Significantly fast synthesis of S-glycosyl N-substituted dithiocarbamate and S-glycosyl S-substituted trithiocarbonate derivatives under solvent-free conditions

Article abstract of DOI:10.1055/s-0032-1317521

A series of S-glycosyl N-substituted dithiocarbamate and S-glycosyl S-substituted trithiocarbonate derivatives have been synthesized under solvent-free conditions. Three-component reaction of glycosyl bromides with carbon disulfide and thiols or amines in the presence or absence of triethylamine furnished excellent yields of the target compounds in a short reaction time. Copyright

Full text of DOI:10.1055/s-0032-1317521

LETTER
▌2789
lSetitegr nificantly Fast Synthesis of S-Glycosyl N-Substituted Dithiocarbamate and
S-Glycosyl S′-Substituted Trithiocarbonate Derivatives under Solvent-Free
Conditions
Dithiocarbamate and Trithiocarbonate Derivatives
Manas Jana, Anup Kumar Misra*
Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India
Fax +91(33)23553886; E-mail: akmisra69@gmail.com
Received: 17.08.2012; Accepted after revision: 08.10.2012
vent, and preferably, in the absence of a catalyst, could
Abstract: A series of S-glycosyl N-substituted dithiocarbamate and
furnish the desired compounds. Herein, we report our
S-glycosyl S′-substituted trithiocarbonate derivatives have been
findings on the solvent-free synthesis of S-glycosyl N-
substituted dithiocarbamate and S-glycosyl S′-substituted
synthesized under solvent-free conditions. Three-component reac-
tion of glycosyl bromides with carbon disulfide and thiols or amines
in the presence or absence of triethylamine furnished excellent trithiocarbonate derivatives by such three-component re-
yields of the target compounds in a short reaction time.
actions (Scheme 1 and Scheme 2).
Key words: dithiocarbamate, trithiocarbonate, carbohydrates, car-
bon disulfide, three-component reaction, solvent-free
R1R2NH (1.2 equiv)
CS2 (1.5 equiv)
S
R1
R2
O
O
AcO
AcO
S
N
r.t., 30–45 min
80–92%
Br
(1.0 equiv)
R
R
1 = alkyl
2 = H; alkyl
Dithiocarbamate derivatives are an important class of
molecules having wide applications as pharmaceuticals1
and agrochemicals.2 They have been used as intermedi-
ates in the synthesis of different classes of organic mole-
cules.3 Several reports can be found in the literature for the
synthesis of dithiocarbamate derivatives in organic4–6 and
aqueous media7 as well as under solvent-free conditions.8
Similar to dithiocarbamate derivatives, organic trithiocar-
bonate derivatives have significant applications in organic
synthesis,9 pharmaceutics,10 and materials science.11
Numbers of reports are also available for the synthesis of
trithiocarbonate derivatives in organic solvents.12–15 How-
ever, most of the reported methods for the synthesis of
these compounds suffer from serious shortcomings, such
as use of toxic and sensitive reagents, use of organic sol-
vents, extended reaction times, tedious workup, or unsat-
isfactory yield.
Scheme 1 Solvent-free and catalyst-free three-component reaction
of glycosyl halide, carbon disulfide, and amine
ArSH (1.2 equiv)
CS2 (1.5 equiv)
S
O
O
AcO
AcO
S
SAr
Et3N (0.1 eqvui)
r.t., 2–5 min
85–95%
Br
(1.0 equiv)
Ar = aryl
Scheme 2 Triethylamine-catalyzed solvent-free three-component
reaction of glycosyl halide, carbon disulfide, and thiol
Initially, stirring equimolar mixture of piperidine, carbon
disulfide, and 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl
bromide (1) at room temperature resulted in the exclusive
formation of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl
1-piperidine carbodithioate (4) in 75% yield as a white
solid in 30 minutes. After a series of experimentation it
was observed that yield of compound 4 can be raised to
90% under optimized reaction conditions.18 A scaled-up
preparation of compound 4 was also carried out on a 5.0
gram scale, and the yield was comparable to the smaller
scale (0.5 g) reaction. Previously, compound 4 has been
prepared in 82% yield by the treatment of compound 1
with piperidine and carbon disulfide in the presence of so-
dium hydride in DMF at 0 °C to room temperature for one
hour.16g In order to generalize the reaction conditions, a
series of primary and secondary amines was allowed to re-
act with a mixture of carbon disulfide and various glyco-
pyranosyl bromides (mono- and disaccharides) at room
temperature to give the corresponding S-glycosyl N-sub-
stituted dithiocarbamate derivatives (Table 1). Excellent
yields of solid products were obtained in all reactions. Pri-
mary amines were also effective to furnish S-glycosyl N-
substituted dithiocarbamate products (Table 1, entries 5
and 6).
We required S-glycosyl N-substituted dithiocarbamate
and S-glycosyl S′-substituted trithiocarbonate derivatives
as synthetic precursors. Syntheses of S-glycosyl N-substi-
tuted dithiocarbamate derivatives16 have been reported by
the reaction of glycosyl halide derivatives with amine car-
bodithioate salts in organic solvents or under phase-trans-
fer conditions or reaction of glycal derivatives16h with in
situ generated amine carbodithioate salts. However, re-
ports on the synthesis of S-glycosyl S′-substituted trithio-
carbonate derivatives are limited.17 Previously, S-glycosyl
N-substituted dithiocarbamate derivatives have been used
as glycosyl donors in stereoselective glycosylations for
the synthesis of oligosaccharides.16g,h We envisaged that a
multicomponent one-pot reaction of glycosyl halides, car-
bon disulfide, and amines or thiols without organic sol-
SYNLETT 2012, 23, 2789–2794
Advanced online publication: 13.11.2012
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0032-1317521; Art ID: ST-2012-D0694-L
© Georg Thieme Verlag Stuttgart · New York

2790
M. Jana, A. K. Misra
LETTER
Table 1 Solvent-Free Reaction of Glycosyl Bromides, Carbon Disulfide, and Amines at Room Temperature for the Synthesis of S-Glycosyl
N-Substituted Dithiocarbamate Derivatives
Entry
Glycosyl bromide
Amine
S-Glycosyl N-substituted dithiocarbamate
Time (min) Yield (%)a
OAc
S
OAc
O
O
AcO
AcO
AcO
AcO
30
90
S
S
S
N
N
N
1
40b
88b
AcO
NH
Br
OAc
416g
1
OAc
S
S
O
AcO
O
AcO
2
3
1
1
30
30
92
85
O
NH
OAc
5
OAc
O
AcO
AcO
HN
HN
OAc
6
7
8
OAc
S
O
AcO
AcO
S
N
4
5
1
1
1
30
25
86
82
OAc
Bn
Bn
OAc
S
O
AcO
H2N
S
N
H
AcO
OAc
OAc
S
O
AcO
AcO
O
O
O
O
H2N
N
S
H
6
7
8
25
30
30
85
92
92
OAc
9
AcO
OAc
O
AcO
AcO
OAc
O
S
N
S
AcO
AcO
NH
Br
OAc
1016g
2
2
AcO
OAc
O
S
S
O
N
N
S
S
AcO
O
NH
OAc
11
AcO
OAc
O
AcO
9
2
30
82
HN
OAc
12
Synlett 2012, 23, 2789–2794
© Georg Thieme Verlag Stuttgart · New York

LETTER
Dithiocarbamate and Trithiocarbonate Derivatives
2791
Table 1 Solvent-Free Reaction of Glycosyl Bromides, Carbon Disulfide, and Amines at Room Temperature for the Synthesis of S-Glycosyl
N-Substituted Dithiocarbamate Derivatives (continued)
Entry
Glycosyl bromide
Amine
S-Glycosyl N-substituted dithiocarbamate
Time (min) Yield (%)a
AcO
OAc
O
S
10
2
30
45
80
85
N
S
AcO
HN
OAc
13
AcO
AcO
AcO
OAc
OAc
O
OAc
O
OAc
O
O
S
S
O
AcO
O
AcO
AcO
S
N
AcO
11
12
AcO
NH
AcO
OAc
Br
3
14
AcO
OAc
O
OAc
O
AcO
O
AcO
S
AcO
N
OAc
3
45
80
HN
15
a Isolated yield.
b Scale = 5.0 g.
After successful preparation of S-glycosyl N-substituted be ineffective to catalyze the reaction, maybe due to their
dithiocarbamate derivatives, the same solvent-free reac- insolubility in the reaction medium. However, a very low
tion conditions were applied to the preparation of S-glyco- yield of product formation (ca. 15%) was observed using
syl S′-substituted trithiocarbonate derivatives. A mixture NaOH or KOH together with the formation of unwanted
of p-methylthiophenol (1.2 mmol), carbon disulfide (1.5 byproducts over a longer reaction time. The reaction con-
mmol), and compound 1 (1.0 mmol) was allowed to stir at ditions were further extended to the synthesis of a series
room temperature. Unfortunately, the reaction did not of S-glycosyl S′-substituted trithiocarbonate derivatives
proceed even after five hours at room temperature. In or- by the reaction of a series of aryl and heteroaryl thiols with
der to activate the reaction, a catalytic amount of triethyl- carbon disulfide and glycosyl halides (mono- and disac-
amine was added to the reaction mixture and, gratifyingly, charides; Table 2). Compound 16 was also prepared on a
the product, S-(2,3,4,6-tetra-O-acetyl-β-D-glucopyrano- 5.0 gram scale, and its yield was similar to that obtained
syl)-S′-(p-methylphenyl)trithio carbonate (16) was from smaller scale (0.5 g scale) synthesis. A noteworthy
formed immediately (2 min) on addition of the base. After point of the two sets of reaction conditions is the exclusive
optimization, it was observed that the addition of 0.1 formation of β-glycosidic products, with no trace of α-
equivalent of triethylamine to the three-component sol- product being detected. It is also worth stressing that the
vent-free reaction with the above-mentioned ratio of the reactions did not require any organic solvent. All products
substrates furnished 16 in excellent yield (92%).19 Use of were unambiguously characterized by their melting point,
other commonly used solid bases such as Na2CO3, NMR spectroscopic, and mass spectrometric analysis.
NaHCO3, K2CO3, NaOH, KOH, and Cs2CO3 was found to
Table 2 Triethylamine-Catalyzed Solvent-Free Reaction of Glycosyl Bromides, Carbon Disulfide, and Thiols for the Preparation of S-Glyco-
syl S′-Substituted Trithiocarbonate Derivatives
Entry
Glycosyl bromide
Thiol
S-Glycosyl S′-substituted trithiocarbonate
Time Yield
(min) (%)a
1
2
92
OAc
O
CH3
OAc
S
5b
90b
AcO
AcO
O
AcO
AcO
S
S
AcO
Br
OAc
1
SH
16
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2789–2794

2792
M. Jana, A. K. Misra
LETTER
Table 2 Triethylamine-Catalyzed Solvent-Free Reaction of Glycosyl Bromides, Carbon Disulfide, and Thiols for the Preparation of S-Glyco-
syl S′-Substituted Trithiocarbonate Derivatives (continued)
Entry
Glycosyl bromide
Thiol
S-Glycosyl S′-substituted trithiocarbonate
Time Yield
(min) (%)a
OAc
S
O
O
AcO
AcO
S
S
2
1
5
90
OMe
OAc
SH
SH
17
OAc
S
O
AcO
S
S
AcO
3
4
5
6
1
1
1
1
2
5
2
2
95
92
86
88
OAc
18
OAc
S
O
AcO
S
S
AcO
OAc
SH
19
OAc
S
S
O
AcO
N
N
S
S
S
S
AcO
N
N
OAc
N
SH
20
OAc
O
AcO
AcO
N
OAc
SH
21
AcO
OAc
CH3
AcO
AcO
OAc
O
S
O
S
S
AcO
7
8
2
95
85
AcO
Br
OAc
SH
2
22
AcO
OAc
O
Ph
N
S
Ph
S
AcO
S
N
N
HS
2
10
OAc
N
N
N
N
N
23
AcO
OAc
O
AcO
AcO
OAc
O
OAc
O
OAc
O
S
O
AcO
AcO
O
AcO
AcO
9
5
2
88
S
AcO
S
S
AcO
Br
OAc
SH
3
3
24
AcO
OAc
O
OAc
O
AcO
O
AcO
10
S
AcO
S
OAc
25
a Isolated yield.
b Scale = 5.0 g.
Synlett 2012, 23, 2789–2794
© Georg Thieme Verlag Stuttgart · New York

LETTER
Dithiocarbamate and Trithiocarbonate Derivatives
2793
(9) (a) Metzner, P. Pure Appl. Chem. 1996, 68, 863. (b) Quiclet-
Sire, B.; Zard, S. Z. Top. Curr. Chem. 2006, 252, 201.
(c) Martin, D. J.; Greco, C. C. J. Org. Chem. 1968, 33, 1275.
(d) Jordis, U.; Rudolf, M. Phosphorus Sulfur Relat. Elem.
1984, 19, 279. (e) Corey, E. J.; Carey, F. A.; Winter, R. A.
E. J. Am. Chem. Soc. 1965, 87, 934. (f) Leriverend, C.;
Metzner, P.; Capperucci, A.; Degl’lnnocenti, A.
In summary, a three-component reaction of glycosyl ha-
lides, carbon disulfide, and amines or thiols has been car-
ried out under solvent-free conditions to furnish S-
glycosyl N-substituted dithiocarbamate or S-glycosyl S′-
substituted trithiocarbonate derivatives in excellent yield.
The preparation of dithiocarbamates was achieved with-
out using any catalyst, while preparation of trithiocarbon-
ate derivatives required triethylamine as the catalyst. The
advantageous features of the present methodology over
the earlier reported preparations of S-glycosyl N-substi-
tuted dithiocarbamate or S-glycosyl S′-substituted trithio-
carbonate derivatives are that it is an operationally simple,
exceptionally high-yielding, and highly stereoselective
conversion with no requirement for organic solvents. Fur-
ther utilization of these compounds in glycosylation reac-
tions is in progress in our laboratory.
Tetrahedron 1997, 53, 1323.
(10) (a) Johnson, D. J.; Amarnath, V.; Amarnath, K.; Valentine,
H.; Valentine, W. M. Toxicol. Sci. 2003, 76, 65. (b) Godt, H.
C.; Wann, R. E. J. Org. Chem. 1961, 26, 4047.
(c) Burkhardt, C.; Dehmel, F.; Weinbrenner, S.; Julius, H.;
Ciossek, T.; Maier, T.; Stengel, T.; Fettis, K.; Wieland, H.;
Beckers, T. J. Med. Chem. 2008, 51, 3985. (d) Wegener, D.;
Wirsching, F.; Riester, D.; Schwienhorst, A. Chem. Biol.
2003, 10, 61. (e) Dehmel, F.; Weinbrenner, S.; Julius, H.;
Ciossek, T.; Maier, T.; Stengel, T.; Fettis, K.; Burkhardt, C.;
Wieland, H.; Beckers, T. J. Med. Chem. 2008, 51, 3985.
(11) (a) Anand, O. N.; Kumar, V.; Singh, A. K.; Bist, R. P. S.
Lubrication Sci. 2007, 19, 159. (b) El-khateeb, M.; Roller,
A. Polyhedron 2007, 26, 3920. (c) Efrima, S.; Pradhan, N. C.
R. Chim. 2003, 6, 1035.
Acknowledgment
M.J. thanks CSIR, New Delhi for providing junior research fellow-
ship. This work was supported by Department of Science and Tech-
nology (DST), New Delhi (Project No. SR/S1/OC-83/2010).
(12) (a) Duus, F. In Comprehensive Organic Chemistry; Vol. 3;
Barton, D.; Ollis, W. D., Eds.; Pergamon: New York, 1979,
432. (b) Goldt, H. C.; Wanns, A. E. J. Org. Chem. 1961, 26,
4047.
(13) Wood, M. R.; Duncalf, D. J.; Rannard, S. P.; Perrier, S. Org.
Lett. 2006, 8, 553.
References and Notes
(14) (a) Degani, I.; Fochi, R.; Gatti, A.; Regondi, V. Synthesis
1986, 894. (b) Aoyagi, N.; Ochiai, B.; Mori, H.; Endo, T.
Synlett 2006, 636.
(15) Chaturvedi, D.; Chaturvedi, A. K.; Mishra, N.; Mishra, V.
Tetrahedron Lett. 2008, 49, 4886.
(1) (a) Ranise, A.; Spallarossa, A.; Schenone, S.; Burno, O.;
Bondavalli, F.; Vargiu, L.; Marceddu, T.; Mura, M.; Colla,
P. L.; Pani, A. J. Med. Chem. 2003, 46, 768. (b) Cao, S. L.;
Feng, Y. P.; Jiang, Y. Y.; Liu, S. Y.; Ding, G. Y.; Li, R. T.
Bioorg. Med. Chem. Lett. 2005, 15, 1915. (c) Chen, D.; Cui,
Q. C.; Yang, H.; Dou, Q. P. Cancer Res. 2006, 66, 10425.
(2) (a) Len, C.; Postal, D.; Ronco, G.; Villa, P.; Goubert, C.;
Jeufrault, E.; Mathon, B.; Simon, H. J. Agric. Food Chem.
1997, 45, 3. (b) Soloneski, S.; Gonzalez, M.; Piaggio, E.;
Apezteguia, M.; Reigosa, A. A.; Larramendy, M. L.
Mutagenesis 2001, 16, 487.
(3) (a) Greene, T. W.; Wuts, P. G. M. Protecting Groups in
Organic Synthesis, 3rd ed.; Wiley Interscience: New York,
1999, 484. (b) Barton, D. H. R. Tetrahedron 1992, 48, 2529.
(c) Crich, D.; Quintero, L. Chem. Rev. 1989, 89, 1413.
(d) Yu, T.; Yamada, T.; Weiss, R. G. Chem. Mater. 2010,
22, 5492. (e) Mukherjee, A. K.; Ashare, A. Chem. Rev.
1991, 91, 1.
(4) (a) Burke, J. T. R.; Bajwa, B. S.; Jacobsen, A. E.; Rice, K.
C.; Streaty, R. A.; Klee, W. A. J. Med. Chem. 1984, 27,
1570. (b) Walter, W.; Bode, K. D. Angew. Chem., Int. Ed.
Engl. 1967, 6, 281.
(5) Chaturvedi, D.; Ray, S. Tetrahedron Lett. 2006, 47, 1307.
(6) Ranu, B. C.; Saha, A.; Banerjee, S. Eur. J. Org. Chem. 2008,
519.
(7) (a) Bhadra, S.; Saha, A.; Ranu, B. C. Green Chem. 2008, 10,
1224. (b) Azizi, N.; Aryanasab, F.; Torkiyan, L.; Ziyaei, A.;
Saidi, M. R. J. Org. Chem. 2006, 71, 3634. (c) Azizi, N.;
Aryanasab, F.; Tourkian, L.; Saidi, M. R. Synth. Commun.
2011, 41, 94.
(8) (a) Azizi, N.; Aryanasab, F.; Saidi, M. R. Org. Lett. 2006, 8,
5275. (b) Azizi, N.; Ebrahimi, F.; Aakbari, E.; Aryanasab,
F.; Saidi, M. R. Synlett 2007, 2797. (c) Azizi, N.; Pourhasan,
B.; Aryanasab, F.; Saidi, M. R. Synlett 2007, 1239.
(d) Bardajee, G. R.; Afsari, H. S.; Sadraei, S.; Taimoory, S.
Phosphorus, Sulfur Silicon Relat. Elem. 2012, 187, 871.
(e) Bardajee, G. R.; Sadraei, S.; Taimoory, S.; Abtin, E.
Asian J. Biochem. Pharm. Res. 2011, 1, 178. (f) Chaturvedi,
D.; Mishra, N.; Mishra, V. J. Sulfur Chem. 2007, 28, 607.
(16) (a) Horita, Y.; Takii, T.; Kuroishi, R.; Chiba, T.; Ogawa, K.;
Kremer, L.; Sato, Y.; Lee, Y. S.; Hasegawa, T.; Onozaki, K.
Bioorg. Med. Chem. Lett. 2011, 21, 899. (b) Horita, Y.;
Takii, T.; Chiba, T.; Kuroishi, R.; Maeda, Y.; Kurono, Y.;
Inagaki, E.; Nishimura, K.; Yamamoto, Y.; Abe, C.; Mori,
M.; Onozaki, K. Bioorg. Med. Chem. Lett. 2009, 19, 6313.
(c) Tejima, S.; Ishiguro, S. Chem. Pharm. Bull. 1967, 15,
255. (d) Szeja, W.; Bogusiak, J. Synthesis 1988, 224.
(e) Gabhe, B. S.; Deshmukh, S. P. Int. J. Chem. Sci. 2010, 8,
2083. (f) Ishiguru, S.; Tejima, S. Chem. Pharm. Bull. 1967,
15, 1478. (g) Fügedi, P.; Garegg, P. J.; Oscarson, S.; Rosen,
G.; Silwanis, B. A. Carbohydr. Res. 1991, 211, 157.
(h) Padungros, P.; Alberch, L.; Wei, A. Org. Lett. 2012, 14,
3380. (i) Mangte, D. V.; Deshmukh, S. P.; Bhokare, D. D.;
Deshpande, A. R. Ind. J. Pharm. Sci. 2007, 69, 295.
(j) Bhagat, S. K.; Fokmare, A. K.; Deshmukh, S. P. Orient.
J. Chem. 2001, 17, 437. (k) Mangte, D. V.; Deshmukh, S. P.
Int. J. Chem. Sci. 2004, 2, 159. (l) Mannerstedt, K.; Ekelof,
K.; Oscarson, S. Carbohydr. Res. 2007, 342, 631.
(m) Lichtenthaler, F. W.; Klares, U.; Lergenmuller, M.;
Schwidetzky, S. Synthesis 1992, 179. (n) Li, R.-T.; Ding, P.-
Y.; Han, M.; Cai, M.-S. Synth. Commun. 1998, 28, 295.
(o) Bogusiak, J.; Szeja, W. Polish J. Chem. 1993, 67, 2181.
(p) Lee, B. H.; Bertram, B.; Schmezer, P.; Frank, N.;
Wiessler, M. J. Med. Chem. 1994, 37, 3154. (q) Wei, A. US
20080124776 A1 20080529, 2008.
(17) (a) Doane, W. M. Methods Carbohydr. Chem. 1972, 6, 413.
(b) Narendra, N.; Lalithamba, H. S.; Sureshbabu, V. V.
Tetrahedron Lett. 2010, 51, 6169. (c) Zhou, Y.; Beck, W. J.
Organomet. Chem. 1994, 479, 217.
(18) General Experimental Conditions for the Synthesis of S-
Glycosyl N-Substituted Dithiocarbamate Derivatives
A mixture of amine (1.2 mmol), CS2 (1.5 mmol) was
allowed to stir for 5 min at r.t. To the reaction mixture was
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2789–2794

2794
M. Jana, A. K. Misra
LETTER
added glycosyl bromide (1.0 mmol), and the reaction
mixture was allowed to stir at r.t. for the appropriate time as
mentioned in Table 1. Excess reagents were removed under
reduced pressure. H2O was added to the crude product, and
the mixture was stirred at r.t. The solid product, which
precipitated out immediately, was filtered, washed with H2O
dried, and recrystallized from EtOH. Representative
spectroscopic data of selected products are as follows.
2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl 4-
(19) General Experimental Conditions for the Synthesis of S-
Glycosyl S′-Substituted Trithiocarbonate Derivative
To a mixture of thiol (1.2 mmol), CS2 (1.5 mmol) and
glycosyl bromide (1.0 mmol) was added Et3N (0.1 mmol),
and the reaction mixture was allowed to stir at r.t. for the
appropriate time as mentioned in Table 2. Excess reagents
were removed under reduced pressure. H2O was added to the
crude product, and the mixture was stirred at r.t. The solid
product which precipitated out immediately was filtered,
washed with H2O, dried, and recrystallized from EtOH.
Representative spectroscopic data of selected products are as
follows.
Morpholine Carbodithioate (5)
White solid; mp 132–133 °C; [α]D +26.3 (c 0.5, CHCl3). IR
(KBr): 2966, 1747, 1469, 1426, 1377, 1219, 1112, 1057,
1030, 996, 922, 825, 610 cm–1. 1H NMR (500 MHz, CDCl3):
δ = 5.86 (d, J = 10.5 Hz, 1 H, H-1), 5.34 (t, J = 9.5 Hz, 1 H,
H-2), 5.29 (t, J = 9.5 Hz, 1 H, H-3), 5.11 (t, J = 10.0 Hz, 1 H,
H-4), 4.28 (dd, J = 13.0, 5.0 Hz, 1 H, H-6a), 4.12 (dd, 12,5,
2.0 Hz, 1 H, H-6b), 3.89–3,85 (m, 1 H, H-5), 3.80–3.70 (m,
S-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)-S′-(p-
methylphenyl) Trithiocarbonate (16)
White solid; mp 107–108 °C. [α]D –17.2 (c 0.5, CHCl3). IR
(KBr): 2939, 1747, 1382, 1224, 1039, 918, 809, 604 cm–1. 1H
NMR (500 MHz, CDCl3): δ = 7.37 (d, J = 9.0 Hz, 2 H, ArH),
7.08 (d, J = 9.0 Hz, 2 H, ArH), 5.16 (t, J = 9.5 Hz, 1 H, H-3),
4.98 (t, J = 9.5 Hz, 1 H, H-2), 4.89 (t, J = 9.5 Hz, 1 H, H-4),
4.60 (d, J = 10.0 Hz, 1 H, H-1), 4.21–4.13 (m, 2 H, H-6ab),
3.68–3.64 (m, 1 H, H-5), 2.34 (s, 3 H, CH3), 2.09, 2.07, 2.02,
1.99 (4 s, 12 H, 4 COCH3). 13C NMR (125 MHz, CDCl3): δ
= 194.7 (C=S), 170.3, 170.0, 169.2, 169.0 (4 COCH3),
138.7–127.4 (ArC), 85.7 (C-1), 75.8 (C-5), 74.0 (C-3), 69.9
(C-2), 68.1 (C-4), 62.0 (C-6), 21.2 (CH3), 20.7, 20.6 (2 C),
20.5 (4 COCH3). ESI-MS: m/z = 553.0 [M + Na]+. Anal.
Calcd for C22H26O9S3 (530.07): C, 49.80; H, 4.94. Found: C,
49.64; H, 5.14.
4 H, CH2), 2.07, 2.04, 2.03, 2.01 (4 s, 12 H, 4 COCH3). 13
C
NMR (125 MHz, CDCl3): δ = 192.4 (C=S), 170.4, 169.8,
169.4, 169.3 (4 COCH3), 86.7 (C-1), 76.3 (C-5), 74.3 (C-3),
68.5 (C-4), 68.0 (C-2), 66.2 (CH2), 65.9 (CH2), 61.6 (C-6),
51.6 (CH2), 50.7 (CH2), 20.8, 20.7, 20.6 (2 C, 4 COCH3).
ESI-MS: m/z = 516.1 [M + Na]+. Anal. Calcd for
C19H27NO10S2 (493.10): C, 46.24; H, 5.51. Found: C, 46.10;
H, 5.70.
(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)-N-
cyclopropylmethyl-N-propyl Dithiocarbamate (6)
White solid; mp 78–80 °C. [α]D +12.5 (c 0.5, CHCl3). IR
(KBr): 2940, 1747, 1478, 1382, 1243, 1222, 1079, 1036,
913, 830, 606 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.87
(d, J = 10.0 Hz, 1 H, H-1), 5.35 (t, J = 9.0 Hz, 1 H, H-3), 5.27
(t, J = 9.5 Hz, 1 H, H-2), 5.11 (t, J = 9.0 Hz, 1 H, H-4), 4.29
(dd, J = 12.5, 4.5 Hz, 1 H, H-6a), 4.12 (d, J = 12.0 Hz, 1 H,
H-6b), 4.03–3.96 (m, 1 H), 3.92–3.87 (m, 2 H, H-5, CH2),
3.86–3.72 (m, 1 H), 3.65–3.51 (m, 2 H), 2.07, 2.03, 2.01, (3
s, 12 H, 4 COCH3), 1.80–1.65 (m, 2 H), 1.35–1.25 (m, 1 H),
0.98–0.90 (m, 3 H), 0.63–0.57 (m, 2 H), 0.35–0.32 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 192.0 (C=S), 170.5, 169.8,
169.3, (2 C, 4 COCH3), 87.2 (C-1), 76.2 (C-5), 74.5 (C-3),
68.6 (C-4), 68.1 (C-2), 61.6 (C-6), 59.4 (CH2), 57.0 (CH2),
19.3 (CH2), 20.8, 20.7, 20.6, 20.5 (4 COCH3), 11.3 (CH3),
8.9 (CH), 4.3, 4.0 (CH2). ESI-MS: m/z = 542.1 [M + Na]+.
Anal. Calcd for C22H33NO9S2 (519.16): C, 50.85; H, 6.40.
Found: C, 50.70; H, 6.60.
S-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)-S′-(p-
methoxylphenyl) Trithiocarbonate (17)
White solid; mp 88–90 °C. [α]D –20.4 (c 0.5, CHCl3). IR
(KBr): 2940, 1747, 1494, 1383, 1226, 1038, 831 cm–1. 1H
NMR (500 MHz, CDCl3): δ = 7.45 (d, J = 9.0 Hz, 2 H, ArH),
6.84 (d, J = 9.0 Hz, 2 H, ArH), 5.19 (t, J = 9.5 Hz, 1 H, H-3),
4.99 (t, J = 9.5 Hz, 1 H, H-2), 4.88 (t, J = 9.5 Hz, 1 H, H-3),
4.56 (d, J = 10.0 Hz, 1 H, H-1), 4.22–4.16 (m, 2 H, H-6ab),
3.81 (s, 3 H, OCH3), 3.69–3.66 (m, 1 H, H-5), 2.10, 2.07,
2.01, 1.98 (4 s, 12 H, 4 COCH3). 13C NMR (125 MHz,
CDCl3): δ = 195.3 (C=S), 170.6, 170.2, 169.4, 169.2 (4
COCH3), 160.4–114.4 (ArC), 85.6 (C-1), 75.7 (C-5), 74.0
(C-3), 69.9 (C-2), 68.1 (C-4), 62.0 (C-6), 55.3 (OCH3), 20.8,
20.7, 20.6, 20.5 (4 COCH3). ESI-MS: m/z = 569.0 [M +
Na]+. Anal. Calcd for C22H26O10S3 (546.06): C, 48.34; H,
4.79. Found: C, 48.17; H, 4.95.
Synlett 2012, 23, 2789–2794
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