Synthesis of D-glucosamine-modified benzo[d][1,2]selenazol-3-(2H)-one derivatives

Article abstract of DOI:10.1080/00397910903434562

A new class of organoselenium-saccharide derivatives, 2-amino-2-deoxy - D-glucose-modified benzo[d][1,2]selenazol-3-(2H)-one derivatives, has been synthesized via the cyclization reaction of 2-(chloroseleno)benzoyl chloride and O-protected D-glucosamine derivatives. An efficient synthetic method for the preparation of this type of compounds was developed. It has been found that acetone can react with the chloroseleno group under basic conditions, and organoselenium-saccharide derivatives with free hydroxy groups were obtained only when the OH-1 group of the saccharide was protected. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910903434562

Synthetic Communications1, 40: 3438–3446, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903434562
SYNTHESIS OF D-GLUCOSAMINE-MODIFIED
BENZO[d][1,2]SELENAZOL-3-(2H)-ONE DERIVATIVES
Zhongwei Zhang, Sumei Ren, Shengbiao Wan, Wei Li, and
Tao Jiang
School of Medicine and Pharmacy, Key Laboratory of Marine Drugs,
Ministry of Education, Ocean University of China, Qingdao, China
A new class of organoselenium-saccharide derivatives, 2-amino-2-deoxy-b-D-glucose-
modified benzo[d][1,2]selenazol-3-(2H)-one derivatives, has been synthesized via the
cyclization reaction of 2-(chloroseleno)benzoyl chloride and O-protected D-glucosamine
derivatives. An efficient synthetic method for the preparation of this type of compounds
was developed. It has been found that acetone can react with the chloroseleno group under
basic conditions, and organoselenium-saccharide derivatives with free hydroxy groups were
obtained only when the OH-1 group of the saccharide was protected.
Keywords: Benzoisoselenazolone; organoselenium-saccharide derivatives; reaction mechanism
INTRODUCTION
In the past few decades, organoselenium compounds have attracted consider-
able attention because of their beneficial biological effects and extensive uses in
organic synthesis.[1–4] Among them, benzoisoselenazol-3-(2H)-ones, particularly
ebselen (1a), are extensively studied as biological response modifiers for their inter-
esting therapeutic properties such as anti-inflammatory activities.[5–7] In addition,
selenazofurin (1b), a selenium-containing glycoside, has been shown to exhibit both
antiviral and antitumor activities.[8] We reasoned that other glycoside-containing
derivatives of benzoisoselenazol-3-(2H)-ones, such as compound 1c (Fig. 1), may
also have interesting biological properties.
For example, ebselen (1a) possesses poor solubility, which results in its low bio-
availability and the difficulty of developing formulations for clinical use. However,
solubility can be improved when they are modified with a sugar moiety. Monosacchar-
ides have long been known as biologically relevant scaffolds. Some of the advantages
of using saccharides are their high density of functional groups, availability as single
enantiomers, and multiple sites for attachment of recognition groups.[9,10]
2-Acetamido-2-deoxy-D-glucose is one of the most important monosaccharides used
Received April 30, 2009.
Address correspondence to Tao Jiang, School of Medicine and Pharmacy, Key Laboratory of
Marine Drugs, Ministry of Education, Ocean University of China, Qingdao 266003, China. E-mail:
jiangtao@ouc.edu.cn
3438

D-GLUCOSAMINE-MODIFIED SELENAZOLONE DERIVATIVES
3439
Figure 1. Structures of some benzoisoselenazol-3-(2H)-one derivatives.
in the glycosylation of human proteins. We intended to prepare benzoisoselenazol-
3-(2H)-one derivatives of D-glucosamine.
Although a number of research reports on the preparation of organoselenium-
saccharide derivatives have been reported,[11–13] there is no ebselen-saccharide
derivatives with free hydroxy groups because of the chemical activity of the Se-N
bond and hemiacetal in sugar moiety. Thus, efficient and facile methods for the
preparation of these types of compounds are still highly needed. As part of an
ongoing investigation on selenium-containing compounds, we were interested in
the preparation of organoselenium-saccharide derivatives related to compound 1c.
We herein report the synthesis of different saccharide-modified derivatives of
benzoisoselenazol-3-(2H)-ones.
RESULTS AND DISCUSSION
The 2-(chloroseleno)benzoyl chloride, 1,3,4,6-tetra-O-acetyl-2-deoxy-b-D-glu-
copyranosylamine 3a and 1,3,4,6-tetra-O-benzyl-2-deoxy-b-D-glucopyranosylamine
3b were prepared according to their respective literature procedures.[14–16] The
synthesis of compounds 4a–b (Scheme 1) were obtained by an efficient cyclization
reaction starting from 2-(chloroseleno)benzoyl chloride and the OH-protected
amino-saccharide derivative in a good yield. The simultaneous selenenylation and
acylation of the protected 2-amino-2-deoxy-D-glucose was similar to that reported
in the literature.[17]
When acetone was used as the solvent instead of CHCl3 and catalyzed by sodium
bicarbonate, compound 11 was isolated in 60% yield while no compound 4a was
obtained. Initial test using aniline-o-phthalic acid as developing reagent indicated
Scheme 1. Reagents and conditions: Et3N, chloroform, 0 ꢀC, 4 h, 62.5% for 4a, 65% for 4b.

3440
Z. ZHANG ET AL.
Scheme 2. Synthesis of compound 11 and the possible reaction mechanism.
the presence of sugar moiety and the ultraviolet detection revealed the presence of the
aromatic group. The structure of this new compound 11 was characterized by 1H and
13C NMR and MS. For the possible reaction mechanism, according to the litera-
ture,[17,18] 2-(chloroseleno)benzoyl chloride has two electrophilic centers, acyl chloride
(hard electrophilic center) and chloroseleno (soft electrophilic center). It is selenylated
preferentially when reacted with a soft nucleophilic center (the Principle of Hard and
Soft Acids and Bases) such as acetone anion in this reaction, so the reaction could be
explained as follows: the acetone anion generated under the alkaline condition could
attack the chloroseleno group preferentially and then subsequent acylation could take
place. The formation of compound 11 and the possible reaction mechanism are shown
in Scheme 2.
We also prepared a sugar-modified derivative of ebselen, namely compound 7,
according to Scheme 3. Compounds 10a and 10b, using methylene and substituted
methylene as linkers, which are different from compound 7, were obtained through
similar procedures as described in Scheme 4.
For the synthesis of compounds 10a and 10b, 2-amino-N-(tetra-acetyl-gluco-
syl) acetamide (9a) and 2-amino-N-(tetra-acetyl-glucosyl)propanamide (9b) were
synthesized first and then used as the intermediates for the subsequent coupling with
2-(chloroseleno)benzoyl chloride respectively. The targeted compounds 10a and 10b
were obtained successfully.
Scheme 3. Reagents and conditions: (a) Et3N, DCM, 0 ꢀC, 2 h; (b) H2, Pd=C, formamide, 6 h; and
(c) 2-(chloroseleno)benzoyl chloride, Et3N, 0 ꢀC, 4 h, 35%.

D-GLUCOSAMINE-MODIFIED SELENAZOLONE DERIVATIVES
3441
Scheme 4. Reagents and conditions: (a) DCC, DCM, 0 ꢀC, 2 h; (b) Pd=C, H2; and (c) 2-(chloroseleno) ben-
zoyl chloride, Et3N, 0 ꢀC, 4 h, 40% for 10a, 50% for 10b.
To remove the acetyl protecting groups, we tried various conditions, including
MeONa=MeOH, K2CO3=MeOH, and CH3COCl=MeOH with compounds 4a, 4b,
and 7. No targeted products were obtained. We suspected that the free hemiacetal
group of the sugar may react with the Se-N bond of benzoisoselenazolones. To
Scheme 5. Reagents and conditions: (a) CbzCl, NaHCO3, H2O, 0 ꢀC, 14 h, 91%; (b) Ac2O, pyridine, 16 h,
95%; (c) TMSOTf, DCM, ꢁ15 ꢀC, 5 h, 60%; (d) H2, Pd=C, 98%; and (e) 2-(chloroseleno)benzoyl chloride,
Et3N, 0 ꢀC, 4 h, 40%; (f) MeONa=MeOH, 0 ꢀC, 93%.

3442
Z. ZHANG ET AL.
confirm our hypothesis, we protected the OH-1 of the saccharide with a methyl
group and prepared the precursor compound 16 (Scheme 5). When compound 16
was treated with sodium methoxide in methanol, the targeted product 17 was
obtained successfully. This supported our proposal that OH-1 in the saccharide
needs to be protected for the preparation of this kind of organoselenium-saccharide
derivative.
CONCLUSIONS
A series of sugar-modified derivatives of benzoisoselenazol-3-(2H)-ones were
prepared. It has been found that acetone can react with the chloroseleno group
under basic conditions, and organoselenium-saccharide derivatives with free
hydroxy groups were obtained only when OH-1 of the saccharide was protected.
These prepared sugar-modified derivatives of benzoisoselenazol-3-(2H)-ones will
be screened for their potential antitumor and anti-inflammation activities.
EXPERIMENTAL
Solvents were purified in a conventional manner. Thin-layer chromatography
(TLC) was performed on precoated E. Merck silica-gel 60 F254 plates. Flash-column
chromatography was performed on silica gel (200–300 mesh, Qingdao, China). Melt-
ing points were determined on a Mitamura–Riken micro-hot stage and were not cor-
1
rected. H NMR and 13C NMR spectra were obtained on a Jeol JNM-ECP 600
spectrometer with tetramethylsilane (Me4Si) as the internal standard, and chemical
shifts were recorded in d values. Mass spectra were recorded on a Q-TOF Global
mass spectrometer.
All reagents and solvents were purchased from Sinopharm Chemical Reagent
Co., Ltd. The 2-(chloroseleno)benzoyl chloride (2), 2-(chloroseleno)benzoyl chloride,
1,3,4,6-tetra-O-acetyl-2-deoxy-b-D-glucopyranosylamine 3a, and 1,3,4,6-tetra-O-
benzyl-2-deoxy-b-D-glucopyranosylamine 3b were prepared according to their
respective literature procedures.[14–16] The intermediate compounds 9a, 9b, and 15
were prepared according to the literature.[19,20]
2-(1,3,4,6-Tetra-O-acetyl-2-deoxy-b-D-glucopyranosyl)-
1,2-benzisoselenazol-3(2H)-one (4a)[21]
Compound 3a (350 mg, 1 mmol) was dissolved in dry CHCl3(30 mL). Then
solutions of 2-(chloroseleno)benzoyl chloride (254 mg, 1 mmol) in dry CHCl3
(10 mL) and triethylamine (0.3 mL, 2 mmol) in dry CHCl3 (10 mL) were added drop-
wise to the solution at 0 ꢀC over a period of 30 min. The reaction mixture was
allowed to stir for an additional 2 h at rt. The organic layer was washed successively
with water and aqueous NaHCO3 and dried over Na2SO4, and the solvent was
removed under reduced pressure to afford a crude product. The purification of the
residue by column chromatography gave 4a (yellow power, 330 mg, 62.5%);
1
Rf ¼ 0.2 (EtOAc=n-hexane, 1:3); mp: 125–127 ꢀC; H NMR (CDCl3, 600 MHz) d:
7.41–8.07 (m, 4H, ArH), 6.16 (s, br, 1H, C01ꢁH), 4.72–5.63 (m, 3H,
C02ꢁH; C30 ꢁH; C04ꢁH), 4.35 (dd, 1H, J ¼ 4.4, 12.5 Hz, C60 ꢁH1), 4.16 (dd, 1H,

D-GLUCOSAMINE-MODIFIED SELENAZOLONE DERIVATIVES
3443
J ¼ 2.2, 12.4 Hz, C06ꢁH2), 3.99–4.01 (m, 1H, C05ꢁH), 1.90–2.12 (4 s, 12H, Ac-H);
electrospray ionization–low-resolution mass spectrometry (ESI-LRMS): found m=z
530.0 [M þ H]þ.
2-(1,3,4,6-Tetra-O-benzyl-2-deoxy-b-D-glucopyranosyl)-1,2-
benzisoselenazol-3(2H)-one (4b)
The preparation and purification procedures of 4b were similar to those of 4a,
and compound 3b (595 mg, 1 mmol) was used. Compound 4b as yellow power
(505 mg, 65%) had the following properties: Rf ¼ 0.4 (EtOAc=n-hexane, 1:2); mp:
1
127–129 ꢀC; H NMR (CDCl3, 600 MHz) d: 7.25–8.04 (m, 24H, Ar-H), 6.60 (d,
1H, J ¼ 7.1 Hz C01ꢁH), 5.29–6.21 (m, 3H, C20 ꢁH; C30 ꢁH; C04ꢁH), 4.65 (m, 1H,
C06ꢁH1), 4.48–4.52 (m, 2H, C60 ꢁH2; C50 ꢁH); 13C NMR (CDCl3, 150 MHz) d:
168.2, 166.3, 165.6, 165.2, 164.6, 138.1, 133.9, 133.5, 133.4, 133.2, 132.6, 130.3,
129.9, 129.6, 129.2, 128.7, 128.6, 128.5, 128.4, 128.4, 126.5, 126.4, 124.2, 92.7,
73.2, 72.6, 69.9, 62.8; ESI-LRMS: found m=z 778.1 [M þ H]þ; HRMS (ESI): calcd.
for C41H32NO10Seþ 778.1191; found 778.1170.
2-(3-Oxo-1,2-benzisoselenazol-2(3H)-yl)-N-(1,3,4,6-tetra-O-acetyl-
2-deoxy-b-D-glucopyranosyl)-benzamide (7)
Compound 6 (466 mg, 1 mmol) was dissolved in dry THF (20 mL). Then solu-
tions of 2-(chloroseleno)benzoyl chloride (254 mg, 1 mmol) in dry THF (10 mL) and
triethylamine (0.3 mL, 2 mmol) in dry THF (10 mL) were added dropwise at 0 ꢀC
over a period of 30 min into the solution. The reaction mixture was allowed to stir
for a further 4 h at rt. When the reaction was completed (monitored by TLC), puri-
fication of the crude residue by column chromatography gave compound 7 (226 mg,
35%) as a yellow power; Rf ¼ 0.2 (EtOAc=n-hexane, 1:2); mp: 226–229 ꢀC; 1H NMR
(CDCl3, 600 MHz) d: 7.48–8.13 (m, 8H, ArH), 6.61 (d, 1H, J ¼ 9.2 Hz, N-H), 5.83 (d,
1H, J ¼ 8.7 Hz, C01ꢁH), 5.36 (t, 1H, J ¼ 10.1 Hz, C04ꢁH), 5.23 (t, 1H, J ¼ 9.6 Hz,
C03ꢁH), 4.58 (m, 1H, C20 ꢁH), 4.31 (dd, 1H, J ¼ 4.6, 12.4 Hz, C60 ꢁH1), 4.16 (dd,
1H, J ¼ 1.9, 12.4 Hz, C06ꢁH2), 3.85–3.88 (m, 1H, C05ꢁH), 2.00–2.12 (4 s, 12H,
Ac-H); 13C NMR (CDCl3, 150 MHz) d: 171.5, 170.7, 169.6, 169.3, 166.4, 165.9,
142.5, 137.4, 133.1, 131.1, 129.5, 128.3, 127.3, 126.9, 124.8, 123.8, 92.8, 73.1, 72.8,
67.9, 61.8, 53.3, 20.9, 20.8, 20.7, 20.6; ESI-LRMS: found m=z 671.1 [M þ Na]þ;
HRMS (ESI): calcd. for C28H29N2O11Seþ 649.0937; found 649.0911.
2-(3-Oxo-1,2-benzisoselenazol-2(3H)-yl)-N-(1,3,4,6-tetrA-O-acetyl-
2-deoxy-b-D-glucopyranosyl)-acetamide (10a)
The preparation and purification procedures of 10a were similar to those of
compound 7, and compound 9a (404 mg, 1 mmol) was used. Compound 10a as yel-
low power (234 mg, 40%) had the following properties: Rf ¼ 0.3 (EtOAc=n-hexane,
1
1:1); mp: 222–225 ꢀC; H NMR (CDCl3, 600 MHz) d: 7.41–8.02 (m, 4H, ArH),
7.04 (d, 1H, J ¼ 9.1 Hz, N-H), 5.84 (d, 1H, J ¼ 8.7 Hz, C01ꢁH), 5.29 (t, 1H,
J ¼ 9.6 Hz, C04ꢁH), 5.09 (t, 1H, J ¼ 9.6 Hz, C30 ꢁH), 4.38 (s, 2H, N-CH2), 4.26 (dd,
1H, J ¼ 4.6, 12.4 Hz, C06ꢁH1), 4.18 (dd, 1H J ¼ 9.1 Hz, C02ꢁH), 4.08 (dd, 1H,

3444
Z. ZHANG ET AL.
J ¼ 2.3, 12.4 Hz, C06ꢁH2), 3.99–4.01 (m, 1H, C50 ꢁH), 1.92–2.09 (4 s, 12H, Ac-H); 13C
NMR (CDCl3, 150 MHz) d: 170.9, 170.8, 170.1, 169.7, 168.8, 168.3, 139.1, 132.9,
129.2, 126.7, 126.1, 124.3, 78.5, 73.9, 72.9, 70.5, 68.3, 61.9, 48.4, 20.9, 20.8, 20.7,
20.6; ESI-LRMS: found m=z 608.8 [M þ Na]þ; HRMS (ESI): calcd. for
C23H27N2O11Seþ 587.0780; found 587.0796.
L-2-(3-Oxo-1,2-benzisoselenazol-2(3H)-yl)-N-(1,3,4,6-tetra-O-
acetyl-2-deoxy-b-D-glucopyranosyl)-propionamide (10b)
The preparation and purification procedure of 10b was similar to that of com-
pound 7, and compound 9b (418 mg, 1 mmol) was used. Compound 10b as yellow
power (301 mg, 50%) had the following properties: Rf ¼ 0.4 (EtOAc=n-hexane,
1:1); mp: 108–110 ꢀC; 1H NMR (CDCl3, 600 MHz) d: 7.36–7.95 (m, 4H, ArH),
7.23 (d, 1H, J ¼ 9.2 Hz, N-H), 5.89 (d, 1H, J ¼ 8.7 Hz, C01ꢁH), 5.29 (t, 1H,
J ¼ 10.1 Hz, C04ꢁH), 5.16 (m, 1H, N-C-H) 5.10 (t, 1H, J ¼ 10.1 Hz, C03ꢁH), 4.26
(dd, 1H, J ¼ 4.1, 12.4 Hz, C06ꢁH1), 4.20 (m, 1H, C02ꢁH), 4.08 (dd, 1H, J ¼ 2.3,
12.4 Hz, C06ꢁH2), 3.78–3.81 (m, 1H, C50 ꢁH), 1.92–2.09 (4 s, 12H, Ac-H), 1.51 (d,
3H, J ¼ 6.84 Hz, C-CH3); 13C NMR (CDCl3, 150 MHz) d: 170.9, 170.7, 169.9,
169.8, 169.4, 167.7, 138.5, 132.4, 129.0, 126.9, 126.5, 123.7, 77.9, 73.6, 72.8, 70.2,
67.9, 61.6, 52.5, 20.7, 20.5, 20.4, 19.9, 17.1; ESI-LRMS: found m=z 601.1 [M þ H]þ;
HRMS (ESI): calcd. for C24H29N2O11Seþ 601.0937; found 601.0921.
N-(1,3,4,6-Tetra-O-acetyl-2-deoxy-b-D-glucopyranosyl)-
2-(2-oxopropylselanyl) Benzamide (11)
1,3,4,6-Tetra-O-acetyl-2-deoxy-b-D-glucopyranosylamine (347 mg, 1 mmol)
was dissolved in acetone (30 mL), and a solution of bicarbonate sodium (252 mg,
3 mmol) in 10 mL water was added. Then a solution of 2-(chloroseleno)benzoyl
chloride (254 mg, 1 mmol) in dry acetone (10 mL) was added to the mixture dropwise
at 0 ꢀC over a period of 30 min. The reaction was allowed to stir for a further 2 h at
rt. When the reaction was completed, purification of the crude residue by column
chromatography gave compound 11 (465 mg, 60%) as yellow power; Rf ¼ 0.2
1
(EtOAc=n-hexane, 1:1); mp: 221–223 ꢀC; H NMR (CDCl3, 600 MHz) d: 7.21–7.59
(m, 4H, Ar-H), 6.67 (1H, d, J ¼ 9.5 Hz, N-H), 5.82 (d, 1H, J ¼ 8.8 Hz, C01ꢁH),
5.32 (dd, 1H, J ¼ 9.5, 10.6 Hz, C04ꢁH), 5.20 (t, 1H, J ¼ 9.5 Hz, C03ꢁH), 4.52–4.56
(m, 1H, C0 ꢁH), 4.29 (dd, 1H J ¼ 4.4, 12.4 Hz, C60 ꢁH1), 4.16 (dd, 1H, J ¼ 1.9,
12.4 Hz, C062ꢁH2), 3.85–3.87 (m, 1H, C50 ꢁH), 3.65 (s, 2H, Se-CH2), 2.29 (s, 3H,
CH3), 2.05–2.14 (4s, 12H, Ac-H); 13C NMR (CDCl3, 150 MHz) d: 204.5, 171.3,
170.7, 169.6, 169.3, 168.3, 135.0, 131.7, 131.4, 131.2, 127.3, 126.7, 92.5, 72.9, 72.4,
67.8, 61.6, 53.3, 36.3, 28.4, 21.0, 20.8, 20.7, 20.6; ESI-LRMS: found m=z 588.1
[M þ H]þ; HRMS (ESI): calcd. for C24H30NO11Seþ 588.0984; found 588.0998.
2-(1-Methoxy-3,4,6-tri-O-acetyl-2-deoxy-b-D-glucopyranosyl)-
1,2-benzisoselenazol-3(2H)-one (16)
The preparation and purification procedures of 16 were similar to those of 4a,
and compound 15 (310 mg, 1 mmol) was used. Compound 16 (211 mg, 40%) as

D-GLUCOSAMINE-MODIFIED SELENAZOLONE DERIVATIVES
3445
yellow power had the following properties: Rf ¼ 0.3 (EtOAc=n-hexane, 1:1); mp:
1
92–95 ꢀC; H NMR (CDCl3, 600 MHz): d 8.05–7.45 (m, 4H, ArH), 5.72 (br s, 1H,
C01ꢁH), 5.18 (dd, 1H, J ¼ 9.2, 10.1 Hz C40 ꢁH), 5.12 (br s, 1H, C03ꢁH), 4.35
(dd, 1H, J ¼ 4.6, 11.9 Hz, C06ꢁH1), 4.24 (br s, 1H, C02ꢁH), 4.20 (dd, 1H, J ¼ 2.3,
11.9 Hz, C06ꢁH2), 3.88 (m, 1H, C05ꢁH), 3.48 (s, 3H, OMe-H), 2.11–1.90 (3 s, 9H,
Ac-H); ESI-LRMS: found m=z 502.1 [M þ H]þ.
2-(1-Methoxy-2-deoxy-b-D-glucopyranosyl)-
1,2-benzisoselenazol-3(2H)-one (17)
Freshly prepared sodium methoxide (0.63 M, 1 mL) was added to a mixture of
compound 16 (210 mg, 0.4 mmol) in methanol–chloroform (10 mL, V:V ¼ 1:1) at
0 ꢀC. After stirring at rt for 1 h, the resulting precipitate was collected and washed
with methanol to obtain compound 17 (139 mg, 93%) as a yellow powder. Rf ¼ 0.5
(EtOAc=CH3OH, 2:1) mp: 147–149 ꢀC; 1H NMR (DMSO-d6, 600 MHz) d:
8.05–7.43 (m, 4H, ArH), 5.18 (d, 1H, J ¼ 5.9 Hz, -OH), 5.17 (d, 1H, J ¼ 5.5 Hz,
-OH), 4.65 (d, 1H, J ¼ 8.3 Hz, C01ꢁH), 4.62 (t, 1H, J ¼ 5.9 Hz, -OH), 4.09 (dd, 1H,
J ¼ 8.2, 10.1 Hz, C02ꢁH), 3.75 (m, 1H, C60 ꢁH1), 3.66 (m, 1H, C03ꢁH), 3.54 (m,
C06ꢁH2), 3.34 (m, 1H, C50 ꢁH), 3.31 (s, 3H, -OMe), 3.24 (m, 1H, C04ꢁH); 13C
NMR (DMSO-d6, 150 MHz) d: 166.9, 139.5, 131.3, 128.6, 127.4, 125.7, 125.6,
101.5, 76.9, 74.5, 70.8, 60.9, 59.2, 55.9; ESI-LRMS: found m=z 376.1 [M þ H]þ;
HRMS (ESI): calcd. for C14H18NO6Seþ 376.0299; found 376.0310.
ACKNOWLEDGMENT
This work was financially supported by the Key International Cooperation
Project of the Chinese Ministry of Science and Technology (Grant No.
2008DFA31040).
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