Zn/RuCl3-promoted cleavage of diselenides: An efficient michael addition of zinc selenolates to conjugated alkenes in aqueous media

Article abstract of DOI:10.1055/s-2007-984495

A simple and highly efficient one-pot route to β-selenocarbonyl compounds and nitriles has been developed by Zn/RuCl₃-catalyzed cleavage of diselenides and subsequent Michael addition of zinc selenolates to conjugated alkenes in aqueous media. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-984495

1954
LETTER
Zn/RuCl3-Promoted Cleavage of Diselenides: An Efficient Michael Addition of
Zinc Selenolates to Conjugated Alkenes in Aqueous Media
Z
n/RuCl -Promo
a
d
Cleavag
r
e
of
D
is
a
e
lenides hman Movassagh,*a,b Ameneh Tatara
3
a
Department of Chemistry, K. N. Toosi University of Technology, P.O. Box, 16315-1618, Tehran, Iran
b
Kermanshah Oil Refining Company, Kermanshah, Iran
Fax +98(21)22853650; E-mail: bmovass1178@yahoo.com
Received 15 March 2007
Zn/RuCl3
X
X
Abstract: A simple and highly efficient one-pot route to b-seleno-
carbonyl compounds and nitriles has been developed by Zn/RuCl3-
catalyzed cleavage of diselenides and subsequent Michael addition
of zinc selenolates to conjugated alkenes in aqueous media.
3
R1SeSeR1
[(R1Se)2Zn]
MeCN–H2O, 80 °C
R1Se
1
2
4
R1 = aryl, benzyl
X = COR2, CHO, CO2R2, CN
R2 = alkyl
Key words: zinc selenolates, Michael addition, a,b-unsaturated
carbonyl compounds, zinc, diselenides
Scheme 1
Over the last three decades, many investigators have
described important chemical transformations that were
efficiently achieved using organoselenium reagents.
Organoselenium compounds are of considerable interest
because of their involvement as key intermediates in
organic synthesis and use as a food supplement.1 These
compounds are no longer systematically classified as
toxic and, thus, much effort is being devoted to accom-
plishing the synthesis of organic selenides. Although
numerous reports on the synthesis of organoselenium
compounds have already been published,1,2 most of them,
with the exception of three recent reports,3 usually require
the handling of unstable reagents, strongly acidic or basic
reaction conditions, and two-step procedures. Hence, the
development of a one-pot synthetic method using stable
reagents under neutral conditions is in demand.
carbonyl compounds and nitriles to give the correspond-
ing b-selenocarbonyl compounds and nitriles (Scheme 1).
Simple stirring of diselenides 1 with metallic zinc dust in
the presence of ruthenium(III) chloride (10 mol%) in
MeCN–H2O (4:1) mixed solvent at 80 °C produced the
zinc selenolate 2. This was followed by addition of a,b-
unsaturated carbonyl compounds and nitriles 3 which
gave, after workup, the desired product 4 with yields rang-
ing from 55–98% (Table 1).9 Both diaryl and dialkyl
(dibenzyl) diselenides react with a variety of conjugated
alkenes by this procedure to produce the corresponding
adducts. The conjugated alkenes include a,b-unsaturated
ketones, aldehydes, carboxylic esters, and nitriles. The
reaction of diaryl diselenides with methyl vinyl ketone
(Table 1, entries 1 and 11) took place faster with higher
yields than the others. a,b-Unsaturated carbonyl com-
pounds and nitriles having substituents at either the a-
(Table 1, entry 7) or the b-position (Table 1, entries 2, 3,
5, and 10) show lower yields than the unsubstituted deriv-
atives.
Reductive cleavage of Se–Se bonds, especially cleavage
of diphenyl or other diaryl diselenides, has attracted con-
siderable attention due to the fact that selenide anion
formed can be used for preparation of wide variety of
compounds. Several reducing agents, including LiAlH4,
NaBH4, Bu3SnH, and Na/NH3, have been introduced for
Se–Se bond cleavage.4
Synthetically, preparation of a,b-phenylseleno carbonyl
compounds enables a number of useful transformations
based on the syn-elimination of phenyl selenoxide10 to be
performed.
Organometallic reactions in aqueous media have attracted
considerable attention in organic synthesis.5 Recently,
transition-metal selenolates or complexes have been
widely used in synthesis of organoselenium compounds,6
but reports exploring zinc selenolates are rare.3a,7 As a part
of our interest in zinc chemistry,7,8 we are in constant
search for novel applications of zinc selenolates and zinc
thiolates in chemical reactions. In the present paper we de-
scribe the use of zinc metal–ruthenium(III) chloride (Zn/
RuCl3)3a system for the cleavage of diselenides and in situ
Michael addition of selenolate anion to a,b-unsaturated
In conclusion, this Zn/RuCl3-promoted one-pot procedure
for the Michael addition of diselenides to conjugated alk-
enes in aqueous media provides an efficient methodology
for the synthesis of b-selenocarbonyl compounds and
nitriles. This method offers significant advantages with
regards to operation, yield, time, handling of catalysts,
and cost and thus presents an alternative to the existing
procedures.11
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Advanced online publication: 25.06.2007
DOI: 10.1055/s-2007-984495; Art ID: D07607ST
© Georg Thieme Verlag Stuttgart · New York

LETTER
Zn/RuCl3-Promoted Cleavage of Diselenides
1955
Table 1 Reductive Cleavage of Diselenides and Conjugated Addition to Michael Acceptors in the Presence of Zn/RuCl3 System in
MeCN–H2O
Entry
1
R1
Ph
Alkene
Time (h)
1.25
Product
Yield (%)a,b
9611b
COMe
COMe
PhSe
O
O
2
3
Ph
Ph
3
6411b
SePh
PhSe
Ph
COMe
COMe
4.5
7111b
Ph
CHO
CHO
CHO
4
5
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2.5
2.5
3.25
3.5
3
8712
PhSe
PhSe
CHO
7612
CN
CN
6
8111a
7511a
8011a
7311c
5511a
CN
PhSe
CN
7
PhSe
PhSe
PhSe
COOEt
COOEt
8
COOn-Bu
COOi-Pr
COOn-Bu
COOi-Pr
9
3.5
4.75
10
PhSe
COMe
COMe
COMe
11
12
4-ClC6H4
Bn
1
98
81
RSe
R = 4-ClC6H4
COMe
3.75
RSe
R = Bn
a Yields refer to those of pure isolated products characterized by IR, 1H NMR, and 13C NMR spectroscopy.
b References for known compounds.
(3) (a) Zhao, X.; Yu, Z.; Yan, S.; Wu, S.; Liu, R.; He, W.; Wang,
L. J. Org. Chem. 2005, 70, 7338. (b) Nishino, T.; Okada,
M.; Kuroki, T.; Watanabe, T.; Nishiyama, Y.; Sonoda, N. J.
Org. Chem. 2002, 67, 8696. (c) Ranu, B. C.; Mandal, T.;
Samanta, S. Org. Lett. 2003, 5, 1439.
Acknowledgment
We thank the K. N. Toosi University of Technology Research
Council and Kermanshah Oil Refining Company for financial
support.
(4) (a) Bhasin, K. K.; Singh, N.; Kumar, R.; Deepali, D. G.;
Mehta, S. K.; Klapoetke, T. M.; Crawford, M.-J. J.
Organomet. Chem. 2004, 689, 3327. (b) Yoshimatsu, M.;
Sato, T.; Shimizu, H.; Hori, M.; Kataoka, T. J. Org. Chem.
1994, 59, 1011. (c) Crich, D.; Grant, D. J. Org. Chem. 2005,
70, 2384. (d) Andreadou, I.; Menge, W. M. P. B.;
Commandeur, J. N. M.; Worthington, E. A.; Vermeulen, N.
P. E. J. Med. Chem. 1996, 39, 2040. (e) Sakakibara, M.;
Katsumata, K.; Watanabe, Y.; Toru, T.; Ueno, Y. Synthesis
1992, 377.
References and Notes
(1) (a) Krief, A.; Hevesi, L. Organoselenium Chemistry, Vol. 1;
Springer: Berlin, 1988. (b) Krief, A. In Comprehensive
Organometallic Chemistry; Trost, B. M., Ed.; Pergamon:
Oxford, 1991, 85; and references therein.
(2) (a) Patai, S.; Rappoport, Z. The Chemistry of Organic
Selenium and Tellurium Compounds, Vol. 1; Wiley and
Sons: New York, 1986. (b) Krief, A.; Derock, M.
Tetrahedron Lett. 2002, 43, 3083. (c) Patai, S.; Rappoport,
Z. The Chemistry of Organic Selenium and Tellurium
Compounds, Vol. 2; Wiley and Sons: New York, 1987.
(d) Paulmier, C. Selenium Reagents and Intermediates in
Organic Synthesis; Pergamon: Oxford, 1986.
(5) (a) Lubineau, A.; Auge, J.; Queneau, Y. Synthesis 1994,
741. (b) Li, C. J. Chem. Rev. 1993, 93, 2023.
Synlett 2007, No. 12, 1954–1956 © Thieme Stuttgart · New York

1956
B. Movassagh, A. Tatar
LETTER
(6) (a) Meunier, P.; Gaotheron, B.; Mazouz, A. J. Chem. Soc.,
Chem. Commun. 1986, 424. (b) Osuka, A.; Ohmasa, N.;
Suzuki, H. Synthesis 1982, 857. (c) Bao, W.; Zhang, Y.
Synth. Commun. 1995, 25, 1825.
subjected to preparative TLC (silica gel, eluent, n-hexane–
EtOAc = 4:1) to afford pure 4-(4-chlorophenylseleno)butan-
2-one (255 mg, 98%, Table 1, entry 11) as a pale yellow oil.
IR (neat): 1720, 1478, 739 cm–1. 1H NMR (300 MHz,
CDCl3): d = 2.14 (s, 3 H), 2.84 (t, 2 H, J = 7.2 Hz), 3.05 (t, 2
H, J = 7.2 Hz), 7.25 (d, 2 H, J = 8.5 Hz), 7.42 (d, 2 H, J = 8.5
Hz) ppm. 13C NMR (75 MHz, CDCl3): d = 20.8, 30.0, 43.9,
127.9, 129.3, 133.3, 134.3, 206.8 ppm. MS: m/z (%) = 264
(46) [(M + 4]+ , 262 (90) [M + 2]+, 260 (49) [M+], 219 (15),
191 (20), 151 (24), 71 (55), 43 (100). Anal. Calcd for
C10H11ClOSe: C, 45.91; H, 4.24. Found: C, 46.30; H, 4.51.
Spectroscopic Data for Entry 12, Table 1
(7) (a) Movassagh, B.; Mirshojaei, F. Monatsh. Chem. 2003,
134, 831. (b) Movassagh, B.; Shamsipoor, M. Synlett 2005,
121. (c) Movassagh, B.; Shamsipoor, M. Synlett 2005,
1316. (d) Movassagh, B.; Shamsipoor, M.; Joshaghani, M. J.
Chem. Res., Synop. 2004, 148. (e) Movassagh, B.; Fazeli,
A. Z. Naturforsch., B: Chem. Sci. 2006, 61, 194.
(8) (a) Movassagh, B.; Zakinezhad, Y. Chem. Lett. 2005, 34,
1330. (b) Movassagh, B.; Mossadegh, A. Synth. Commun.
2004, 34, 1685. (c) Movassagh, B.; Zakinezhad, Y. Z.
Naturforsch., B: Chem. Sci. 2006, 61, 47. (d) Lakouraj, M.
M.; Movassagh, B.; Fadaei, Z. Synth. Commun. 2002, 32,
1237.
IR (neat): 1710, 1478, 738 cm–1. 1H NMR (500 MHz,
CDCl3): d = 2.13 (s, 3 H), 2.69–2.71 (m, 2 H), 2.74–2.77 (m,
2 H), 3.84 (s, 2 H), 7.24–7.33 (m, 5 H) ppm. 13C NMR (125
MHz, CDCl3): d = 17.0, 28.1, 30.4, 44.7, 127.2, 128.9,
129.3, 139.7, 207.6 ppm. MS: m/z (%) = 242 (30) [M + 2]+,
240 (16) [M+], 181 (10), 91 (100), 65 (22), 43 (51). Anal.
Calcd for C11H14OSe: C, 54.78; H, 5.85. Found: C, 54.51; H,
5.64.
(9) 4-(4-Chlorophenylseleno)butan-2-one – Typical
Procedure
In a typical experiment, a mixture of bis(4-chloro-
phenyl)diselenide (190 mg, 0.5 mmol), zinc dust (229 mg,
3.5 mmol), and ruthenium(III) chloride hydrate (13 mg, 0.05
mmol) was suspended in MeCN (8 mL) and H2O (2 mL).
The mixture was stirred at 80 °C for 1.5 h, during which time
the zinc powder was almost completely consumed. Then,
methyl vinyl ketone (73 mg, 1.05 mmol) was added at once
to the mixture and stirring was continued at that temperature
for 1 h in air. After completion of the reaction, the solution
was filtered, the solvent was evaporated, and the residue was
(10) Sevrin, M.; Krief, A. Tetrahedron Lett. 1978, 187.
(11) (a) Ranu, B. C.; Das, A. Adv. Synth. Catal. 2005, 347, 712.
(b) Miyashita, M.; Yoshikoshi, A. Synthesis 1980, 664.
(c) Zhou, L.-H.; Zhang, Y.-M. Synth. Commun. 1999, 29,
533. (d) Detty, M. R. Tetrahedron Lett. 1978, 5087.
(12) Nishiyama, Y.; Asano, T.; Kishimoto, Y.; Itoh, K.; Ishii, Y.
Tetrahedron Lett. 1998, 39, 8685.
Synlett 2007, No. 12, 1954–1956 © Thieme Stuttgart · New York

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