Aerobic oxidation of thiols to disulfides catalyzed by trichlorooxyvanadium

Article abstract of DOI:10.1248/cpb.52.625

Thiols were converted into disulfide by the aerobic oxidation catalyzed by trichlorooxyvanadium in the presence of molecular sieves 3A.

Full text of DOI:10.1248/cpb.52.625

May 2004
Notes
Chem. Pharm. Bull. 52(5) 625—627 (2004)
625
Aerobic Oxidation of Thiols to Disulfides Catalyzed by
Trichlorooxyvanadium
,
a
a
a
a
b
Masayuki KIRIHARA,* Kumiko OKUBO, Tomoyuki UCHIYAMA, Yo ko K ATO, Yuta OCHIAI,
a
a
c
Shinya MATSUSHITA, Akihiko HATANO, and Kan KANAMORI
a
Department of Materials Science, Shizuoka Institute of Science and Technology; 2200–2 Toyosawa, Fukuroi, Shizuoka
b
4
37–8555, Japan: Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University; 2630 Sugitani,
c
Toyama 930–0194, Japan: and Faculty of Science, Department of Chemistry, Toyama University; 3190 Gofuku, Toyama
9
30–8555, Japan. Received December 16, 2003; accepted February 9, 2004
Thiols were converted into disulfide by the aerobic oxidation catalyzed by trichlorooxyvanadium in the pres-
ence of molecular sieves 3A.
Key words thiol; disulfide; oxidative coupling; aerobic oxidation
Oxidative coupling of thiols to disulfides is of interest
from both a synthetic and a biological point of view, because
1—3)
disulfides are useful reagent in organic synthesis
and es-
Chart 1
sential moieties of biologically active compounds for peptide
4)
and protein stabilization. Thiols can be easily over-oxidized, Table 1
and therefore, several selective methods of converting thiols
into disulfides have been developed. For example, iodine/
0
.4 eq VOCl , O , solvent
3 2
CH (CH ) –SH
3
2 11
5)
6,7)
1/2 CH (CH ) S–S(CH ) CH
3 2 11 2 11 3
hydrogen iodide, bromine, potassium permanganate/cop-
8
)
9)
per(II) sulfate, hydrogen peroxide in trifluoroethanol, and
10—12)
Run
Solvent
C H
CH Cl
AcOEt
Time
Yield
dimethyl sulfoxide
are used for this purpose. Most of
the existing methods suffer from drawbacks such as the use
of stoichiometric amounts of reagents that generate undesir-
able waste materials. To overcome these drawbacks, catalytic
oxidation using oxygen as a co-oxidant has been developed
1
2
3
4
5
5 d
44 h
22 h
26 h
51 h
52%
51%
93%
82%
Trace
6
6
2
2
CH CN
CH OH
3
13—18)
3
by several groups.
We have been investigating the aerobic oxidation of or-
ganic compounds catalyzed by higher valent vanadium com-
1
9—36)
pounds.
Stoichiometric higher valent vanadium com- Table 2
37,38)
pounds are known to oxidize thiols to produce disulfides,
0
.4 eq catalyst, O2
and a catalytic amount of vanadyl acetylacetonate is also
known to cause the oxidative coupling of thiols in the pres-
ence of t-butylhydroperoxide. However, there have been no
reports about the aerobic oxidative coupling of thiols cat-
alyzed by vanadium compounds. We now describe a novel
aerobic oxidative coupling of thiols to disulfides using
n-Bu–SH
1/2 n-BuS–Sn-Bu
AcOEt
39)
Run
Catalyst
Time
Yield
1
2
3
VOCl3
VOCl2
VO(acac)
3 h
41 h
41 h
Quant
13%
28%
trichlorooxyvanadium (VOCl ) as a catalyst (Chart 1).
2
3
We first examined the oxidation of didodecylthiol as a
model substrate with 0.4 eq of VOCl under an oxygen at-
3
mosphere in several kinds of solvents (Table 1). The reaction Table 3
efficiently proceeded in aprotic polar solvents such as ethyl
acetate (run 3) and acetonitrile to provide didodecyl
catalyst, O , AcOEt
2
n-Bu–SH
1/2 n-BuS–Sn-Bu
40)
disulfide (run 4).
We then investigated the reaction of butanthiol with sev-
eral higher valent vanadium catalysts in ethyl acetate under
an oxygen atmosphere (Table 2). Dibutyl disulfide was
Run
Catalyst
Time
Yield
41)
1
2
3
0.4 eq VOCl3
0.3 eq VOCl3
0.2 eq VOCl3
3 h
28 h
24 h
Quant
66%
30%
quantitatively obtained in the case of VOCl (a pentavalent
3
vanadium) (run 1). On the other hand, tetravalent vanadiums
{
vanadyl chloride (VOCl ) (run 2) and vanadyl acetylaceto-
2
nate [VO(acac) ] (run 3)} did not have sufficient catalytic ac-
2
tivity.
pling of a thiol deactivated the vanadium catalyst. Therefore,
Although the oxidation of butanthiol smoothly proceeded molecular sieves 3A were added to the reaction mixture to
42,43)
to afford the disulfide, over 0.4 eq of VOCl was required to remove the water.
In the presence of the molecular sieves
3
complete the reaction (Table 3).
3A, only 0.05 eq VOCl was enough to complete the reaction
3
We assumed that water produced from the oxidative cou- (Chart 2).
∗
To whom correspondence should be addressed. e-mail: kirihara@ms.sist.ac.jp
© 2004 Pharmaceutical Society of Japan

6
26
Vol. 52, No. 5
ence Promotion Program of Japan Science and Technology Corporation), for
his helpful suggestions.
References
Chart 2
1)
For example, see: Ogawa A., Nishiyama Y., Kambe N., Murai S., So-
noda N., Tetrahedron Lett., 28, 3271—3274 (1987).
Table 4
2) For example, see: Antebi S., Alper H., Tetrahedron Lett., 26, 2609—
612 (1985).
3) For example, see: Bischoff L., David C., Martin L., Meudal H.,
2
0
.05 eq VOCl , O , AcOEt
3
2
RSH
1/2 RS–SR
Roques B.-P., Fournié-Zaluski M.-C., J. Org. Chem., 62, 4848—4850
molecular sieves 3A, rt
(1997).
4)
Bodanszky M., “Principles of Peptide Synthesis: Reactivity and Struc-
ture Concepts in Organic Chemistry,” Springer Verlag, Hiderberg,
a)
Entry
Thiol
Product
Time (h) Yield (%)
1
984, p. 307.
5) Aida T., Akasaka T., Furukawa N., Oae S., Bull. Chem. Soc. Jpn., 49,
441—1442 (1976).
6) Wu X., Reike R. D., Zhu L., Synth. Commun., 26, 191—196 (1996).
Drabowicz J., Mikolajczyk M., Synthesis, 1980, 32—34 (1980).
8) Noureldin N. A., Caldwell M., Hendry J., Lee D. G., Synthesis, 1998,
587—1589 (1998).
9) Kesavan V., Bonnet-Delpon D., Bégué J.-P., Synthesis, 2000, 223—225
2000).
0) Tam J. P., Wu C.-R., Liu W., Zhang J.-W., J. Am. Chem. Soc., 113,
657—6662 (1991).
4
4
4
0
1
4
111
88
(93)
98
(quant)
84
1
2
3
4
b)
b)
(22)
1
43
b)
b)
(3)
7)
1.5
0.5)
1
b)
b)
b)
(
4
(
(75)
1
c)
53
13
45
b)
5)
(93)
(
1
1
5
6
7
109
80
6
1) Sanz R., Aguado R., Pedrosa M. R., Arnáiz F. J., Synthesis, 2002,
5
2
93
(99)
856—858 (2002).
1
1
3
6
b)
b)
b)
b)
(22)
12) Karimi B., Hazarkhani H., Zareyee D., Synthesis, 2002, 2513—2516
2002).
(
74
(
91
(99)
13) For example: Liu K.-T., Tong Y.-C., Synthesis, 1978, 669—670
4)
(1978).
1
1
1
4) For example: Simándi L. I., Németh S., Rumelis N., J. Mol. Catal., 42,
4
4
6
6
3
57—360 (1987).
8
9
20
66
96
98
5) For example: Cervilla A., Corma A., Fornes V., Llopis E., Palanca P.,
Rey F., Ribera A., J. Am. Chem. Soc., 116, 1595—1596 (1994).
6) For example: Iranpoor N., Zeynizadeh B., Synthesis, 1999, 49—50
(1999).
a) The physical data of the products were consistent with those of references.
17) For example: Rao T. V., Rao K. N., Jain S. L., Sain B., Synth. Com-
mun., 32, 1151—1157 (2002).
b) 0.4 eq of VOCl was used without molecular sieves 3A. c) Unidentified by-prod-
3
ucts were obtained.
18) For example: Shah S. T. A., Khan K. M., Fecker M., Voelter W., Tetra-
hedron Lett., 44, 6789—6791 (2003).
This method is equally applicable for the oxidative cou- 19) For example: Kirihara M., Takizawa S., Momose T., J. Chem. Soc.
Perkin Trans. 1, 1998, 7—8 (1998).
0) For example: Kirihara M., Ichinose M., Takizawa S., Momose T.,
Chem. Commun., 1998, 1691—1692 (1998).
1) For example: Kirihara M., Ochiai Y., Takizawa S., Takahata H.,
Nemoto H., Chem. Commun., 1999, 1387—1388 (1999).
2) For example: Kirihara M., Ochiai Y., Arai N., Takizawa S., Momose
T., Nemoto H., Tetrahedron Lett., 40, 9055—9057 (1999).
3) Organic syntheses using vanadium reagents developed by other
groups: Hirao T., Chem. Rev., 97, 2707—2724 (1997).
pling of several kinds of thiols (Table 4). In the parentheses,
2
2
2
2
we also show the results of the reaction using 0.4 eq VOCl3
without molecular sieves. Although the reaction rates were
relatively slow, dislufides were efficiently obtained in most
cases. As noted in the entry 3, 2-mercaptoethanol was oxi-
dized much faster than in the other cases. The reason for this
interesting phenomenon has not been clarified.
In conclusion, the VOCl -catalyzed aerobic oxidative cou-
3
24) Organic syntheses using vanadium reagents developed by other
pling of thiols should be a good method to prepare disulfides.
groups: Takada T., Sakurai H., Hirao T., J. Org. Chem., 66, 300—302
(2001).
Experimental
25) Organic syntheses using vanadium reagents developed by other
groups: Hirao T., Morimoto C., Takada T., Sakurai H., Tetrahedron
Lett., 42, 1961—1963 (2001).
General Procedures Thiols and vanadium compounds were obtained
from Wako Pure Chemical Industries, Kanto Kagaku, Nacalai Tesque, or
Tokyo Kasei Kogyo without purification. Products were characterized by 26) Organic syntheses using vanadium reagents developed by other
comparison of their physical data with those of known samples.
groups: Hirao T., Morimoto C., Takada T., Sakurai H., Tetrahedron,
The Aerobic Oxidation of Thiols Catalyzed by Trichlorooxyvanadium
57, 5073—5079 (2001).
in the Presence of Molecular Sieves 3A: General Procedures To a 27) Organic syntheses using vanadium reagents developed by other
stirred mixture of thiol (4.0 mmol), molecular sieves 3A (1.0 g) and ethyl ac-
groups: Hirao T., Takada T., Sakurai H., Org. Lett., 2, 3659—3661
etate (4.0 ml) was added VOCl (35 mg, 0.2 mmol) under an oxygen atmos-
(2000).
3
phere at room temperature. The reaction was monitored by thin layer chro- 28) Organic syntheses using vanadium reagents developed by other
matography and was continuously stirrered under the same conditions until
the thiol disappeared. After the reaction was completed, a drop of saturated
aqueous sodium bicarbonate was added and diluted with ethyl acetate
groups: Ishikawa T., Nonaka S., Ogawa A., Hirao T., Chem. Commun.,
1998, 1209—1210 (1998).
29) Organic syntheses using vanadium reagents developed by other
groups: Ishikawa T., Ogawa A., Hirao T., J. Am. Chem. Soc., 120,
5124—5125 (1998).
(30 ml). The resulting mixture was filtered with Cerite and the filtrate was
dried over anhydrous magnesium sulfate. The solvent was evaporated and
the residue was purified by silica gel column chromatography (hexane–ethyl 30) Organic syntheses using vanadium reagents developed by other
acetate as the eluents) to afford the pure products.
groups: Ishikawa T., Ogawa A., Hirao T., Organometallics, 17, 5713—
716 (1998).
5
Acknowledgments This work was supported in part by the Regional
Science Promotion Program of Japan Science and Technology Corporation.
We would like to express our appreciation to Mr. Masao Yaso (Regional Sci-
31) Organic syntheses using vanadium reagents developed by other
groups: Hirao T., Asahara M., Muguruma Y., Ogawa A., J. Org.
Chem., 63, 2812—2813 (1998).

May 2004
627
32) Organic syntheses using vanadium reagents developed by other
groups: Hirao T., J. Inorg. Biochem., 80, 27—33 (2000).
mun., 31, 1477—1480 (2001).
40) Huang Y., Zhang Y., Wang Y., Synth. Commun., 27, 1043—1047
33) Organic syntheses using vanadium reagents developed by other
groups: Hoshino Y., Yamamoto H., J. Am. Chem. Soc., 122, 10452—
(1997).
41) Iranpoor N., Firouzabadi H., Zolfigol M. A., Synth. Commun., 28,
1
0453 (2000).
367—375 (1998).
34) Organic syntheses using vanadium reagents developed by other 42) Molecular sieves are used to remove water formed during the vana-
groups: Bolm C., Küehn T., Synlett, 2000, 899—901 (2000).
5) Organic syntheses using vanadium reagents developed by other
groups: Chien C.-T., Kuo J.-H, Li C.-H., Barhate N. B., Hon S.-W., Li
T.-W., Chao S.-D., Liu C.-C., Li Y.-C., Chang I.-H., Lin J.-S., Liu C.-
J., Chou Y.-C., Org. Lett., 3, 3729—3732 (2001).
dium compound-catalyzed aerobic oxidation of propargylic alcohols.
See: Maeda Y., Kakiuchi N., Matsumura S., Nishimura T., Uemura S.,
Tetrahedron Lett., 42, 8877—8879 (2001).
3
43) Molecular sieves are used to remove water formed during the vana-
dium compound-catalyzed aerobic oxidation of propargylic alcohols.
See: Maeda Y., Kakiuchi N., Matsumura S., Nishimura T., Kawamura
T., Uemura S., J. Org. Chem., 67, 6718—6724 (2002).
36) Organic syntheses using vanadium reagents developed by other
groups: Hwang D.-R., Chen C.-P., Uang B.-J., Chem. Commun., 1999,
1
207—1208 (1999).
44) Meshram H. M., Bandyopadhyay A., Reddy G. S., Yadav J. S., Synth.
Commun., 30, 701—706 (2000).
45) “Aldrich Handbook of Fine Chemicals 2003—2004,” Aldrich Chemi-
cal Company, Milwaukee, 2003.
3
3
7) Hill J., McAuley A., J. Chem. Soc. A, 1968, 2405—2408 (1968).
8) Pickering W. F., McAuley A., J. Chem. Soc. A, 1968, 1173—1176
(1968).
3
9) Raghavan S., Rajender A., Joseph S. C., Rasheed M. A., Synth. Com- 46) Huang X., Chan C.-C., Synthesis, 1982, 1091—1092 (1982).