Isolation and Stereochemistry of Optically Active Selenoximines

Article abstract of DOI:10.1246/bcsj.77.375

Asymmetric selenoximines were synthesized and their optical isomers were isolated for the first time by optical resolution using chromatography with a chiral column. The absolute configuration was determined by comparing their specific rotations and their

Full text of DOI:10.1246/bcsj.77.375

ꢀ 2004 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 77, 375–378 (2004)
375
Isolation and Stereochemistry of Optically Active Selenoximines
ꢀ
Toshio Shimizu, Kazuhiko Mitsuya, Kazunori Hirabayashi, and Nobumasa Kamigata
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University,
Minami-ohsawa, Hachioji, Tokyo 192-0397
Received September 4, 2003; E-mail: kamigata-nobumasa@c.metro-u.ac.jp
Asymmetric selenoximines were synthesized and their optical isomers were isolated for the first time by optical re-
solution using chromatography with a chiral column. The absolute configuration was determined by comparing their spe-
cific rotations and their circular dichroism spectra with those of a corresponding sulfur analogue with known absolute
configuration. No racemization of the optically active selenoximines occurred under neutral, acidic, and basic conditions,
and only decomposition was observed under aqueous acidic and basic conditions.
Recently, we have focused our interest on optically active
tricoordinated chalcogen compounds,1,2 and have reported the
isolation and stereochemistry of such optically active selenium
compounds3 as selenoxide,4,5 selenonium ylide,6 selenonium
imide,7 selenonium salt,8 and seleninic acid.9 In sulfur chemis-
try, tetracoordinated chiral compounds have also been studied.1
Sulfoximine is an example of tetracoordinated chiral com-
pounds, and its optical isomers have been isolated; their stereo-
chemistry was widely studied approximately 30 years ago.10,11
On the other hand, a corresponding optically active selenium
compound, selenoximine, has not yet been studied, and there
are few reports on the synthesis of even symmetric achiral sam-
ples.12 We have synthesized some asymmetric diaryl selenoxi-
mines, and optically resolved them into their enantiomers for
the first time. We describe herein the isolation of optically ac-
tive selenoximines, their optical properties, and their stereo-
chemistry.
(hexane/2-propanol = 70/30), two peaks corresponding to
each of the enantiomers of 1 were observed on the chromato-
gram. Using the same column, N-tosyl( p-methoxyphenyl)-
phenylselenoximine (rac-2), N-tosyl(phenyl)( p-trifluorometh-
ylphenyl)selenoximine (rac-3), and N-tosyl(2-naphthyl)phen-
ylselenoximine (rac-4) were also resolved into two peaks cor-
responding to their optical isomers, respectively.
The optical resolution of the racemic selenoximines into
their optical isomers on a preparative scale was achieved by us-
ing a larger column (10 ꢁ 250 mm) of the same type. In the
case of optical resolution of rac-1, an enantiomer obtained from
the first eluate had a positive specific rotation {½ꢀꢂD þ11:3 (c
1.22, CHCl3)}, whereas that obtained from the second eluate
had a negative specific rotation {½ꢀꢂD ꢃ12:1 (c 1.05, CHCl3)}.
Both enantiomers (þ)- and (ꢃ)-1 were found to be optically
pure by HPLC analysis. Similarly, the optical resolution of rac-
emic selenoximines rac-2–4 yielded their optically pure iso-
mers, respectively. The enantiomers obtained from the first el-
uate also showed positive specific rotations in all cases, where-
as the second-eluted enantiomers showed negative specific ro-
tations, as listed in Table 1.
Results and Discussion
Asymmetric selenoximines 1–4 were synthesized by react-
ing the corresponding selenones with N-sulfinyl-p-toluenesul-
fonamide in the presence of anhydrous magnesium sulfate in
67, 61, 52, and 33% yields, respectively, whereas 1-naphthyl-
(phenyl)- and mesityl(phenyl)selenoximines could not be ob-
tained in similar reactions, probably because of their bulkiness
(Scheme 1).
When racemic N-tosyl(phenyl)-p-tolylselenoximine (rac-1)
was subjected to an optically active column (4:6 ꢁ 250 mm)
packed with cellulose carbamate derivative/silica gel using
high-performance liquid chromatography on an analytical scale
Optically active selenoximines with positive specific rota-
tions (þ)-1, (þ)-2, and (þ)-4 showed positive Cotton effects
at 241, 252, and 242 nm, respectively, and negative Cotton ef-
fects at 226, 229, and 225 nm on their circular dichroism spec-
tra in acetonitrile, as shown in Fig. 1. In contrast, (ꢃ)-1, (ꢃ)-2,
and (ꢃ)-4 showed negative Cotton effects at 239–252 nm and
Table 1. Specific Rotations of Optically Active Sele-
noximinesa)
25
½ꢀꢂD (CHCl3)
O
Ph Se Ar
O
O
Ph Se Ar
NTs
Selenoximine
First enantiomer
Second enantiomer
TsNSO, MgSO4
1
2
3
4
þ11:3 (c 1.22)
þ16:1 (c 1.09)
þ44:6 (c 1.01)
þ67:1 (c 1.09)
ꢃ12:1 (c 1.05)
ꢃ15:5 (c 1.01)
ꢃ42:4 (c 1.12)
ꢃ65:0 (c 1.09)
C6H6, 70 °C
1: Ar = p-CH3C6H4
2: Ar = p-CH3OC6H4
3: Ar = p-CF3C6H4
4: Ar = 2-Naphthyl
a) Daicel Chiralcel OD was used as a chiral column, and hex-
ane/2-propanol (70/30 for 1, 50/50 for 2–4) was used as the
mobile phase.
Scheme 1.
Published on the web February 10, 2004; DOI 10.1246/bcsj.77.375

376 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Optically Active Selenoximines
Fig. 1. Circular dichroism spectra of optically active selenoximines in acetonitrile.
red in the presence of hydrochloric acid for 24 h, 10% of (S)-
(þ)-1 was hydrolyzed to give the corresponding selenone and
p-toluenesulfonamide as sole products. (þ)-2–4 were also hy-
drolyzed under similar conditions to yield the respective sele-
nones and p-toluenesulfonamide. Under basic conditions,
35% of (S)-(þ)-1 was consumed and the corresponding sele-
none and sulfonamide were formed after stirring for 24 h in ace-
tonitrile in the presence of a sodium hydroxide solution. (þ)-2–
4 also afforded hydrolyzed products under the same conditions.
However, no racemization was observed in the recovered sele-
noximines (þ)-1–4 under both acidic and basic conditions, dif-
fering from many optically active tricoordinated selenium com-
pounds.3 This result means that the condensation reaction of se-
lenone with p-toluenesulfonamide, formed by hydrolysis under
these conditions, to give selenoximine did not proceed, since
the reverse reaction should give racemic selenoximine.
In this study, optically active selenoximines could be isolat-
ed for the first time, and their absolute configurations were de-
termined. The stability toward the hydrolysis of selenoximines
and that toward racemization of their optical isomers were also
clarified.
NTs
S
O
H3C
(S)-(+)-5
Chart 1.
positive Cotton effects at 225–229 nm. However, (þ)-3, which
possesses a p-trifluoromethylphenyl substituent, showed a neg-
ative Cotton effect at 238 nm and a positive Cotton effect at 224
nm. To determine their absolute configuration, optically active
N-tosyl(phenyl)-p-tolylsulfoximine (S)-(þ)-5 (Chart 1), of
which the relationship between the absolute configuration and
the specific rotation had been clarified, was synthesized.13 Sul-
foximine (S)-(þ)-5 {½ꢀꢂD þ20:4 (c 0.71, CHCl3)} showed a
positive Cotton effect at 243 nm and a negative Cotton effect
at 223 nm in acetonitrile, which corresponded well with those
of the optically active selenoximines with positive specific ro-
tations (þ)-1, (þ)-2, and (þ)-4. Therefore, based on the simi-
larity of the signs of their specific rotations and their circular
dichroism spectra, the absolute configuration of selenoximines
(þ)-1, (þ)-2, and (þ)-4 was assigned to be S-form, whereas
that of (ꢃ)-1, (ꢃ)-2, and (ꢃ)-4 was R.
Experimental
Typical Procedure for Synthesis of Selenoximines. To a ben-
zene solution (5 mL) of the corresponding selenone (1.0 mmol) and
N-sulfinyl-p-toluenesulfonamide (1.2 mmol) was added anhydrous
magnesium sulfate (300 mg) under nitrogen. The solution was
ꢄ
heated at 70 C for the desired period (1: 4 h, 2: 13 h, 3: 16 h, 4:
Selenoximine (S)-(þ)-1 was stable under neutral conditions,
and neither racemization nor decomposition was observed in
acetonitrile containing water, even after 14 d. (S)-(þ)-1 was
stable even in a refluxing acetonitrile solution containing water.
Optically active selenoximines (þ)-2–4 were also stable at
room temperature under neutral conditions. However, the de-
composition of (S)-(þ)-1 occurred under both acidic and basic
conditions. When an acetonitrile solution of (S)-(þ)-1 was stir-
5 h). Magnesium sulfate was filtered off, and the filtrate was con-
centrated. The product was purified by gel-permeation chromatog-
raphy (chloroform) (1: 67%, 2: 61%, 3: 52%, 4: 33%).
ꢄ
N-Tosyl(phenyl)-p-tolylselenoximine (1): Mp 52.0–54.0 C
1
(colorless powder); H NMR (500 MHz, CDCl3) ꢁ 2.38 (s, 3H),
2.44 (s, 3H), 7.23 (d, 2H, J ¼ 8:2 Hz), 7.40 (d, 2H, J ¼ 8:3 Hz),
7.60 (t, 2H, J ¼ 8:0 Hz), 7.67 (t, 1H, J ¼ 8:0 Hz), 7.90 (d, 2H, J ¼
8:2 Hz), 7.91 (d, 2H, J ¼ 8:3 Hz), 8.02 (d, 2H, J ¼ 8:0 Hz);

T. Shimizu et al.
Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
377
13C NMR (125 MHz, CDCl3) ꢁ 21.4, 21.6, 126.5, 127.1 (dupli-
cate), 129.1, 130.4, 131.1, 134.3, 137.1, 140.7, 141.5, 142.1,
145.7; 77Se NMR (95 MHz, CDCl3) ꢁ 884; IR (KBr) ꢂmax 2924,
1598, 1447, 1300, 1144, 1088, 1059, 928 (N=Se=O), 858, 809,
745, 711, 668, 573, 550, 488, 463, 405 cmꢃ1; UV (MeCN) ꢃmax
232 (" 2:52 ꢁ 104), 262 (sh, " 2:70 ꢁ 103) nm; MS m=z 248
{Mþ(80Se)-C7H7NO3S, 41%}, 246 {Mþ(78Se)-C7H7NO3S,
21%}, 168 (100%), 107 (24%), 91 (93%), 65 (45%). Anal. Calcd
for C20H19NO3SSe: C, 55.56; H, 4.43; N, 3.24%. Found: C,
55.38; H, 4.49; N, 3.19%.
dissolved in eluent (0.5 mL), was charged to an optically active
column (Daicel Chiralcel OD: 250 ꢁ 10 mm) and eluted with hex-
ane containing 30 (for 1) and 50 (for 2–4) vol % 2-propanol at a
flow rate of 1.0 mL minꢃ1. Each ca. 8 mg of optically active sele-
noximine was collected from the first and second eluates, respec-
tively.
(S)-(þ)-N-Tosyl(phenyl)-p-tolylselenoximine {(S)-(þ)-1}:
Colorless oil; 100% ee; ½ꢀꢂD þ11:3 (c 1.22, CHCl3); CD (MeCN)
ꢃ
226 ([ꢄ] ꢃ1:44 ꢁ 104), 241 ([ꢄ] 2:43 ꢁ 104), 273 ([ꢄ]
1
7:85 ꢁ 102). H and 13C NMR were almost the same as those of
N-Tosyl( p-methoxyphenyl)phenylselenoximine (2):
Mp
the racemic one.
(R)-(ꢀ)-N-Tosyl(phenyl)-p-tolylselenoximine {(R)-(ꢀ)-1}:
Colorless oil; 100% ee; ½ꢀꢂD ꢃ12:1 (c 1.05, CHCl3); CD (MeCN)
54.0–56.0 ꢄC (colorless amorphous); 1H NMR (500 MHz, CDCl3)
ꢁ 2.37 (s, 3H), 3.86 (s, 3H), 7.06 (d, 2H, J ¼ 8:9 Hz), 7.22 (d, 2H,
J ¼ 8:2 Hz), 7.60 (t, 2H, J ¼ 8:0 Hz), 7.66 (t, 1H, J ¼ 8:0 Hz),
7.90 (d, 2H, J ¼ 8:0 Hz), 7.95 (d, 2H, J ¼ 8:9 Hz), 8.01 (d, 2H,
J ¼ 8:2 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 21.5, 55.9, 115.8,
126.5, 127.1, 129.2, 129.3, 130.4, 130.6, 134.2, 141.1, 141.5,
142.1, 164.2; 77Se NMR (95 MHz, CDCl3) ꢁ 890; IR (KBr) ꢂmax
3061, 2943, 2579, 1585, 1491, 1446, 1411, 1301, 1285, 1264,
1173, 1143, 1087, 1061, 1020, 927 (N=Se=O), 831, 815, 745,
711, 682, 573, 549, 514, 463, 380 cmꢃ1; UV (MeCN) ꢃmax 227
(" 5:01 ꢁ 104), 248 (" 4:45 ꢁ 104) nm; MS m=z 264 {Mþ(80Se)-
C7H7NO3S, 66%}, 262 {Mþ(78Se)-C7H7NO3S, 25%}, 184
(100%), 169 (25%), 155 (22%), 91 (66%), 77 (25%), 65 (27%).
Anal. Calcd for C20H19NO4SSe: C, 53.57; H, 4.27; N, 3.12%.
Found: C, 53.09; H, 4.32; N, 3.04%.
ꢃ
226 ([ꢄ] 1:70 ꢁ 104), 241 ([ꢄ] ꢃ2:38 ꢁ 104), 273 ([ꢄ]
ꢃ1:09 ꢁ 103). 1H and 13C NMR were almost the same as those
of the racemic one.
(S)-(þ)-N-Tosyl( p-methoxyphenyl)phenylselenoximine {(S)-
(þ)-2}: Colorless oil; 100% ee; ½ꢀꢂD þ16:1 (c 1.09, CHCl3); CD
1
(MeCN) ꢃ 229 ([ꢄ] ꢃ8:07 ꢁ 104), 252 ([ꢄ] 6:27 ꢁ 104). H and
13C NMR were almost the same as those of the racemic one.
(R)-(ꢀ)-N-Tosyl( p-methoxyphenyl)phenylselenoximine
{(R)-(ꢀ)-2}: Colorless oil; 100% ee; ½ꢀꢂD ꢃ15:5 (c 1.01, CHCl3);
1
CD (MeCN) ꢃ 229 ([ꢄ] 9:84 ꢁ 104), 251 ([ꢄ] ꢃ6:03 ꢁ 104). H
and 13C NMR were almost the same as those of the racemic one.
(þ)-N-Tosyl(phenyl)( p-trifluoromethylphenyl)selenoximine
{(þ)-3}: Mp 108.0–109.5 ꢄC (decomp, colorless powder); 100%
ee; ½ꢀꢂD þ44:6 (c 1.01, CHCl3); CD (MeCN) ꢃ 224 ([ꢄ]
1:04 ꢁ 104), 238 ([ꢄ] ꢃ6:76 ꢁ 103), 276 ([ꢄ] 1:43 ꢁ 103). 1H
and 13C NMR were almost the same as those of the racemic one.
(ꢀ)-N-Tosyl(phenyl)( p-trifluoromethylphenyl)selenoximine
{(ꢀ)-3}: Mp 108.0–110.0 ꢄC (decomp, colorless powder); 100%
ee; ½ꢀꢂD ꢃ42:4 (c 1.12, CHCl3); CD (MeCN) ꢃ 225 ([ꢄ]
ꢃ1:01 ꢁ 104), 239 ([ꢄ] 7:26 ꢁ 103), 277 ([ꢄ] ꢃ1:96 ꢁ 103). 1H
and 13C NMR were almost the same as those of the racemic one.
(S)-(þ)-N-Tosyl(2-naphthyl)phenylselenoximine {(S)-(þ)-
4}: Colorless oil; 100% ee; ½ꢀꢂD þ67:1 (c 1.09, CHCl3); CD
(MeCN) ꢃ 225 ([ꢄ] ꢃ5:87 ꢁ 104), 242 ([ꢄ] 1:03 ꢁ 105), 277 ([ꢄ]
N-Tosyl(phenyl)( p-trifluoromethylphenyl)selenoximine (3):
Mp 108.5–109.5 ꢄC (decomp, colorless prisms from ethyl ace-
tate–hexane); 1H NMR (500 MHz, CDCl3) ꢁ 2.38 (s, 3H), 7.24
(d, 2H, J ¼ 8:3 Hz), 7.64 (t, 2H, J ¼ 8:0 Hz), 7.72 (t, 1H, J ¼
8:0 Hz), 7.87 (d, 2H, J ¼ 8:6 Hz), 7.90 (d, 2H, J ¼ 8:3 Hz),
8.06 (d, 2H, J ¼ 8:0 Hz), 8.20 (d, 2H, J ¼ 8:6 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 21.3, 122.7 (q, J ¼ 273 Hz), 126.5, 127.2,
127.4 (q, J ¼ 7:3 Hz), 127.9, 129.2, 130.7, 134.8, 135.9 (q, J ¼
33 Hz), 139.4, 141.1, 142.5, 144.4; 77Se NMR (95 MHz, CDCl3)
ꢁ 887; IR (KBr) ꢂmax 3093, 1598, 1496, 1448, 1402, 1323, 1144,
1088, 1054, 1011, 997, 915 (N=Se=O), 839, 815, 745, 710, 692,
591, 573, 549, 498, 465, 392 cmꢃ1; UV (MeCN) ꢃmax 227 ("
2:27 ꢁ 104), 264 (sh, " 3:02 ꢁ 103) nm; MS m=z 300
{Mþ(80Se)-C7H7NO3S, 62%}, 298 {Mþ(78Se)-C7H7NO3S,
28%}, 221 (100%), 156 (22%), 91 (40%), 77 (45%), 65 (21%).
Anal. Calcd for C20H16F3NO3SSe: C, 49.08; H, 3.91; N, 2.86%.
Found: C, 49.46; H, 3.51; N, 2.91%.
1
9:16 ꢁ 104). H and 13C NMR were almost the same as those of
the racemic one.
(R)-(ꢀ)-N-Tosyl(2-naphthyl)phenylselenoximine {(R)-(ꢀ)-
4}: Colorless oil; 100% ee; ½ꢀꢂD ꢃ65:0 (c 1.09, CHCl3); CD
(MeCN) ꢃ 226 ([ꢄ] 6:61 ꢁ 104), 241 ([ꢄ] ꢃ9:90 ꢁ 104), 277 ([ꢄ]
ꢃ7:18 ꢁ 103). 1H and 13C NMR were almost the same as those
of the racemic one.
N-Tosyl(2-naphthyl)phenylselenoximine (4):
Mp 114.0–
ꢄ
116.0 C (decomp, colorless powder from ethyl acetate–hexane);
1H NMR (500 MHz, CDCl3) ꢁ 2.36 (s, 3H), 7.21 (d, 2H, J ¼ 8:3
Hz), 7.61 (t, 2H, J ¼ 8:0 Hz), 7.65–7.71 (m, 4H), 7.91–7.95 (m,
3H), 8.00 (d, 1H, J ¼ 8:0 Hz), 8.04 (d, 1H, J ¼ 8:9 Hz), 8.09 (d,
2H, J ¼ 8:3 Hz), 8.65 (s, 1H); 13C NMR (125 MHz, CDCl3) ꢁ
21.3, 121.2, 126.5, 127.2, 128.1, 128.2, 129.0, 129.1, 129.2,
129.8, 130.5, 130.9, 132.5, 134.3, 135.4, 137.0, 140.6, 141.5,
142.2; 77Se NMR (95 MHz, CDCl3) ꢁ 891; IR (KBr) ꢂmax 3058,
2366, 1597, 1446, 1300, 1143, 1087, 911 (N=Se=O), 814, 744,
710, 682, 572, 549, 475, 462 cmꢃ1; UV (MeCN) ꢃmax 237 ("
8:28 ꢁ 103), 270 (sh, " 1:70 ꢁ 103) nm; MS m=z 284
{Mþ(80Se)-C7H7NO3S, 35%}, 282 {Mþ(78Se)-C7H7NO3S,
22%}, 204 (100%), 155 (16%), 126 (19%), 115 (42%), 91
(55%), 77 (25%), 65 (18%). Anal. Calcd for C23H19NO3SSe: C,
58.97; H, 4.09; N, 2.99%. Found: C, 58.60; H, 4.13; N, 3.02%.
Optical Resolution of Racemic Selenoximines by Means of
Medium-Pressure Column Chromatography Using an Optical-
ly Active Column. Typically, the racemic selenoximine (25 mg),
(S)-(þ)-N-Tosyl(phenyl)-p-tolylsulfoximine {(S)-(þ)-5}:13
Colorless oil; 1H NMR (500 MHz, CDCl3) ꢁ 2.38 (s, 3H), 2.40
(s, 3H), 7.22 (d, 2H, J ¼ 8:0 Hz), 7.30 (d, 2H, J ¼ 8:3 Hz), 7.50
(t, 2H, J ¼ 8:3 Hz), 7.57 (t, 1H, J ¼ 8:3 Hz), 7.84 (d, 2H, J ¼
8:3 Hz), 7.87 (d, 2H, J ¼ 8:3 Hz), 7.98 (d, 2H, J ¼ 8:0 Hz);
13C NMR (125 MHz, CDCl3) ꢁ 21.4, 21.5, 126.6, 127.5, 127.7,
129.1, 129.4, 130.1, 133.5, 136.6, 140.1, 140.9, 142.6, 145.0;
100% ee; ½ꢀꢂD þ20:4 (c 0.75, CHCl3); CD (MeCN) ꢃ 223 ([ꢄ]
ꢃ9:11 ꢁ 103), 243 ([ꢄ] 1:41 ꢁ 104), 276 ([ꢄ] 1:46 ꢁ 103).
Stability of Optically Active Selenoximines. To an acetoni-
trile solution (5 mL) of optically active selenoximine (2.3 mmol)
was added water (0.5 mL), 1 M-HClaq (1 M = 1 mol dmꢃ3) (0.2
mL), or 1 M-NaOHaq (0.2 mL) and stirred at room temperature
for 24 h. No racemization was observed in all of the selenoximines
under all of the conditions. No decomposition was observed in the
acetonitrile–water solution in all of the selenoximines. However,
they were partly hydrolyzed to the corresponding selenones and
p-toluenesulfonamide under both acidic and basic conditions, as

378 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Optically Active Selenoximines
follows. Under acidic conditions: {decomposition: (þ)-1: 10%,
(þ)-2: 4%, (þ)-3: 23%, (þ)-4: 10%}. Under basic conditions: {de-
composition: (þ)-1: 35%, (þ)-2: 70%, (þ)-3: 100%, (þ)-4: 80%}.
1469. c) T. Shimizu, N. Seki, H. Taka, and N. Kamigata, J. Org.
Chem., 61, 6013 (1996). d) N. Kamigata, H. Taka, A. Matsuhisa,
H. Matsuyama, and T. Shimizu, J. Chem. Soc., Perkin Trans. 1,
1994, 2257.
8
a) T. Shimizu, T. Urakubo, P. Jin, M. Kondo, S. Kitagawa,
This work was financially supported in part by a Grant-in-
Aid for Scientific Research from the Ministry of Education,
Culture, Sports, Science and Technology.
and N. Kamigata, J. Organomet. Chem., 539, 171 (1997). b) M.
Kobayashi, K. Koyabu, T. Shimizu, K. Umemura, and H.
Matsuyama, Chem. Lett., 1986, 2117.
9
a) T. Shimizu, Y. Nakashima, I. Watanabe, K. Hirabayashi,
and N. Kamigata, J. Chem. Soc., Perkin Trans. 1, 2002, 2151. b) T.
Shimizu, I. Watanabe, and N. Kamigata, Angew. Chem., Int. Ed.,
40, 2460 (2001).
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