6188 J . Org. Chem., Vol. 66, No. 18, 2001
Notes
of their spectral (1H, 13C, and [R]D) data with those reported in
the literature, when possible.
Hz), 0.97 (d, 1H, J ) 6.7 Hz). 13C NMR (CD3CN, 50.3 MHz): δ
170.49, 154.14, 135.53, 132.77, 129.77, 129.65, 129.54, 128.91,
127.32, 80.01, 56.32, 14.98. GC-MS m/z: 281 (M+, 2%), 237 (M+
Red u ction of Tetr a eth yl Eth ylen etetr a ca r boxyla te, 2.
The electrolysis was carried out at a constant potential of -1.2
V vs SCE in a divided cell (cathode, Hg; anode, Pt) at room
temperature on a solution of MeCN-0.1 mol dm-3 TEAP (30
mL) containing tetraethyl ethylenetetracarboxylate (0.5 mmol)
and (R)-(-)-4-phenyl-2-oxazolidinone (0.5 mmol) in which N2 was
continuously bubbling. After the consumption of 1.0 F mol-1 of
PB, the current was switched off and benzoic anhydride (0.5
mmol) was added to the cathodic solution, which was stirred
overnight at room temperature and then analyzed.
Red u ction of Azoben zen e, 3. The electrolysis was carried
out at a constant potential of -1.5 V vs SCE in a divided cell
(cathode, Hg; anode, Pt) at room temperature on a solution of
MeCN-0.1 mol dm-3 TEAP (30 mL) containing azobenzene (0.5
mmol) and (R)-(-)-4-phenyl-2-oxazolidinone (0.5 mmol) in which
N2 was continuously bubbling. After the consumption of 1.0 F
mol-1 of PB, the current was switched off and benzoic anhydride
(0.5 mmol) was added to the cathodic solution, which was stirred
overnight at room temperature and then analyzed.
Red u ction of Dioxygen , 4. The electrolysis was carried out
at a constant potential of -1.0 V vs SCE in a divided cell
(cathode, Hg; anode, Pt) at room temperature on a solution of
MeCN-0.1 mol dm-3 TEAP (30 mL) containing (R)-(-)-4-phenyl-
2-oxazolidinone (0.5 mmol) in which O2 was continuously bub-
bling. After the consumption of 1.0 F mol-1 of PB, the current
was switched off, N2 was bubbled into the solution, and benzoic
anhydride (0.5 mmol) was added to the catholyte, which was
stirred overnight at room temperature and then analyzed.
Red u ction of Eth yl r-Br om oisobu tyr a te, 5. The electro-
lysis was carried out at a constant potential of -1.2 V vs SCE
in a divided cell (cathode, Hg; anode, Pt) at room temperature
on a solution of MeCN-0.1 mol dm-3 TEAP (30 mL) containing
ethyl R-bromoisobutyrate (0.5 mmol) and (R)-(-)-4-phenyl-2-
oxazolidinone (0.5 mmol) in which N2 was continuously bubbling.
When the current dropped to the preelectrolysis value (after the
consumption of 2.0 F mol-1 of PB), the current was switched
off, and benzoic anhydride (0.5 mmol) was added to the cathodic
solution, which was stirred overnight at room temperature and
then analyzed.
- CO2, 2%), 105 (PhCO+, 100%), 77 (53%). [R]20 +46.6 (c 0.88,
D
AcOEt).
(4S, 5R)-3-Ben zoyl-4,5-d ip h en yl-2-oxa zolid in on e, 8a : mp
139-140 °C. 1H NMR (CD3CN, 200 MHz): δ 7.74-7.49 (m, 5H),
7.18-7.04 (m, 10H), 6.13 (d, AB, 1H, J AB ) 8.1 Hz, ∆ν ) 41.0
Hz), 5.92 (d, AB, 1H, J AB ) 8.1 Hz, ∆ν ) 41.0 Hz). 13C NMR
(CD3CN, 50.3 MHz): δ 169.98, 154.65, 136.55, 135.26, 135.04,
133.03, 129.66, 129.23, 129.02, 128.89, 127.91, 127.48, 80.87,
64.22. GC-MS m/z: M+ absent, 299 (M+ - CO2, 6%), 105
(PhCO+, 100%), 77 (53%). [R]20 -59.6 (c 0.99, AcOEt).
D
(4R)-3-Ben zoyl-4-isop r op yl-2-oxa zolid in on e, 9a : mp 133-
1
134 °C. H NMR (CDCl3, 200 MHz): δ 7.67-7.36 (m, 5H), 4.67
(qd, 1H, J ) 8.9, 5.5, 4.6 Hz), 4.37 (dd, 1H, J ) 8.9, 8.9 Hz),
4.22 (dd, 1H, J ) 8.9, 5.5 Hz), 2.46 (d sept, 1H, J ) 7.1, 4.6 Hz),
0.97 (d, 1H, J ) 7.1 Hz), 0.95 (d, 1H, J ) 7.1 Hz). 13C NMR
(CDCl3, 50.3 MHz): δ 169.82, 153.73, 133.29, 132.30, 129.04,
127.85, 63.48, 58.63, 28.34, 17.82, 15.07. GC-MS m/z: 233 (M+,
22%), 232 (M+ - 1, 27%), 190 (1%), 105 (PhCO+, 100%), 77 (79%).
[R]20 +155.0 (c 1.00, AcOEt).
D
(4R)-3-Ben zoyl-4-ben zyl-2-oxa zolid in on e, 10a : mp 129-
130 °C. 1H NMR (CD3CN, 200 MHz): δ 7.62-7.26 (m, 10H), 4.87
(qd, 1H, J ) 9.0, 7.7, 4.7, 3.8 Hz), 4.38 (dd, 1H, J ) 9.0, 9.0 Hz),
4.25 (dd, 1H, J ) 9.0, 4.7 Hz), 3.25 (dd, 1H, J ) 13.6, 3.8 Hz),
3.09 (dd, 1H, J ) 13.6, 7.7 Hz). 13C NMR (CD3CN, 50.3 MHz):
δ 174.87, 158.71, 141.11, 139.59, 136.92, 134.94, 133.94, 133.83,
133.02, 132.33, 71.93, 60.66, 42.31. GC-MS m/z: 281 (M+, 6%),
190 (2%), 105 (PhCO+, 100%), 77 (48%). [R]20 -75.9 (c 0.94,
D
AcOEt).
(3a R-cis)-3-Ben zoyl-3,3a ,8,8a -tetr a h yd r o-2H-in d en o[1,2-
d ]-oxa zol-2-on e, 11a : mp 216-217 °C. 1H NMR (CDCl3, 200
MHz): δ 7.64-7.18 (m, 10H), 6.01 (d, 1H, J ) 6.8 Hz), 5.45 (app
td, 1H, J ) 6.8, 1.3 Hz), 3.42 (dd, 1H, J ) 17.8, 6.0 Hz), 3.23
(app d, 1H, J ) 17.8 Hz). 13C NMR (CDCl3, 50.3 MHz): δ 170.58,
153.50, 141.62, 140.88, 135.30, 132.47, 130.69, 129.61, 128.87,
128.66, 127.97, 126.44, 79.78, 64.96, 38.66. GC-MS m/z: M+
absent, 235 (M+ - CO2, 8%), 105 (PhCO+, 100%), 77 (63%). [R]20
-173.4 (c 0.94, AcOEt).
D
(4R)-3-Bu ta n oyl-4-p h en yl-2-oxa zolid in on e, 6c: 1H NMR
(CDCl3, 200 MHz): δ 7.40-7.24 (m, 5H), 5.39 (dd, 1H, J ) 8.7,
3.6 Hz), 4.78 (dd, 1H, J ) 8.7, 8.7 Hz), 4.22 (dd, 1H, J ) 8.7, 3.6
Hz), 2.88 (t, 2H, J ) 7.4 Hz), 1.61 (q, 2H, J ) 7.4 Hz), 0.89 (t,
3H, J ) 7.4 Hz). 13C NMR (CDCl3, 50.3 MHz): δ 172.59, 153.70,
139.23, 129.10, 128.58, 125.83, 69.89, 57.51, 37.32, 17.58, 13.48.
GC-MS m/z: 233 (M+, 1%), 189 (M+ - CO2, 5%), 162 (9%), 71
Isola ted P r od u cts. (4R)-3-Acetyl-4-phenyl-2-oxazolidinone
(6b),16 (4R)-3-(2-(E)-butenoyl)-4-phenyl-2-oxazolidinone (6d ),17
(4R)-3-(3-phenyl-2-(E)-propenoyl)-4-phenyl-2-oxazolidinone (6e),18
(4R)-4-phenyl-3-propionyl-2-oxazolidinone (6g),4 (4R,5S)-4-me-
thil-5-phenyl-3-propionyl-2-oxazolidinone (7b),4 and (4S)-4-ben-
zyl-3-propionyl-2-oxazolidinone (10b)4 gave spectral data in
accordance with that reported in the literature.
(57%), 43 (100%). [R]20 -77.8 (c 0.84, AcOEt).
(4R)-3-Ben zoyl-4-p h en yl-2-oxa zolid in on e, 6a : mp 187-
188 °C. 1H NMR (CD3CN, 200 MHz): δ 7.71-7.33 (m, 10H), 5.60
(dd, 1H, J ) 8.4, 7.6 Hz), 4.78 (dd, 1H, J ) 9.1, 8.4 Hz), 4.22
D
(4R)-3-(3-P h en ylpr opan oyl)-4-ph en yl-2-oxazolidin on e, 6f:
mp 126-127 °C. 1H NMR (CDCl3, 200 MHz): δ 7.37-7.16 (m,
10H), 5.39 (dd, 1H, J ) 8.9, 3.4 Hz), 4.64 (dd, 1H, J ) 8.9, 8.9
Hz), 4.24 (dd, 1H, J ) 8.9, 3.4 Hz), 3.26 (t, 2H, J ) 7.6 Hz), 2.92
(t, 2H, J ) 7.6 Hz). 13C NMR (CDCl3, 50.3 MHz): δ 171.85,
153.65, 140.36, 139.03, 129.16, 128.66, 128.47, 128.40, 126.17,
125.86, 69.97, 57.56, 37.07, 30.14. GC-MS m/z: 295 (M+, 4%),
251 (M+ - CO2, 2%), 104 (100%), 91 (52%), 77 (29%). [R]20D -67.4
(c 0.96, AcOEt).
(dd, 1H, J ) 9.1, 7.6 Hz). 13C NMR (CD3CN, 50.3 MHz):
δ
170.32, 154.92, 139.74, 135.04, 133.18, 130.03, 129.88, 129.53,
128.97, 127.48, 71.08, 59.72. GC-MS m/z: M+ absent, 223 (M+
- CO2, 8%), 105 (PhCO+, 100%), 77 (68%). [R]20 -75.9 (c 0.94,
D
AcOEt).
(4R, 5S)-3-Ben zoyl-4-m eth yl-5-p h en yl-2-oxa zolid in on e,
1
7a : mp 128-129 °C. H NMR (CD3CN, 200 MHz): δ 7.68-7.40
(m, 10H), 5.86 (d, 1H, J ) 7.6 Hz), 4.92 (app quint, 1H, J ) 6.7
Ack n ow led gm en t. The authors thank Mr. M. Di
Pilato for his contribution to the experimental part of
this work. This work was supported by research grants
from MURST (Cofin 2000) and CNR, Roma, Italy.
(16) Romines, K. R.; Lovasz, K. D.; Mizsak, S. A.; Morris, J . K.; Seest,
E. P.; Han, F.; Tulinsky, J .; J udge, T. M.; Gammill, R. B. J . Org. Chem.
1999, 64, 1733-1737.
(17) Martinelli, M. J . J . Org. Chem. 1990, 55, 5065-5073.
(18) Nicola´s, E.; Russell, K. C.; Hruby, V. J . J . Org. Chem. 1993,
58, 766-770.
J O010038+