abasic site analog.6 This molecule
is a dipolar probe, where the excited state is a charge
transfer transition.7 This probe has proven effective in
time-resolved Stokes shift experiments with duplex
DNA.8,9
The synthesis of both probes used a reliable Heck
coupling13 between aryl triflate 6 and deoxyribose gly-
cal 7.14 The resulting enol ether 5 was converted to
* Corresponding author. Tel.: 614-292-4548; fax: 614-292-4647;
e-mail: coleman@chemistry.ohio-state.edu
0040-4039/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)02791-0

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R. S. Coleman, M. A. Mortensen / Tetrahedron Letters 44 (2003) 1215–1219
ketone 4 by desilylation, either as a separate step or in
the workup of the Heck coupling. The carbonyl group
of 4 was reduced diastereoselectively to provide the
2%-deoxyribose system contained in 3. The regioisomeric
anthracene system 2 was constructed in an identical
manner starting from 2-hydroxyanthracene. While the
synthetic scheme for the synthesis of 2 and 3 is straight-
forward, it is far from trivial largely because the
regioisomeric hydroxyanthracenes are difficult com-
pounds to access, particularly the 2-hydroxy isomer.
2-hydroxyanthracene (11). Installation of the tri-
fluoromethanesulfonate ester proceeded in high yield to
afford coupling partner 12.
Synthesis of the regioisomeric 1-hydroxyanthracene
(14) proceeded uneventfully in good yield after opti-
mization using a Bucherer reaction18 of commercially
available 1-aminoanthracene (13) to afford 14. Installa-
tion of the trifluoromethanesulfonate ester under stan-
dard conditions proceeded in high yield to afford
coupling partner 6.
3. Stereocontrolled C-glycoside construction
Heck coupling of triflate 12 with glycal 7 (prepared
conveniently from thymidine in three steps14), under
conditions slightly modified from our previous work,5
followed by in situ fluoride-promoted desilylation,
afforded the aryl b-C-glycoside 15 in 78% yield for the
two steps (1.2 mmol scale). The use of the phase-trans-
fer compound tetrabutylammonium bromide in Heck
couplings under anhydrous conditions significantly
improves reaction yields.19 However, under these reac-
tion conditions, the predominate product was ketone
15, accompanied by only a small amount of the
expected silyl enol ether; we treated the crude reaction
mixture with HF·pyridine prior to purification. (In the
coupling reaction with triflate 6, this added step was
not necessary.)
2. Synthesis of 1- and 2-hydroxyanthracene
The existing syntheses of 2-hydroxyanthracene or the
corresponding anthraquinone are cumbersome or
lengthy,15 so we combined the more attractive aspects
of several existing routes into a workable route to this
phenol. 2-Aminoanthraquinone (8) proved to be a suit-
able starting material, and was converted to 2-bromo-
anthraquinone (9) by a Sandmeyer-like reaction. A
solution of 8 in THF was added to a mixture of
tert-butyl nitrite and cupric bromide in acetonitrile.16
Only trace amounts of anthraquinone were observed as
a side-product.
The amount of Ph3P significantly affected the reaction
yield: 2 equiv. relative to palladium resulted in a slow
coupling accompanied by noticeable amounts of the
C4% epimerized compound; with no Ph3P the reaction
proceeded much more rapidly on a small scale, but
these conditions were not amenable to scale-up, as
yields were lowered because of catalyst instability; in
the presence of one equivalent of Ph3P, the reaction
The quinone of 9 was reduced to the aromatic system
by three-step sequence of reduction, elimination, and
reduction17 to afford 2-bromoanthracene (10). Conver-
sion of the bromide of 10 to the corresponding phenol
proceeded in modest yield via the intermediate anthra-
cenyllithium species, which was trapped as the ditri-
butyl borinate that was oxidized in situ to afford

R. S. Coleman, M. A. Mortensen / Tetrahedron Letters 44 (2003) 1215–1219
1217
proceeded at a rate not noticeably slower than that
4.3. 1%-Anthracen-1-yl-3%-keto-2%-deoxy-C-riboside (4)
observed in the absence of phosphine, and only trace
amounts (55%) of the C4% epimerized product were
evident. These results suggest that the Heck coupling is
proceeding via a non-polar pathway.20 Hydroxyl-
directed reduction of the ketone of 15 using tetra-
methylammonium triacetoxyborohydride21 in the
presence of acetic acid provided the diol 2 in acceptable
yields. Use of sodium triacetoxyborohydride proved
less effective due to the insolubility of ketone 15 in
acetonitrile.
Trifluoromethanesulfonate 6 (209.6 mg, 0.642 mmol),
NaHCO3 (175.1 mg, 2.08 mmol, 3.24 equiv.), n-Bu4NBr
(210 mg, 0.651 mmol, 1.01 equiv.), and 4 A molecular
,
sieves (285.6 mg) were added to a 10 mL flask and
placed under vacuum for 30 min. Glycal 7 was dis-
solved in dry DMF (3.5 mL) and added to the flask
under N2. The reaction mixture was warmed at 80°C.
The Pd(OAc)2 (37.5 mg, 0.167 mmol, 0.26 equiv.), and
Ph3P (42.5 mg, 0.162 mmol, 0.252 equiv.) were added to
the reaction mixture. After 2 h at 80°C, the reaction
mixture was filtered through Celite (CH2Cl2 wash), the
filtrate was extracted with water (3×30 mL), and the
organic layer was dried (Na2SO4) and concentrated.
The residue was purified by flash chromatography (2.5×
20 cm silica, 35% EtOAc/hexanes) to afford ketoalco-
The synthesis of the regioisomeric 1-anthracenyl b-C-
glycoside 3 proceeded uneventfully from 6 and 7 using
essentially identical reaction conditions. It this case, a
separate fluoride-promoted desilylation was unneces-
sary after the Heck coupling, as the ketone 4 was the
sole product of this reaction (86%, 0.64 mmol scale). As
it turns out, 2-bromoanthracene (10) participates only
slightly less effectively than triflate 6 in the Heck cou-
pling (67%, 1.0 mmol scale).
1
hol 4 (161.8 mg, 86%) as a light yellow oil: H NMR
(400 MHz, CDCl3) l 8.60 (s, 1H), 8.50 (s, 1H), 8.03 (m,
3H), 7.75 (d, J=6.9 Hz, 1H), 7.51 (m, 3H), 6.08 (dd,
J=11.1, 5.8 Hz, 1H), 4.28 (t, J=3.5 Hz, 1H), 4.09 (m,
2H), 3.22 (dd, J=18.1, 5.8 Hz, 1H), 2.79 (dd, J=18.1,
11.1 Hz, 1H), 2.06 (dd, J=7.0, 6.1, 1H); 13C NMR (100
MHz, CDCl3) l 214.0, 135.4, 132.1, 132.0, 131.6, 129.5,
129.0, 128.6, 128.1, 127.6, 126.1, 126.0, 124.9, 122.5,
122.1, 82.5, 75.6, 61.8, 44.9; IR (neat) wmax 3448, 3048,
2919, 2866, 1756, 1452, 1387, 1308, 1164, 1105, 1046,
876, 732, 691, 468 cm−1; HRMS (ES), m/z 315.0997
(calcd for C19H16O3+Na: 315.0992).
4. Experimental
4.1. 1-Hydroxyanthracene (14)
1-Aminoanthracene (13) (1.01 g, 5.23 mmol) and etha-
nol (9.5 mL) were warmed in a 25 mL flask to effect
dissolution. Slow addition of water (19 mL) formed a
suspension. After addition of a saturated aqueous
NaHSO3 solution (28 mL), the reaction mixture was
warmed at reflux for 24 h. While still hot, aqueous
KOH (6 M, 25 mL) was added to the clear orange
mixture and the reaction was stirred for an additional 2
h. Concentrated aqueous HCl (27.5 mL) was added
dropwise until bubbling ceased; the reaction mixture
was stirred for 30 min, and was cooled and filtered,
affording a yellowish residue that was dissolved in ether
(100 mL) and filtered. The filtrate was concentrated to
give 1-hydroxyanthracene (14) (820.2 mg, 81%) as a
yellow–gray solid that was sufficiently pure to be used
without further purification: 1H NMR (400 MHz,
CDCl3) l 8.78 (s, 1H), 8.41 (s, 1H), 8.06 (m, 1H), 8.00
(m, 1H), 7.63 (d, J=8.6 Hz, 1H), 7.48 (m, 2H), 7.31
(dd, J=8.6, 7.2 Hz, 1H), 6.78 (d, J=7.1 Hz, 1H), 5.34
(s, 1H); 13C NMR (100 MHz, acetone-d6) l 154.4,
134.4, 133.3, 132.3, 129.9, 129.2, 127.1, 126.8, 126.8,
126.3, 122.3, 120.6, 107.0, 106.9; HRMS (ES), m/z
194.0713 (calcd for C14H10O: 194.0726).
4.4. 1%-Anthracen-1-yl-2%-deoxy-C-riboside (3)
Ketoalcohol 4 (32.4 mg, 0.11 mmol) and glacial acetic
acid (20 mL, 0.373 mmol, 3.37 equiv.) were warmed in
THF (2 mL) to effect dissolution. Me4NBH(OAc)3
(206.1 mg, 0.783 mmol, 7.1 equiv.) was added to this
mixture at 24°C. After stirring for 3 h at this tempera-
ture, saturated aqueous NH4OH (0.8 mL) was added
followed by an aqueous sodium potassium tartrate
solution (1M, 3 mL). After stirring for 40 min, the
organic layer was separated and the aqueous layer was
extracted with CH2Cl2. The combined extracts were
dried (Na2SO4) and concentrated. The residue was
purified by flash chromatography (1×12 cm silica,
EtOAc) to afford the diol 3 (27.9 mg, 86%) as a
1
light-yellow solid: H NMR (400 MHz, CDCl3) l 8.66
(s, 1H), 8.47 (s, 1H), 8.04 (m, 1H), 8.00 (m, 1H), 7.97
(d, J=8.4 Hz, 1H), 7.65 (d, J=7.0 Hz, 1H), 7.50 (m,
2H), 7.46 (dd, J=8.4, 7.0 Hz, 1H), 6.06 (dd, J=10.0,
5.8 Hz, 1H), 4.58 (m, 1H), 4.22 (q, J=4.0, 1H), 3.97
(m, 1H), 3.89 (m, 1H), 2.66 (ddd, J=13.2, 5.8, 2.3 Hz,
1H), 2.26 (ddd, J=13.1, 9.8, 6.5 Hz, 1H), 1.98 (br d,
1H), 1.90 (br t, 1H); 13C NMR (100 MHz, acetone-d6)
l 140.0, 133.4, 132.9, 132.6, 130.5, 129.8, 129.1, 129.0,
128.1, 126.8, 126.7, 126.3, 123.6, 122.9, 89.1, 78.2, 74.4,
64.3, 44.4; IR (neat) wmax 3376, 2919, 2853, 1455, 1375,
1302, 1260, 1091, 1062, 871, 732, 467 cm-1; HRMS
(ES), m/z 317.1141 (calcd for C19H18O3+Na: 317.1148).
4.2. 1-Hydroxyanthracene trifluoromethanesulfonate (6)
1H NMR (400 MHz, CDCl3) l 8.65 (s, 1H), 8.51 (s,
1H), 8.11 (m, 1H), 8.04 (m, 2H), 7.57 (m, 2H), 7.46 (m,
2H); 13C NMR (100 MHz, CDCl3) l 146.1, 132.7,
132.6, 132.5, 129.2, 128.9, 128.3, 127.2, 126.9 (2C),
124.9, 124.0, 120.2, 119.1 (q, J=320.6 Hz), 117.0; IR
(neat) wmax 1420, 1211, 1139, 1124, 997, 887, 824, 725,
596, 469 cm-1; HRMS (EI), m/z 326.0199 (calcd for
C15H9O3SF3: 326.0219).
4.5. 2-Bromoanthraquinone (9)
Cupric bromide (55.5 g, 0.249 mol, 2 equiv.) was dis-
solved in CH3CN (300 mL) in a 2 L flask. tert-Butyl

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R. S. Coleman, M. A. Mortensen / Tetrahedron Letters 44 (2003) 1215–1219
nitrite (30 mL) was added to the reaction mixture with
stirring. 2-Aminoanthraquinone (8) (24.03 g, 124.4
mmol) was dissolved in THF (400 mL) and placed in an
addition funnel affixed to the reaction flask. The
anthraquinone solution was added at 25°C over a 20
min period, and the reaction mixture was stirred for 20
h. The reaction mixture was concentrated and the solid
residue was triturated with water. This slurry was
filtered and the solid was washed with H2O. The solid
was washed with CH2Cl2 through the filter paper and
the organic filtrate was concentrated. This trituration
process was repeated. The organic filtrate was extracted
with H2O and the organic layer was concentrated.
Although this procedure provided reasonably pure
material (26.9 g, 75%), it was further purified from
polar material by flash chromatography (8×20 cm sil-
ica, 15% EtOAc/hexanes) to afford 2-bromoanthra-
butyl borate (20 mL, 74.1 mmol, 3.11 equiv.) was
added. As the mixture warmed to 0°C, it turned a light
yellow color. At 0°C, a saturated aqueous (NH4)2SO4
solution (50 mL) was added and the mixture was stirred
for 15 min. The organic layer was separated and con-
centrated to provide a yellow residue, which was dis-
solved in methanol (200 mL) and water (50 mL).
Hydrogen peroxide (20 mL, 30% aqueous solution) was
added to this mixture at 0°C with stirring. After 3 h, a
saturated aqueous (NH4)2SO4 solution (100 mL) was
added and the mixture was extracted with CH2Cl2. The
organic layer was concentrated and the residue was
purified by flash chromatography (4×15 cm silica, 15%
CH2Cl2/hexanes then 25% EtOAc/hexanes) to afford
2-hydroxyanthracene (11) (2.364 g, 51%) as a yellow
1
solid: H NMR (400 MHz, acetone-d6) l 8.77 (br s,
1H), 8.43 (s, 1H), 8.25 (s, 1H), 7.97 (m, 3H), 7.43 (dt,
J=8.2, 1.4 Hz, 1H), 7.38 (dt, J=8.2, 1.2 Hz, 1H), 7.31
(d, J=2.2 Hz, 1H), 7.21 (dd, J=9.1, 2.4 Hz, 1H); 13C
NMR (100 MHz, acetone-d6) l 155.6, 134.1, 133.1,
130.9, 130.8, 129.0, 128.8, 128.2, 127.0, 126.2, 124.9,
124.0, 121.0, 107.6.
1
quinone 9 (24.21g, 68%) as a yellow solid: H NMR
(400 MHz, CDCl3) l 8.45 (d, J=2.0 Hz, 1H), 8.33 (m,
2H), 8.19 (d, J=8.3 Hz, 1H), 7.94 (dd, J=8.3, 2.0 Hz,
1H), 7.84 (m, 2H); HRMS (EI) m/z 285.9615 (calcd for
C14H7O2Br: 285.9624).
4.6. 2-Bromoanthracene (10)
4.8. 2-Hydroxyanthracene trifluoromethanesulfonate
(12)
2-Bromoanthraquinone (9) (24.21 g, 84.3 mmol) and
isopropanol (300 mL) were added to a 500 mL flask at
25°C and stirred to create a suspension. The reaction
mixture was treated with NaBH4 (13.64 g, 360 mmol,
4.3 equiv.) and was stirred, as the yellow suspension
turned brown and then green. After 15 h at 25°C, the
suspension was poured onto an ice-water mixture and
filtered to give a light yellow brown solid that was used
without purification. The solid was placed in a 1 L
flask, treated with aqueous HCl (3 M, 500 mL), and
heated at 75°C for 8 h. The suspension was cooled and
filtered (H2O wash) to give a brownish-yellow solid that
was used without further purification. The solid was
placed in a 500 mL flask with and dissolved in iso-
propanol (300 mL). The reaction mixture was treated
with NaBH4 (19.05 g, 503.6 mmol, 6 equiv.) at 25°C
and the mixture was warmed at reflux for 20 h.
Aqueous 3 M HCl was added until bubbling ceased and
the mixture was filtered to provide an off-yellow residue
that was washed through the filter paper with CH2Cl2.
The filtrate was concentrated to provide a yellowish
solid that was purified by flash chromatography (8×15
cm silica, 10% CH2Cl2/hexane) to afford 2-bromoan-
thracene (10) (11.7 g, 54%) as a yellow solid that was
contaminated with 20 mol% anthracene. Spectral data
for 10: 1H NMR (400 MHz, CDCl3) l 8.44 (s, 1H), 8.34
(s, 1H), 8.19 (d, J=1.0, 1H), 8.01 (m, 2H), 7.89 (d,
J=9.2 Hz, 1H), 7.51 (m, 3H); HRMS (EI) m/z
255.9861 (calcd for C14H9Br 255.9882).
1H NMR (400 MHz, CDCl3) l 8.47 (s, 1H), 8.45 (s,
1H), 8.08 (d, J=9.3 Hz, 1H), 8.03 (m, 2H), 7.91 (d,
J=2.3 Hz, 1H), 7.55 (m, 2H), 7.36 (dd, J=9.3, 2.4 Hz,
1H); 13C NMR (100 MHz, CDCl3) l 146.9, 132.6,
132.5, 131.5, 130.8, 130.2, 128.5, 128.2, 127.2, 127.1,
126.7, 126.5, 119.7, 119.3, 119.1 (q, J=320.8 Hz); IR
(KBr) wmax 1620, 1437, 1420, 1248, 1208, 1126, 956, 897,
808, 744, 597, 503, 468 cm−1; HRMS (EI), m/z 326.0199
(calcd for C15H9O3SF3: 326.0219).
4.8.1. 1%-Anthracen-2-yl-3%-keto-2%-deoxy-C-riboside (15).
Triflate 12 (385.9 mg, 1.18 mmol), NaHCO3 (310.3 mg,
3.69 mmol, 3.12 equiv.), n-Bu4NBr (394.6 mg, 1.224
,
mmol, 1.04 equiv.), 3 A molecular sieves (474.8 mg),
Pd(OAc)2 (66.8 mg, 0.298 mmol, 0.252 equiv.) and
Ph3P (77.4 mg, 0.295 mmol, 0.250 equiv.) were added to
a 4 dram vial and placed under vacuum for 1 h. A
solution of glycal 7 (806.1 mg, 3.50 mmol, 2.96 equiv.)
in dry DMF (4 mL) and added to the vial under N2,
and the vial was warmed at 60°C. After 40 min, addi-
tional Pd(OAc)2 was added (14.4 mg, 0.064 mmol,
0.054 equiv.). After 2 h at 60°C, the reaction mixture
was filtered through Celite (CH2Cl2 wash), the filtrate
was extracted with water (3×30 mL) and the organic
layer was dried (Na2SO4) and concentrated. The residue
was dissolved in dry THF (40 mL) and was treated with
HF/pyridine (1.5 mL) for 6 h at 27°C. The reaction
mixture was concentrated and the residue was purified
by flash chromatography (4×12 cm silica, 35% EtOAc/
CH2Cl2) to afford ketoalcohol 15 (268.6 mg, 78%) as a
4.7. 2-Hydroxyanthracene (11)
1
light yellow solid: H NMR (400 MHz, CDCl3) l 8.46
2-Bromoanthracene (10) (6.12 g, 23.8 mmol) was dis-
solved in dry THF (200 mL) under N2. A solution of
n-BuLi (18.0 mL, 2.27 M in hexane, 40.9 mmol, 1.7
equiv.) was added to the reaction mixture at −78°C to
afford a dark red solution upon warming to −15°C.
The reaction mixture was cooled to −78°C and tri-n-
(s, 2 H), 8.08 (d, J=8.9 Hz, 1H), 8.05 (br s, 1H), 8.03
(m, 2H), 7.54 (dd, J=8.8, 1.7 Hz, 1H), 7.50 (m, 2H),
5.45 (dd, J=11.0, 5.8 Hz, 1H), 4.15 (t, J=3.4 Hz, 1H),
4.04 (m, 2H), 3.01 (dd, J=18.1, 5.9 Hz, 1H), 2.73 (dd,
J=18.1, 10.9 Hz, 1H), 2.08 (br s, 1H); 13C NMR (100
MHz, CDCl3) l 213.9, 136.4, 132.3, 132.2, 131.6, 131.3,

R. S. Coleman, M. A. Mortensen / Tetrahedron Letters 44 (2003) 1215–1219
1219
129.6, 128.4, 128.4, 126.8, 126.5, 125.9 (2C), 125.8,
123.4, 82.5, 78.2, 61.9, 45.3; IR (KBr) wmax 3495, 2919,
1752, 1168, 1110, 1066, 1034, 1001, 909, 894, 754, 471
cm-1; HRMS (ES), m/z 315.0995 (calcd for C19H16O3+
Na: 315.0992).
9. Brauns, E. B.; Madaras, M. L.; Coleman, R. S.; Murphy,
C. J.; Berg, M. A. Phys. Rev. Lett. 2002, 88, 158101.
10. The 1-anthracenyl 2%-deoxy-C-riboside stereoisomers are
described in a patent by Kool (CAN 134:326710), but the
coupling of anthracene to the deoxyribose was poorly
stereoselective and it relied on the use of stoichiometric
cadmium followed by an acid catalyzed anomerization.
There are no experimental details in the patent.
11. (a) Morales, R. G. E. J. Phys. Chem. 1982, 86, 2550; (b)
Ghoneim, N.; Suppan, P. Spectrochim. Acta 1995, 51A,
1043; (c) Renge, I. J. Photochem. Photobiol. A: Chem.
1992, 69, 135. For time-resolved measurements, see: (d)
Zhang, Y.; Berg, M. A. J. Chem. Phys. 2001, 115, 4231;
(e) Zhang, Y.; Jiang, J.; Berg, M. A. J. Chem. Phys.,
submitted for publication.
12. (a) Berlman, I. B. Handbook of Fluorescence Spectra of
Aromatic Molecules; Academic Press: New York, 1971;
(b) Lambert, W. R.; Felker, P. M.; Syage, J. A.; Zewail,
A. J. Chem. Phys. 1984, 81, 2195.
13. (a) Cabri, W.; Candiani, I.; DeBernardinis, S.; Fran-
calanci, F.; Penco, S. J. Org. Chem. 1991, 56, 5796; (b)
Cabri, W.; Candiani, I.; Bedeschi, A. J. Org. Chem. 1990,
55, 3654; (c) Cabri, W.; Candiani, I.; Bedeschi, A. J. Org.
Chem. 1992, 57, 3558; (d) Cabri, W.; Candiani, I. Acc.
Chem. Res. 1995, 28, 2.
4.9. 1%-Anthracen-2-yl-2%-deoxy-C-riboside (2)
Following the procedure for the synthesis of 3, ketoal-
cohol 15 (265 mg, 0.906 mmol), glacial acetic acid (200
mL, 3.73 mmol, 4.11 equiv.) and Me4NBH(OAc)3 (1.31
g, 4.98 mmol, 5.49 equiv.) afforded 3 (197 mg, 74%) as
a light-yellow solid: 1H NMR (400 MHz, CDCl3) l 8.42
(s, 2H), 8.02 (m, 3H), 7.99 (d, J=10.4 Hz, 1H), 7.48 (m,
2H), 7.44 (dd, J=8.85, 1.35 Hz, 1H), 5.40 (dd, J=10.2,
5.7 Hz, 1H), 4.54 (m, 1H), 4.12 (q, J=4.0 Hz, 1H), 3.91
(m, 1H), 3.84 (m, 1H), 2.39 (ddd, J=13.4, 5.8, 1.9 Hz,
1H), 2.22 (ddd, J=13.4, 10.2, 6.4 Hz, 1H), 1.94 (br t,
1H), 1.88 (br d, 1H); 13C NMR (100 MHz, acetone-d6)
l 140.9, 133.0, 132.7, 132.6, 132.4, 129.1, 129.1, 129.0,
127.0, 126.9, 126.4, 126.2, 125.5, 125.2, 89.4, 81.0, 74.3,
64.2, 44.9; IR (KBr) wmax 3366, 2925, 1738, 1673, 1459,
1436, 1309, 1085, 1044, 894, 741, 474 cm−1; HRMS
(ES), m/z 317.1169 (calcd for C19H18O3+Na: 317.1148).
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Acknowledgements
This work was supported by a grant from the National
Institutes of Health (R01 GM61292).
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