Organoselenosilane-mediated selective mild access to selenolesters, selenoanhydrides and diacyl diselenides

Article abstract of DOI:10.1055/s-0030-1261195

Reaction of acyl chlorides with phenylselenotrimethyl-silane promoted by TBAF afforded a mild general access to selenolesters in good yields. When acyl chlorides were reacted with bis(trimethylsilyl)selenide (HMDSS) in 2:1 or 1:1 ratio a selective entry t

Full text of DOI:10.1055/s-0030-1261195

2248
LETTER
Organoselenosilane-Mediated Selective Mild Access to Selenolesters,
Selenoanhydrides and Diacyl Diselenides
O
rganoselenosilan
n
e
-Mediated S
t
electiv
o
e
Mild
A
cce
n
ss to Selenol
e
esters lla Capperucci,* Alessandro Degl’Innocenti,* Caterina Tiberi
Department of Chemistry ‘Ugo Schiff’, University of Florence, Via della Lastruccia 3-13, 50019 Sesto Fiorentino (Firenze), Italy
Fax +39(055)4573585; E-mail: alessandro.deglinnocenti@unifi.it
Received 20 June 2011
Dedicated to Professor Alfredo Ricci with admiration, respect, and best wishes on the occasion of his retirement
equivalents of a dithiolane carbanion, a species that can-
Abstract: Reaction of acyl chlorides with phenylselenotrimethyl-
not be directly generated upon metalation.
silane promoted by TBAF afforded a mild general access to selenol-
esters in good yields. When acyl chlorides were reacted with
bis(trimethylsilyl)selenide (HMDSS) in 2:1 or 1:1 ratio a selective
entry to selenoanhydrides or diacyl diselenides respectively was ob-
tained.
In addition, the functionalization of the S–Si bond led us
to access thiocarbonyl compounds,21 or more recently to
transfer a thiol moiety onto ring-strained heterocycles
such as epoxides.22 In recent years also the reactivity of
the Se–Si bond was explored in the possible generation of
selenocarbonyl compounds,23 seleno heterocycles and
diselenides.24
Key words: selenosilanes, selenolesters, diacyl selenides, diacyl
diselenides, fluoride ion
In this context, we thought that selenosilanes could be-
have efficiently as synthetic equivalents of unstable sele-
nols, capable of being easily handled and to release, upon
treatment with appropriate catalysts, nucleophilic species,
able to transfer a seleno group onto different electrophiles.
The chemistry of organoselenium compounds has recent-
ly faced a strong development, due to the fact that several
compounds of this class have been demonstrated to be
versatile reagents in organic synthesis1 and, more recent-
ly, in asymmetric catalysis.2 They also have been effi-
ciently used in the synthesis of molecules with biological
activity,3 steroids and sex hormones.4
With this concept in mind we first wanted to test the abil-
ity of selenosilanes in transferring an organo-selenyl moi-
ety, and we reacted benzoyl chloride (1a) with PhSeSiMe3
(2) under the influence of fluoride ion as a test reaction
(Scheme 1). The reaction proved quite efficient affording
as the only product the selenolester 3a in almost quantita-
tive yield (95%; Scheme 1).
In this context selenolesters have been shown as useful in-
termediates in synthetic organic chemistry. These mole-
cules have in fact been used as precursors of acyl radicals5
and anions,6 reagents for the transfer of acyl moieties7 in
rather mild conditions, in the synthesis of ketones8 and
asymmetric aldol reactions.9 Various synthetic methods
for selenolesters have been reported and usually are based
on the reactions of acyl chlorides or acid anhydrides with
selenols,10 diselenides11 or their metal selenoates,12 as
well as aryl tributylstannyl selenides13a–d and phenylsele-
notris(trimethylsilyl)silane13e have been used. Alkenyl
and alkynyl selenides behave as efficient precursors,14
while selenocyanates and tributylphosphine have been
used to produce selenolesters from carboxylic acids.15
O
O
F–
PhSeSiMe3
+
SePh
Cl
1a
2
3a
Scheme 1
Then, with the aim to evaluate the limits and the potential
of this reaction we extended this reactivity to different
acyl chlorides: this investigation led to the disclosure of a
general and simple methodology to access selenolesters.25
In addition, several papers have recently appeared on their
synthesis mediated by indium metal,16 or in ionic liq-
uids.17 Some other methods are also present in the litera-
ture.18
Examples of this reactivity are summarized in Table 1.
As can be seen from the Table 1, reactions run smoothly
with both aromatic (entries 1–4) and aliphatic acyl chlo-
rides (entries 5 and 6). Interestingly, the reaction occurs
efficiently even on functionalized acyl chlorides, such as
a-chloro propenoyl chloride (entry 6).
We have been interested for a long time in the generation
of synthetic equivalents of nucleophilic species through
the functionalization of the C–Si bond.19
In this context we recently reported the reactivity of sily-
lated dithiolanes toward different electrophiles,20 thus
showing that such molecules can behave as synthetic
It is also noteworthy that the reactions can also be effi-
ciently performed in the presence of phenoxide ion as the
catalyst, with similar results.
Thus, having demonstrated the efficiency of selenosilanes
in transferring a seleno moiety, we moved toward the
functionalization of a more interesting molecule, hexa-
SYNLETT 2011, No. 15, pp 2248–2252
Advanced online publication: 24.08.2011
DOI: 10.1055/s-0030-1261195; Art ID: S05511ST
© Georg Thieme Verlag Stuttgart · New York
x
x
.x
x
.2
0
1
1

LETTER
Organoselenosilane-Mediated Selective Mild Access to Selenolesters
2249
methyldisilaselenane (HMDSS),26 that could have led to
the synthesis of diacyl selenides, another related interest-
ing class of compounds. Such molecules are very efficient
transfer reagents for acyl and aroyl groups.
O
O
O
F–
2
+
Me3SiSeSiMe3
Cl
Se
1a
5a
4
Table 1 Synthesis of Selenolesters 3 and 77Se NMR Chemical
Scheme 2
Shifts
Table 2 Preparation of Selenoanhydrides 5 and Diacyl Diselenides
6
O
O
F–
or PhO–
PhSeSiMe3
+
R
SePh
3a–f
R
Cl
Entry
R
RCOCl/HMDSS Product Yield (%)
2
1a–f
1
2
Ph
2:1
2:1
2:1
2:1
2:1
1:1
1:1
1:1
1:1
1:1
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
80
76
75
50
70
83
78
71
54
73
Entry
R
Product
Yield (%)a 77Se NMR (d)
4-ClC6H4
4-MeOC6H4
MeCHCl
2-thienyl
Ph
1
2
3
4
5
6
Ph
3a
3b
3c
3d
3e
3f
95
75
70
71
61
63
637 ppm
638 ppm
624 ppm
679 ppm
655 ppm
651 ppm
3
4-ClC6H4
4-MeC6H4
2-F3CC6H4
n-Pr
4
5
6
7
4-ClC6H4
4-MeOC6H4
MeCHCl
2-thienyl
n-Pr
8
a Based on isolated compounds
9
Despite their synthetic interest, the synthesis of diacyl se-
lenides and especially diacyl diselenides has been scarce-
ly reported.
10
Even more interesting appeared the reactivity with sto-
ichiometric ratios of acyl chlorides and HMDSS, that af-
forded in very good yields the corresponding diacyl
diselenides (Scheme 3),31 probably arising from oxidation
of the intermediate selenocarboxylic acid (derived from
trimethylsilyl selenolester) in the workup procedure.32
Again, this methodology was extended to different sub-
strates, thus showing its generality. Results are reported in
Table 2 (entries 6–10).
Some methods have been described along the years,27 but
they are affected by several drawbacks, such as the use of
expensive and unstable reagents, the limited availability
of the starting materials, the difficulty in purification, par-
ticularly evident for diacyl selenides and diselenides, and
the high number of steps required.
Diacyl selenides have been obtained from selenoamides,
in turn obtained from arylnitriles and sodium hydrose-
lenide, with acyl chlorides. The yields were satisfactory,
but the method required a tedious preparation of seleno-
amides, which were very unstable.28 More recently
Koketsu, Ishihara and co-workers reported the synthesis
of LiAlHSeH a useful selenating reagent for the synthesis
of a wide range of selenium-containing molecules that al-
lowed an access in high yields and in a single step to dia-
cyl selenides.29 Nonetheless LiAlHSeH is unstable and
requires to be generated in situ and immediately used, thus
somewhat limiting the procedure. Further oxidation of the
so obtained selenoanhydrides with iodine afforded diacyl
diselenides.
O
O
F–
Cl
SeH
+
Me3SiSeSiH2Me3
1a
4
Ox
O
O
Se Se
6a
Scheme 3
Thus, following the results obtained in the functionaliza-
tion of phenylselenotrimethylsilane, we reacted two
equivalents of benzoyl chloride (1a) with HMDSS (4) un-
der the influence of TBAF (Scheme 2), to obtain a 75%
yield of dibenzoyl selenide (5a). So, HMDSS proved to be
another interesting reagent for transferring a selenated
moiety.
Interestingly, no appreciable contamination was ever
found between diacyl selenides and -diselenides in the ar-
omatic series, thus affording a clean and selective entry to
both classes of compounds that are known to be extremely
difficult to separate.
In the case of the alkyl derivative, the diacyl diselenide 6d
was contaminated by a small amount (<10%) of the sele-
noanhydride 5d.
The reaction can be easily extended to different acyl chlo-
rides, as reported in Table 2 (entries 1–5).30
Synlett 2011, No. 15, 2248–2252 © Thieme Stuttgart · New York

2250
A. Capperucci et al.
LETTER
The ratio of 5d and 6d cannot be unequivocally obtained To the best our knowledge, this represents the first exam-
1
either from H NMR or from 13C NMR spectra (the sig- ple of syntheses of selenoanhydrides in ionic liquids, pro-
nals being very similar) but could nonetheless be easily viding evidence of the versatility of this synthetic
obtained through their 77Se NMR spectra, that show very approach.
typical ranges of absorption for the two classes of com-
In conclusion, we have demonstrated that silylselenides
pounds 5 and 6. 77Se NMR chemical shifts are collected in
Table 3.
behave as efficient transfer agents of selenated moieties,
providing selectivity and good yields in rather mild condi-
tions to selenolesters, diacyl selenides and diacyl dise-
lenides.
Table 3 Typical 77Se NMR Chemical Shifts of Compounds 5 and 6
R
Compound 77Se NMR
Compound 77Se NMR
5
(d)
6
(d)
Acknowledgment
Ph
5a
5b
5c
5d
5e
743 ppm
749 ppm
730 ppm
784 ppm
777 ppm
6a
6b
6c
6d
6e
613 ppm
619 ppm
598 ppm
601 ppm
614 ppm
Financial support from MiUR, National Project PRIN 2007 ‘Stereo-
selezione in Sintesi Organica. Metodologie ed Applicazioni’ is gra-
tefully acknowledged. Mrs. B. Innocenti is acknowledged for
carrying out GC–MS analyses.
4-ClC6H4
4-MeOC6H4
MeCHCl
2-thienyl
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O
O
Se
–
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F
+
Me3SiSeSiMe3
O
7
8
O
Scheme 4
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Scheme 5
Synlett 2011, No. 15, 2248–2252 © Thieme Stuttgart · New York

LETTER
Organoselenosilane-Mediated Selective Mild Access to Selenolesters
2251
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J. Chem. Soc., Perkin Trans. 1 2002, 737. (b) Ishihara, H.;
Koketsu, M.; Fukuta, Y.; Nada, F. J. Am. Chem. Soc. 2001,
123, 8408.
(30) Synthesis of 4-Methoxybenzoic Selenoanhydride (5c): A
solution of 4-methoxybenzoyl chloride (24 mL, 0.18 mmol)
and TBAF (1 M in THF, 18 mL, 0.018 mmol) in anhyd THF
(0.5 mL) was cooled under atmosphere at 0 °C, and treated
dropwise with bis(trimethylsilyl)selenide (HMDSS; 21 mg,
0.09 mmol). The red mixture turned to pale yellow after few
minutes. After warming to r.t., and stirring for 2 h, the
solution was diluted with Et2O, washed with brine and dried
over Na2SO4. The crude product was purified by flash
(c) Degl’Innocenti, A.; Capperucci, A.; Nocentini, T.
Tetrahedron Lett. 2000, 42, 4557.
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A. Capperucci et al.
LETTER
column chromatography (n-hexane–CH2Cl2, 1:1) to afford
5c as a yellow solid (24 mg, 75%). 1H NMR (200 MHz,
CDCl3): d = 3.88 (s, 6 H), 6.93–6.98 (m, 4 H), 7.92–7.96 (m,
4 H). 13C NMR (50 MHz, CDCl3): d = 55.6, 114.1, 130.9,
131.5, 164.5, 185.9. 77Se (38 MHz, CDCl3): d = 730.0.
CH2Cl2, 1:1) to produce 6c as a yellow solid (55 mg, 71%).
1H NMR (200 MHz, CDCl3):
d = 3.88 (s, 6 H), 6.92–6.98 (m, 4 H), 7.91–8.07 (m, 4 H). 13
NMR (50 MHz, CDCl3): d = 55.6, 114.2, 129.3, 130.5,
164.4, 186.9. 77Se (38 MHz, CDCl3): d = 598.5.
C
(31) Preparation of 4-Methoxybenzoic Diselenoperoxy-
anhydride (6c): A solution of 4-methoxybenzoyl chloride
(24 mL, 0.18 mmol) in anhyd THF (0.5 mL) was added under
an inert atmosphere with HMDSS (44 mg, 0.19 mmol) and
it was cooled to 0 °C. TBAF (1 M in THF, 38 mL, 0.038
mmol) was then added dropwise. The red mixture so formed
was warmed to r.t. and stirred for 2 h. Upon quenching with
brine, the red solution turned slowly to pale yellow.
(32) Kageyama, H.; Murai, T.; Kanda, T.; Kato, S. J. Am. Chem.
Soc. 1994, 116, 2195.
(33) See also: (a) Sawant, A. D.; Raut, D. G.; Darvatkar, N. B.;
Salunkhe, M. M. Green Chem. Lett. Rev. 2011, 4, 41. (b)
Greaves, T. L.; Drummond, C. J. Chem. Rev. 2008, 108,
206. (c) Chowdhury, S.; Mohan, R. S.; Scott, J. L.
Tetrahedron 2007, 63, 2363. (d) Sheldon, R. Chem.
Commun. 2001, 2399. (e) Wasserscheid, P.; Keim, W.
Angew. Chem. Int. Ed. 2000, 39, 3772. (f) Welton, T.
Chem. Rev. 1999, 99, 207.
Extraction with Et2O, drying over Na2SO4 and removal of
the solvent under vacuum afforded the crude product, which
was purified by flash column chromatography (n-hexane–
Synlett 2011, No. 15, 2248–2252 © Thieme Stuttgart · New York

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