A convenient synthesis of β-phenylselenocarbonyl compounds by In-TMSCL promoted cleavage of diphenyl diselenide and subsequent michael addition

Article abstract of DOI:10.1002/adsc.200404355

A simple and convenient procedure has been developed for the synthesis of β-phenylselenocarbonyl compounds by a one-pot reaction of diphenyl diselenide and α,β-unsaturated ketones, aldehydes, esters and nitriles in the presence of indium metal-trimethylsilyl chloride under sonication. Presumably, the In-TMSCl reagent system reacts with diphenyl diselenide to form an intermediate, PhSeSiMe₃, which then undergoes Michael addition with the α,β-unsaturated carbonyl compounds to produce the products.

Full text of DOI:10.1002/adsc.200404355

UPDATES
A Convenient Synthesis of b-Phenylselenocarbonyl Compounds
by In-TMSCl Promoted Cleavage of Diphenyl Diselenide and
Subsequent Michael Addition
Brindaban C. Ranu,* Arijit Das
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta – 700 032, India
Fax : ( þ91)-33-2473-2805; e-mail: ocbcr@iacs.res.in
Received: November 23, 2004; Accepted: February 14, 2005
Abstract: A simple and convenient procedure has
been developed for the synthesis of b-phenylseleno-
carbonyl compounds by a one-pot reaction of di-
phenyl diselenide and a,b-unsaturated ketones, alde-
hydes, esters and nitriles in the presence of indium
metal-trimethylsilyl chloride under sonication. Pre-
sumably, the In-TMSCl reagent system reacts with
diphenyl diselenide to form an intermediate, PhSe-
SiMe3, which then undergoes Michael addition with
the a,b-unsaturated carbonyl compounds to produce
the products.
triles leading to the synthesis of b-phenylselenocarbonyl
compounds and nitriles (Scheme 1).
Scheme 1.
Keywords: indium; Michael addition; b-selenocar-
bonyl compound; trimethylsilyl chloride; ultrasound
The experimental procedure is very simple. A solution
of diphenyl diselenide and a conjugated alkene in aceto-
nitrile was sonicated in the presence of indium metal
(finely cut) and trimethylchlorosilane and the product
was isolated by usual work-up. Several a,b-unsaturated
ketones, aldehydes, carboxylic esters, and nitriles under-
The interest in organoselenium compounds for organic went facile Michael additions with selenate anions to
synthesis is growing because of their facile participation provide the corresponding b-phenylseleno adducts.
as key intermediates in various reactions.[1] Although The results are summarized in Table 1.
the importance of b-selenocarbonyl compounds as po-
Other indium reagents, such as indium metal, indi-
tential enone b-anion equivalents has been well estab- um(III) chloride and indium(I) iodide which promote
lished,[2] the methods for their synthesis are very limit- similar reactions with diphenyl disulfide,[5k] are not suc-
ed.[3] In general, these methods are not very satisfactory cessful for this selenium Michael addition. Although the
and they suffer from low yields of products, poor gener- exact role of In-TMSCl in this reaction is not very clear
ality and the disadvantage of handling of selenium re- to us at this moment, it is speculated that diphenyl dise-
agents such as benzeneselenol, used as selenium sources
because of their instability towards air and moisture.
Thus, the development of efficient synthetic methods us-
ing a stable and user-friendly selenium reagent under
mild conditions would have significant synthetic value.
Indium metal and its derivatives have made a tremen-
dous impact in organic synthesis in recent times because
of their successful applications in a variety of organic
transformations.[4] As a part of our interest in indium
chemistry,[4e,5] we are in constant search for new indium
reagents with novel applications in chemical reactions.
We report here the use of the indium metal-trimethyl-
chlorosilane reagent system for the cleavage of diphenyl
diselenide and in situ Michael addition of selenoate
anion to a,b-unsaturated carbonyl compounds and ni-
Scheme 2.
712
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adsc.200404355
Adv. Synth. Catal. 2005, 347, 712–714

Synthesis of b-Phenylselenocarbonyl Compounds
UPDATES
Table 1. In-TMSCl-promoted cleavage of diphenyl disele-
nide and addition to conjugated alkenes.
In conclusion, this In-TMSCl-promoted one-pot pro-
cedure for the Michael addition of diphenyl diselenide
to conjugated alkenes in the presence of indium metal
and trimethylsilyl chloride provides an efficient meth-
odology for the synthesis of b-phenylseleno carbonyl
compounds and nitriles. Certainly this method offers
significant advantages with regard to operation, yield,
time and handling of reagents and thus presents a prac-
tical alternative to the existing procedures.[3] Moreover,
this procedure demonstrates the synthetic potential of
the indium-trimethylsilyl chloride reagent system which
has not been explored to a great extent.
Experimental Section
General Experimental Procedure. Representative
Example for the Michael Addition of Diphenyl
Diselenide to Methyl Acrylate (entry 4)
A solution of diphenyl diselenide (344 mg, 1.1 mmol) and
methyl acrylate (172 mg, 2 mmol) in dry acetonitrile (3 mL)
was sonicated in an ultrasonic bath (Eyela, Japan) in the pres-
ence of indium metal (138 mg, 1.2 mmol, finely cut into small
pieces) and freshly distilled trimethylchlorosilane (540 mg,
2.5 mmol) for 3 h (monitored by TLC). The reaction mixture
was then quenched with water or saturated ammonium chlor-
ide solution and extracted with Et2O (3ꢀ10 mL). The ether ex-
tract was washed with brine and dried (Na2SO4). Evaporation
of solvent left the crude product which was purified by column
chromatography (hexane:Et2O, 95:5) to provide the pure addi-
tion product, 3-phenylselenomethyl propanoate, as a pale yel-
low oil; yield: 403 mg (83%). The product was easily identified
by comparison of its spectroscopic data (IR, 1H and 13C NMR)
with those reported.3f
This procedure was followed for all the reactions listed in Ta-
ble 1. All the products are adequately characterized by their
1
spectroscopic data (IR, H and 13C NMR). These values for
the known compounds are in good agreement with those re-
ported (Table 1). The spectroscopic data for new compounds
which are not available in the literature are provided here.
Methyl 2-methyl-3-phenylselenopropanoate (entry 6): Col-
[a]
orless oil; Rf ¼0.60; IR (neat): n¼1735, 1434, 1207, 736 cmꢁ1
;
Yields refer to pure isolated products characterized by
1
spectroscopic data (IR, H and 13C NMR).
1H NMR (300 MHz, CDCl3): d¼1,27 (d, J¼6.99 Hz, 3 H),
2.71–2.78 (m, 1H), 2.90–2.96 (m, 1H), 3.17–3.23 (m, 1H),
3.64 (s, 3H), 7.24–7.28 (m, 3H), 7.50–7.53 (m, 2H); 13C NMR
(75 MHz, CDCl3): d¼18.0, 31.2, 40.7, 52.1, 127.5, 129.4 (2C),
129.5, 133.5 (2C), 175.8; anal. calcd. for C11H14O2Se: C 51.37,
lenide forms an intermediate, PhSeSiMe3 with trime- H 5.49; found: C 51.29, H 5.56.
thylsilyl chloride in presence of indium metal[7] which fa-
cilitates the transfer of phenylselenate to the conjugated
alkene.
The effect of ultrasound to carry out this reaction is
also important. Without ultrasound and under room
temperature stirring only a marginal reaction (10%)
was observed. Under reflux for a prolonged period the
reaction was found to proceed; however, it was not
very clean being associated with undesirable side prod-
ucts.
Isopropyl 3-phenylselenopropanoate (entry 7): Colorless
1
oil; Rf ¼0.65; IR (neat): n¼736, 1107, 1222, 1732 cmꢁ1; H
NMR (300 MHz, CDCl3): d¼1.24 (d, J¼6.39 Hz, 6H), 2.69
(t, J¼7.43 Hz, 2H), 3.11 (t, J¼7.43 Hz, 2H), 4.99–5.07 (m,
1H), 7.26–7.29 (m, 3H), 7.52–7.55 (m, 2H); 13C NMR
(75 MHz, CDCl3): d¼22.1 (2C), 22.2, 35.9, 68.5, 127.6, 129.4
(2C), 129.5, 133.6 (2C), 172.0; anal. calcd. for C12H16O2Se: C
53.14, H 5.95; found: C 53.11, H 5.99.
Methyl 3-phenylselenolbutanoate (entry 8): Yellowish oil;
Rf ¼0.65; IR (neat): n¼1735, 1434, 1211, 736 cmꢁ1; 1H NMR
(300 MHz, CDCl3): d¼1.44 (d, J¼6.82 Hz, 3H), 2.53–2.61
Adv. Synth. Catal. 2005, 347, 712–714
asc.wiley-vch.de
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
713

Brindaban C. Ranu, Arijit Das
UPDATES
(m, 1H), 2.67–2.74 (m, 1H), 3.59–3.70 (m, 1H), 3.66 (s, 3H),
7.24–7.31 (m, 3H), 7.56–7.64 (m, 2H); 13C NMR (75 MHz,
CDCl3): d¼21.8, 33.7, 42.6, 51.7, 127.9, 128.9 (2C), 129.0,
135.5 (2C), 172.0; anal. calcd. for C11H14O2Se: C 51.37, H
5.49; found: C 51.30, H 5.56.
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Ethyl 3-phenylselenobutanoate (entry 9): Colorless oil; Rf ¼
0.62; IR (neat): n¼736, 1022, 1473, 1732 cmꢁ1
;
1H NMR
(300 MHz, CDCl3): d¼1.25 (t, J¼7.11 Hz, 3H), 1.44 (d, J¼
7.11 Hz, 3H), 2.52–2.60 (m, 1H), 2.63–2.73 (m, 1H), 3.61–
3.68 (m, 1H), 4.13 (q, J¼7.11 Hz, 2H), 7.25–7.31 (m, 3H),
7.57–7.63 (m, 2H); 13C NMR (75 MHz, CDCl3): d¼14.5,
22.2, 34.2, 43.1, 60.9, 128.0, 129.3 (2C), 129.4, 135.9 (2C),
171.9; anal. calcd. for C12H16O2Se: C 53.14, H 5.95; found: C
53.10, H 5.98.
Isopropyl 3-phenylselenobutanoate (entry 10): Colorless
1
oil; Rf ¼0.55; IR (neat): n¼740, 1107, 1728 cmꢁ1; H NMR
(300 MHz, CDCl3): d¼1.26 (d, J¼5.99 Hz, 6H), 1.43 (d, J¼
6.93 Hz, 3H), 2.48–2.56 (m, 1H), 2.62–2.69 (m, 1H), 3.57–
3.67 (m, 1H), 4.98–5.06 (m, 1H), 7.25–7.33 (m, 3H), 7.57–
7.62 (m, 2H); 13C NMR (75 MHz, CDCl3): d¼22.1 (2C), 22.2,
34.2, 43.4, 68.3, 128.2, 129.3 (2C), 129.5, 135.9 (2C), 171.4;
anal. calcd. for C13H18O2Se: C 54.74, H 6.36; found: C 54.70,
H 6.40.
Acknowledgements
We are pleased to acknowledge the financial support from
CSIR, New Delhi [Grant No. 01(1739)/02] for this investigation.
A. D. is also thankful to CSIR for his fellowship.
References and Notes
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Org. Chem. 2004, 69, 5793–5795.
[7] Although the formation of PhSeSiMe3 by the reaction of
PhSeSePh with Me3SiCl under sonication in the presence
of In metal is indicated by TLC (compared with that of
authentic sample) we failed to isolate the pure compound
after work-up. Probably, the PhSeSiMe3 formed is not
very stable under the reaction conditions and reacts in-
stantaneously with the conjugated alkene.
[2] a) D. Liotta, P. B. Paty, J. Johnston, G. Zima, Tetrahedron
Lett. 1978, 19, 5091–5094; b) A. Krief, L. Hevesi, in: Or-
714
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asc.wiley-vch.de
Adv. Synth. Catal. 2005, 347, 712–714