Efficient synthesis of selenol esters from acid chlorides mediated by indium metal

Article abstract of DOI:10.1016/j.tet.2009.03.069

This article describes an efficient and easy one-pot route for the synthesis of a wide range of selenol esters from acyl chloride with diselenides in the presence of indium metal. A variety of functional groups can be tolerated within the diorgano diselenide and the acyl chloride coupling partner.

Full text of DOI:10.1016/j.tet.2009.03.069

Tetrahedron 65 (2009) 4614–4618
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Efficient synthesis of selenol esters from acid chlorides mediated by indium metal
,
b
,
a
a
a
Graciane Marin a, Antonio L. Braga a , Anderson S. Rosa , Fabio Z. Galetto , Robert A. Burrow ,
*
´
,
c
Hugo Gallardo b, Marcio W. Paixa˜o a
a
´
Departamento de Quımica, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil
b Departamento de Qu´ımica, Universidade Federal de Santa Catarina, Brazil
c Instituto de Qu´ımica, Universidade de S˜ao Paulo, SP 05508-900, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
This article describes an efficient and easy one-pot route for the synthesis of a wide range of selenol
esters from acyl chloride with diselenides in the presence of indium metal. A variety of functional groups
can be tolerated within the diorgano diselenide and the acyl chloride coupling partner.
Ó 2009 Elsevier Ltd. All rights reserved.
Received 13 February 2009
Received in revised form 21 March 2009
Accepted 23 March 2009
Available online 1 April 2009
1. Introduction
Selenol esters are usually available by the reaction of acylhalides
with selenols13 or dichalcogenides,14 as well as their alkali metal
Great advances on organoselenium chemistry have been made
during the last decades. Selenium compounds have shown an im-
portant role in organic chemistry, acting as versatile and useful
reagents in organic synthesis1 as well as in asymmetric catalysis.2
In this way, organoselenium compounds have emerged as an ex-
ceptional class of structures due to their pivotal role in the syn-
salts.15 In addition, carboxylic acids are also transformed into thiol
and selenol esters by treatment with arylselenocyanates and
tributyl phosphine in dichloromethane.16 Group IIIA organyl chal-
cogenides (B and Al) convert carboxylic acid esters into their sele-
nol analogues.17 Also, aldehydes react under Tishchenko-type
conditions to afford these compounds.18 Miscellaneous methods
are summarized in Ref. 19.
It is well known that the selenium anions are generated in situ
via chemical Se–Se bonds’ cleavage to avoid handling unstable
reagents such as selenols. Thus, research to improve these trans-
formations is of current interest20 as observed in the reports
concerning use of indium iodide(I) for the cleavage of dis-
elenides.21 In recent years, more attention has been paid to the
development of new synthetic methods using indium metal due to
its remarkable efficiency in various synthetic operations, unique
properties, such as stability toward air and moisture compared
with other metals, its nontoxic nature, and its availability in pure
form.22
thesis of
a large number of biological compounds (e.g.,
selenocarbohydrates, selenoamino acids, and selenopeptides).3
2. Results and discussion
In this context, selenol esters are important intermediates in
several organic transformations. Selenol esters have been used as
precursors of acyl radicals4 and anions,5 mild acyl transfer re-
agents,6 intermediates in the synthesis of ketones,7 and for asym-
metric aldol reactions.8 In addition to their synthetic applications,
these compounds have also attracted considerable attention for the
design, synthesis, and investigation of new molecular materials,
especially for conducting or superconducting materials and for
liquid crystals.9 Applications of this class of compounds have been
expanded into the synthesis of proteins by chemical ligation of
chalcogenol esters10 as well as substrates to undergo facile and
efficient radical decarbonylation in the synthesis of the alkaloid
(þ)-geissoschizine.11 Therefore, a convenient method for the syn-
thesis of these compounds with stable reagents under neutral
conditions is still called for.12
As part of our studies with indium mediated reactions, we re-
cently reported the synthesis of a new set of chiral
a-seleno-ami-
nes23a and -seleno-amides23b in straightforward procedures
b
involving stereoselective ring-opening reactions with indium(III)-
chalcogenolates, obtained from indium iodide(I) and diorganoyl
diselenides. Additionally, by these methods, it was possible to
synthesize various selenocysteine derivatives in good to excellent
yields.23 Thus, we propose herein a simple experimental procedure,
with metallic indium system, easy to handle, less expensive than
those with indium(I), and active enough to promote the direct
coupling of diselenides and acyl chlorides21a,b,24 (Scheme 1). The
study resulted in an efficient synthesis of selenol ester derivatives
under mild and neutral conditions.
* Corresponding author. Tel.: þ55 55 32208761; fax: þ55 55 32208998.
E-mail address: albraga@quimica.ufsm.br (A.L. Braga).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.03.069

G. Marin et al. / Tetrahedron 65 (2009) 4614–4618
4615
O
O
In°/ (R2Se)2
solvent
reflux, 12h
Table 2
R1
SeR2
Indium cleavage of diorganyl diselenides to selenol esters
R1
Cl
O
O
1
2
In°
R2SeSeR2
+
R1
SeR2
2b-m
R1
Cl
1a-g
Scheme 1. General synthesis of selenol esters.
CH2Cl2
Reflux, 12h
Entry
1
R1
R2
Product
Yielda (%)
The conditions for carrying out the reaction were optimized by
using benzoyl chloride and PhSeSePh in the presence of indium
metal in different solvents (Table 1).
The first experiment was performed using CH2Cl2 and 1.0 equiv
of indium metal and the desired product was obtained in 86% yield
(Table 1, entry 1).
O
Ph, 1a
o-ClPh
Ph
Se
91
Cl
2b
When dioxane was used as solvent a small decrease in the yield
compared with DCM was observed, affording the corresponding
product in 83% yield (entries 1 vs 2). A number of different solvents,
including DMF, THF, and DMSO, were also investigated, and they
were all less effective than dichloromethane (entries 3–5). Sub-
sequently, the amount of Inꢀ was reduced to 0.8 mol equiv yielding
2a in 64% in relation to benzoyl chloride (entry 6).
Using the optimized conditions, the scope and limitations of this
new methodology were examined as shown in Table 2. A variety of
diorganyl diselenides reacted with benzoyl chloride to generate the
selenol esters in good to excellent yields. Electronic effects showed
a remarkable influence in this reaction; electron withdrawing aryl
diselenides and benzoyl chloride reacted easily (Table 2, entries 1
and 3) while electron rich aryl diselenides, which have a stronger
Se–Se bond, gave the corresponding selenol ester in lower yields
(entries 2 and 4). It is well known that diaryl diselenides are more
reactive than aliphatic ones, and much more easily cleaved.25 We
also extended this method to prepare selenol ester starting from
aliphatic diselenides. Applying the same methodology and using
dibenzyl diselenide as source of selenolate anion, the coupling re-
action with benzoyl chloride furnished the desired product in good
yield (entry 5) whereas using diethyl diselenide as selenium source,
the product was obtained in satisfactory yield (entry 6).
O
2
3
Ph, 1a
Ph, 1a
o-MePh
p-ClPh
65
90
Ph
Se
2c
Cl
O
Ph
Se
2d
OMe
O
4
5
Ph, 1a
Ph, 1a
p-OMePh
58
80
Ph
Se
2e
O
Ph
Se
2f
Bn
O
The combination of a wide range of acyl chlorides with diphenyl
diselenide was also checked in our reaction system (Table 2, entries
7–11). Electron withdrawing substituent attached at the benzoyl
chloride moiety showed a negative effect in the yields, affording the
desired products in moderated yields (entries 7 and 8). The ability
to couple alkyl groups prompted further exploration of this re-
action. By using 2,2-dimethyl-propionyl chloride 1d afforded the
product in a low yield (entry 9), while the similar 3-chloro-2,2-
dimethylpropanoyl chloride 1e furnished the corresponding sele-
nol ester in satisfactory yield (entry 10). Unfortunately, acetyl
Se
6
7
8
Ph, 1a
Et
69
66
63
2g
Cl
O
SePh
o-ClPh, 1b
Ph
Ph
2h
O
Table 1
SePh
Optimization of the reaction conditionsa
p-NO2Ph, 1c
O2N
O
O
In°/ (PhSe)2
2i
Ph
Se
Ph
Cl
Solvent
Reflux,12h
1a
2a
O
Entry
Solvent
Yieldb (%)
9
t-Bu, 1d
Ph
Ph
34
55
SePh
1
2
3
4
CH2Cl2
1,4-Dioxane
DMF
THF
DMSO
CH2Cl2
86
83
62
62
51
64
2j
O
5
6c
10
ClCH2CMe2, 1e
Cl
SePh
a
Reaction was performed using benzoyl chloride, 1 mol equiv of Inꢀ and
0.5 mol equiv of diphenyl diselenide at reflux for 12 h.
2k
b
Isolated yield.
Reaction was performed using 0.8 mol equiv of Inꢀ.
(continued on next page)
c

4616
G. Marin et al. / Tetrahedron 65 (2009) 4614–4618
Table 2 (continued )
radical and indium(I) chloride salt. The acyl radical thus formed
reacts with (PhSe)2 in an SH2 reaction affording respective selenol
Entry
R1
R2
Product
Yielda (%)
esters (Scheme 2).28
O
Exploratory experiments revealed the ability of the Fmoc
modified substrate 2m as an efficient protecting group for selenium
organic coumpounds.29 As depicted in Scheme 3, the Fmoc group
was removed in DMF using piperidine as base furnishing diphenyl
diselenide in 85% yield.
11
Me, 1f
Ph
d
SePh
2l
O
O
O
SePh
12
Ph
>99
O
1g
1) piperidine, DMF
2) Air, 3 h
O
SePh
2m
CO2
(PhSe)
+
+
2
a
Yields related to pure isolated products characterized by spectroscopic data.
2m
Scheme 3.
3. Conclusion
In summary, a simple efficient and broadly applicable general
method for the preparation of selenol esters from readily avail-
able and inexpensive starting materials is reported. Features of
this method include the following: (i) easily accessible acylating
agents were used; (ii) metal indium is stable toward air and
moisture, its nontoxic nature, available in pure form; (iii) neutral
conditions; (iv) various functional groups can be tolerated
within the diorgano diselenide and/or the acyl chloride coupling
partner; (v) good to excellent yields of selenol esters were
obtained. Studies dealing with the application of this method-
ology in the synthesis of liquid crystals and application of
selenol esters as appropriated protecting groups for biologically
relevant selenium compounds are currently in progress in our
laboratory.
Figure 1. X-ray structure of 2m. Selected bond distances: (Å): Se1–C15 1.9288(12),
Se1–C21 1.9224(12), C15–O1 1.3304(14), C15–O2 1.2030(15), C15–Se1–C21 101.13(15),
Se1–C15–O1 112.29(8), O1–C15–O2 126.27(11), Se1–C15–O2 121.42(9), O1–C1–C2
106.78(9), C21–Se1–C15–O1 ꢁ1.41(9); C2–C1–O1–C15 ꢁ170.84(9).
chloride 1f did not produce the desired selenol ester (entry 11). As
a further extension, we attempted to synthesize selenocarbonate
2m bearing interesting functionalities. To our delight, when we
used 9-fluorenylmethyl chloroformate and benzyl chloroformate,
the corresponding selenocarbonate 2m was obtained in quantita-
tive yield (entry 12).
The selenocarbonate 2m was confirmed by a single crystal X-ray
study of the crystalline solid. The molecular structure is shown in
Figure 1 with selected bond lengths in the caption of the figure.
There are very few examples of structural studies of compounds
containing the selenocarbonate moiety. Just two metallo-seleno-
carbonates have been reported in literature.26 This is the first or-
ganic selenocarbonate structure reported. The bond lengths and
angles within the organic parts of 2m are normal. The selenocar-
bonate moiety adopts a synperiplanar conformation around the
oxygen atom and antiperiplanar around the selenium atom. This
contrasts to the syn/syn conformation for the similar dimethyl
thiocarbonate.27
4. Experimental section
IR spectra were recorded in the range of 4000–600 cmꢁ1 using
a Nicolet Magna 550 Spectrometer, and were measured as KBr or as
neat oils. 1H and 13C NMR spectra were recorded at 400 and
100 MHz, respectively, with tetramethylsilane as internal standard.
High-resolution mass spectra were measured at the Institute of
Plant Biochemistry, Halle-Saale, Germany, with a Bruker BioApex
70e FT-ICR (Bruker Daltonics, Billerica, USA) instrument in ESI
mode. Melting points were determined on an MQ APF – 302 digital
melting point apparatus and are uncorrected. Column chromato-
graphy was performed using Merck Silica Gel (230–400 mesh)
following the methods described by Still et al.30 Thin layer chro-
matography (TLC) was performed using Merck Silica Gel GF254
,
0.25 mm thickness. For visualization, TLC plates were either placed
under ultraviolet light, or stained with iodine vapor, or acidic
vanillin. Dichloromethane was refluxed under P2O5 and after dis-
tilled. The diselenides were conveniently prepared from classical
procedures.31 Temperatures above room temperature were main-
tained by use of a mineral oil bath with an electrically heated coil
connected to a Variac controller.
The reaction pathway for the formation of acyl phenyl selenides
is believed to occur firstly through the single-electron transfer
(SET) from indium to acyl chloride with generation of an acyl
O
O
In0
4.1. General procedure for the synthesis of selenol esters
InCl
+
R
Cl
R
In a two neck flask, equipped with reflux condenser, under an
argon atmosphere, indium powder (1 mmol, 0.115 g), appropri-
ate diselenide (0.5 mmol) and acyl chloride (1 mmol) were stir-
red in dry dichloromethane (8 mL) at reflux for 12 h. After this
time, the mixture was cooled to room temperature and
quenched with a solution of HCl 1 M, extracted with CH2Cl2 and
the combined organic fractions were collected, dried over MgSO4
PhSeSePh
O
R
SePh
Scheme 2. Proposed mechanism for the synthesis of selenol esters.

G. Marin et al. / Tetrahedron 65 (2009) 4614–4618
4617
and filtered; the solvent was then removed in vacuo yielding
the crude products 2a–m, which were purified by flash
chromatography.
5H, Ph). 13C NMR (CDCl3, 100 MHz):
d
¼190.1 (CO); 136.3 (Ph); 135.7
(Ph); 135.0 (Ph); 132.3 (Ph); 131.5 (Ph); 130.9 (Ph); 129.1 (Ph); 128.6
(Ph); 127.7 (Ph); 126.5 (Ph). HRMS-ESI m/z calcd for
C13H9ClOSeþNaþ 318.9404, found 318.9411.
4.1.1. Se-Phenyl selenobenzoate 2a
Yield: 0.224 g (86%); yellow solid, mp 37–38 ꢀC, IR (KBr)
4.1.9. Se-Phenyl 4-nitro selenobenzoate 2i
1685 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
¼7.94–7.92 (m, 2H, Ph);
7.63–7.58 (m, 3H, Ph); 7.50–7.42 (m, 5H, Ph). 13C NMR (CDCl3,
100 MHz):
Yield: 0.193 g (63%); yellow solid; mp 136–138 ꢀC, IR (KBr)
1741 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
¼8.35–8.33 (m, 2H, Ph);
8.17–8.00 (m, 2H, Ph); 7.66–7.40 (m, 2H, Ph); 7.30–7.23 (m, 3H, Ph).
13C NMR (CDCl3, 100 MHz):
d
¼193.7 (CO); 138.9 (Ph); 138.4 (Ph); 136.7 (Ph); 134.2
(Ph); 129.7 (Ph); 129.4 (Ph); 129.3 (Ph); 127.7 (Ph); 126.1 (Ph).
HRMS-ESI m/z calcd for C13H10OSeþNaþ 284.9794, found
284.9788.
d
¼192.5 (CO); 150.6 (Ph); 143.0 (Ph);
136.1 (Ph); 131.5 (Ph); 129.6 (Ph); 128.1 (Ph); 124.9 (Ph); 124.2 (Ph).
HRMS-ESI m/z calcd for C13H9NO3SeþNaþ 329.9645, found
329.9639.
4.1.2. Se-2-Chlorophenyl selenobenzoate 2b
Yield: 0.269 g (91%); yellow liquid; IR (liquid film) 1685 cmꢁ1
;
4.1.10. Se-Phenyl 2,2-dimethylpropaneselenoate 2j
1H NMR (CDCl3, 400 MHz):
(CDCl3, 100 MHz):
d
¼7.93–7.24 (m, 9H, Ph). 13C NMR
Yield: 0.08 g (34%); brown oil; IR (liquid film) 1731 cmꢁ1 1H
;
d
¼191.4 (CO); 138.7 (Ph); 137.8 (Ph); 133.6 (Ph);
NMR (CDCl3, 400 MHz):
d
¼7.49–7.46 (m, 2H, Ph); 7.37–7.33 (m, 3H,
130.8 (Ph); 130.3 (Ph); 129.9 (Ph); 129.3 (Ph); 129.1 (Ph); 128.9
(Ph); 127.4 (Ph). HRMS-ESI m/z calcd for C13H9ClOSeþNaþ
318.9405, found 318.9409.
Ph); 1.29 (s, 9H, (CH3)3). 13C NMR (CDCl3, 100 MHz):
d¼207.9 (CO);
136.4 (Ph); 129.1 (Ph); 128.8 (Ph); 126.4 (Ph); 50.0 (C(CH3)3); 27.2
((CH3)3). HRMS-ESI m/z calcd for C11H11OSeþNaþ 265.0107, found
265.0113.
4.1.3. Se-o-Tolyl selenobenzoate 2c
Yield: 0.178 (65%); yellow liquid; IR (liquid film) 1685 cmꢁ1; 1H
4.1.11. Se-Phenyl 3-chloro-2,2-dimethylpropaneselenoate 2k
NMR (CDCl3, 400 MHz):
d
¼7.96–7.80 (m, 2H, Ph); 7.50–7.20 (m,
Yield: 0.151 g (55%); yellow liquid; IR (liquid film) 1700 cmꢁ1; 1H
7H, Ph); 2.35 (s, 3H, Me). 13C NMR (CDCl3, 100 MHz):
d
¼192.7
NMR (CDCl3, 400 MHz):
d
¼7.49–7.35 (m, 5H, Ph); 3.64 (s, 2H, CH2);
(CO); 142.5 (Ph); 138.6 (Ph); 137.7 (Ph); 133.7 (Ph); 130.4 (Ph);
129.8 (Ph); 128.8 (Ph); 127.2 (Ph); 127.2 (Ph); 126.5 (Ph); 22.9
(CH3). HRMS-ESI m/z calcd for C14H12OSeþNaþ 298.9951, found
298.9958.
1.38 (s, 6H, C(CH3)2). 13C NMR (CDCl3, 100 MHz):
d
¼204.8 (CO);
135.8 (Ph); 128.9 (Ph); 128.5 (Ph); 125.2 (Ph); 53.9 (CH2); 51.0
(C(CH3)2); 22.8 ((CH3)2). HRMS-ESI m/z calcd for C11H13ClOSeþNaþ
298.9717, found 298.9712.
4.1.4. Se-4-Chlorophenyl selenobenzoate 2d
4.1.12. O-(9H-Fluoren-9-yl)methyl Se-phenyl carbonoselenoate 2m
Yield: 0.266 g (90%); yellow solid; mp 84–85 ꢀC, IR (KBr)
Yield: 0.379 g (100%); yellow solid; mp 113.1–114.6 ꢀC; IR (KBr)
1690 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
¼7.91–7.89 (m, 5H, Ph);
7.61–7.59 (m, 2H, Ph); 7.50–7.37 (m, 2H, Ph). 13C NMR (CDCl3,
100 MHz):
1772 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
¼7.78–7.26 (m, 13H, Ph);
4.53 (d, J¼7.6 Hz, 2H, CH2); 4.12 (t, J¼7.2 Hz, 1H, CH). 13C NMR
d
¼192.4 (CO); 138.2 (Ph); 137.9 (Ph); 136.4 (Ph); 133.7
(CDCl3, 100 MHz):
d
¼166.5 (CO); 134.8 (Ph); 129.3 (Ph); 128.1 (Ph);
(Ph); 129.2 (Ph); 128.6 (Ph); 127.0 (Ph); 123.6 (Ph). HRMS-ESI m/z
calcd for C13H9ClOSeþNaþ 318.9404, found 318.9410.
127.4 (Ph); 126.9 (Ph); 124.9 (Ph); 119.9 (Ph); 64.9 (CH2); 50.2 (CH).
HRMS-ESI m/z calcd for C21H16O2SeþNaþ 403.0213, found
403.0216.
4.1.5. Se-4-Methoxyphenyl selenobenzoate 2e
Yield: 0.169 g (58%); white solid; mp 60–62 ꢀC, IR (KBr)
Acknowledgements
1675 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
¼7.93–7.90 (m, 2H, Ph);
7.59–7.37 (m, 3H, Ph); 6.96–6.94 (m, 2H, Ph); 6.80–6.78 (m, 2H, Ph);
3.82 (s, 3H, CH3). 13C NMR (CDCl3, 100 MHz):
The authors gratefully acknowledge CAPES and CNPq for a fi-
nancial support and fellowships to G. Marin and F.Z. Galetto. M.W.
Paixa˜o also acknowledges FAPESP for a scholarship. The Bruker X8
Kappa APEX II single crystal diffractometer was purchased with
funding provided by FINEP (Brazil).
d
¼194.2 (CO); 160.4
(Ph); 137.8 (Ph); 135.4 (Ph); 134.5 (Ph); 133.7 (Ph); 128.9 (Ph); 127.3
(Ph); 114.3 (Ph); 55.7 (CH3). HRMS-ESI m/z calcd for
C14H12O2SeþNaþ 314.9900, found 314.9904.
4.1.6. Se-Benzyl selenobenzoate 2f
Yield: 0.220 g (80%); yellow liquid; IR (liquid film) 1664 cmꢁ1
;
Supplementary data
1H NMR (CDCl3, 400 MHz):
3H, Ph); 7.24–7.17 (m, 5H, Ph); 4.30 (s, 2H, CH2); 13C NMR (CDCl3,
100 MHz):
d
¼7.87–7.84 (m, 2H, Ph); 7.49–7.32 (m,
General experimental procedures, IR, HRMS, 1H, and 13C NMR
spectral data for all isolated compounds. This material is available
free of charge via the Internet at http://sciencedirect.com. CCDC
681177 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
d
¼194.5 (CO); 138.9 (Ph); 138.7 (Ph); 133.6 (Ph); 128.9
(Ph); 128.9 (Ph); 128.7 (Ph); 127.1 (Ph); 126.9 (Ph); 29.1 (CH2).
HRMS-ESI m/z calcd for C14H12OSeþNaþ 298.9951, found
298.9945.
4.1.7. Se-Ethyl selenobenzoate 2g
Yield: 0.147 (69%); brown liquid; IR (liquid film) 1660 cmꢁ1; 1H
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2009.03.069.
NMR (CDCl3, 400 MHz):
d
¼7.90–7.40 (m, 5H, Ph); 3.08 (q, 2H, CH2);
1.50 (t, 3H, CH3). 13C NMR (CDCl3, 100 MHz):
d¼195.0 (Ph); 138.8
(Ph); 133.2 (Ph); 130.2 (Ph); 127.0 (Ph); 19.4 (CH2); 15.8 (CH3).
References and notes
HRMS-ESI m/z calcd for C9H10OSeþNaþ 236.9794, found 236.9789.
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4.1.8. Se-Phenyl 2-chlorobenzoselenoate 2h
Yield: 0.195 g (66%); yellow solid; mp 59 ꢀC, IR (KBr) 1741 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d¼7.65–7.59 (m, 4H, Ph); 7.37–7.18 (m,

4618
G. Marin et al. / Tetrahedron 65 (2009) 4614–4618
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