Syntheses of selenoesters through C-H selenation of aldehydes with diselenides under metal-free and solvent-free conditions

Article abstract of DOI:10.1039/c4ra07983c

A DTBP-promoted C-H selenation of aldehydes with diselenides under metal-free and solvent-free conditions is described. This system shows good functional group compatibility, functional groups including bromo, trifluoromethyl, chloro, amine and heterocycle-containing moieties including thiophene and furan are all tolerated by the reaction conditions employed. Both diaryl and dialkyl diselenides reacted smoothly with aldehydes to provide selenoesters in good to excellent yields. This journal is

Full text of DOI:10.1039/c4ra07983c

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Syntheses of selenoesters through C–H selenation
of aldehydes with diselenides under metal-free and
solvent-free conditions†
Cite this: RSC Adv., 2014, 4, 41237
*
Jyun-Cyuan Liou,‡ Satpal Singh Badsara,‡ Yu-Ting Huang and Chin-Fa Lee
A DTBP-promoted C–H selenation of aldehydes with diselenides under metal-free and solvent-free
conditions is described. This system shows good functional group compatibility, functional groups
including bromo, trifluoromethyl, chloro, amine and heterocycle-containing moieties including
thiophene and furan are all tolerated by the reaction conditions employed. Both diaryl and dialkyl
diselenides reacted smoothly with aldehydes to provide selenoesters in good to excellent yields.
Received 1st August 2014
Accepted 26th August 2014
DOI: 10.1039/c4ra07983c
www.rsc.org/advances
Results and discussion
Introduction
Initially, 4-methoxybenzaldehyde (1a) and diphenyl diselenide
(2a) were chosen as the coupling partners to determine the
optimal reaction conditions. The results are summarized in
Table 1. Only trace amount of the selenoester 3a was obtained
Recently, organoselenium compounds have gained much
attention due to their applications in the elds of chemical
biology,1 asymmetric catalysis,2,3 cross-coupling reactions,4
organic synthesis,5–7 materials science,8 and natural products.9
Many methods have been reported for preparing sele-
noesters,10–13 and the transition-metal-catalyzed cross-coupling
reaction of acyl chlorides with nucleophilic selenium reagents is
one of the most popular approaches for preparing such mole-
cules.12,13 Transition metals including Hg,12a Pd,12d,13a Fe,12g
Sm,13b In,12f,13c,13d Rh,13e Cu,13f Zn,13g La13h have been used as the
catalysts for this transformation. However, the above methods
suffered from some synthetic drawbacks due to the issue of air
stability and/or toxicity of the transition metals, starting mate-
rials and solvents; moreover, these systems usually used not
easily available selenium containing precursors.10a,12a,12d,14a
Recently, organo-catalysis15 has been employed as an alternative
choice to replace transition metal mediated transformations,10
and application of this approach to the direct C–H bond sele-
nation of aldehydes with diselenides has received less atten-
tion.10c Very recently, we have reported the DTBP-promoted
cross-coupling of aldehydes with disuldes to provide thio-
esters under metal-free conditions.15a Here, we report that the
selenoesters can be prepared through the coupling of aldehydes
with diselenides in the presence of DTBP as an oxidant without
transition metals under solvent-free conditions.
Table 1 Optimization of the reaction conditionsa
Entry
Oxidant (equiv.)
Yieldb (%)
1c
2
3
4
5
6
7
8
9
10
11d
12e
13f
14g
15h
TBHP (4.0)
TBPB (4.0)
BPO (4.0)
Trace
64
Trace
Trace
N.R.
N.R.
Trace
93
41
21
31
16
K2S2O8 (4.0)
AcOOH (4.0)
m-CPBA (4.0)
H2O2 (4.0)
DTBP (4.0)
DTBP (3.0)
DTBP (2.0)
DTBP (4.0)
DTBP (4.0)
DTBP (4.0)
DTBP (4.0)
DTBP (4.0)
68
59
68
a
Reaction conditions: 4-methoxybenzaldehyde (1.0 mL), diphenyl
diselenide (0.25 mmol) and oxidant (2.0 mmol) were reacted at 120 ꢀC
b
c
for 24 h. Isolated yield based on diphenyl diselenide. TBHP in
Department of Chemistry, National Chung Hsing University, Taichung, Taiwan 402,
Republic of China. E-mail: cfalee@dragon.nchu.edu.tw; Fax: +886-4-2286-2547
† Electronic supplementary information (ESI) available: NMR spectra of
compounds 3a–r and 4a–i. See DOI: 10.1039/c4ra07983c
d
e
f
g
water. 110 ꢀC. 100 ꢀC. 16 h. 0.5 mL of 4-methoxybenzaldehyde
h
was used. Reaction was carried out under microwave conditions for
30 min. (TBHP
¼
tert-butyl hydroperoxide, TBPB
¼
tert-butyl
peroxybenzoate, BPO ¼ benzoyl peroxide, AcOOH ¼ peracetic acid,
DTBP ¼ di-tert-butyl peroxide).
‡ Both authors contributed equally to this work.
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Table 2 DTBP-promoted synthesis of selenoesters from diaryl dis- Table 2 (Contd.)
elenides and aldehydesa
Entry
13
Product
Yieldb (%)
Entry
1
Product
Yieldb (%)
94
60
14
15
65
92
2
88
3
4
76
62
16
88
72
17
5
6
7
8
88
78
86
74
a
Reaction conditions unless otherwise stated: aldehyde (1.0 mL), diaryl
diselenide (0.25 mmol) and DTBP (2.0 mmol) were reacted at 120 ꢀC for
b
24 h using Schlenk tube. Isolated yields based on diselenides.
c
Reactions were carried out using sealed tube.
when the reaction was carried out by using TBHP (tert-butyl
hydroperoxide) as an oxidant14b (Table 1, entry 1). Interestingly,
a 64% yield of the target was obtained when the reaction was
carried using TBPB (tert-butyl peroxybenzoate) as oxidant (Table
1, entry 2). Based on this result, we screened other oxidants
(Table 1, entries 3–8), and DTBP was found to be the best, giving
3a in 93% yield (Table 1, entry 8).16 It was also found that lower
amounts of DTBP (Table 1, entries 9 and 10), lower reaction
temperatures (Table 1, entries 11 and 12) and shorter reaction
time (Table 1, entry 13) diminished the yield of the product.
Lower amount of 4-methoxybenzaldehyde will reduce the yield
of the product (59%) (Table 1, entry 14).
With the optimized reaction conditions in hand, we then
demonstrated the scope of this novel system for a variety of
substrates. As shown in Table 2, a wide range of diaryl dis-
elenides were smoothly coupled with aldehydes, giving the
corresponding selenoesters in good to excellent yields. Diaryl
diselenides bearing electron-donating and electron-with-
drawing groups were successfully reacted with substituted aryl
aldehydes. Remarkably, this system shows good functional
group comparability, functional groups including bromo (Table
2, entries 1–5), triuoromethyl (Table 2, entries 6–11), methoxy
(Table 2, entries 16 and 17), amine (Table 2, entries 12 and 13)
9
77
10
11
59 (90)c
52 (91)c
12
79
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were all tolerated by the reaction conditions employed. More-
over, sterically demanding ortho-substituted aryl aldehydes
underwent the C–Se bond formation with diselenides to provide
the targets in good yields (Table 2, entry 2). Notably, hetero-
aromatic aldehydes such as thiophene-2-carboxaldehyde (Table
2, entries 5, 7, 14 and 16) and furan-containing aldehyde (Table
2, entries 8 and 17) are coupled with different diaryl diselenides
bearing electron-donating and electron-withdrawing groups,
provided the resulting selenoesters in good to excellent yields.
Scheme 1 Plausible mechanism.
Table 3 DTBP-promoted coupling reaction of dialkyl diselenides with
aldehydesa
With the promising results in the coupling of aldehydes with
diaryl diselenides, we next turned our attention to the use of
dialkyl diselenides as the coupling partners in this system, the
results are summarized in Table 3. A variety of aryl aldehydes
bearing electron-withdrawing and electron-donating groups
were successfully coupled with dialkyl diselenides, provided the
corresponding selenoesters in moderate to excellent yields.
Functional groups including chloro (Table 3, entry 8), tri-
uoromethyl (Table 3, entry 4), amine (Table 3, entries 1 and 2)
were tolerated by the reaction conditions. Importantly, thio-
phene-containing alkyl selenoesters could also be formed in a
92% yield when the reaction was carried out by using 2-thio-
phenecarboxaldehyde as the coupling partner (Table 3, entry 3).
A potential mechanism for DTBP-promoted C–Se coupling
reactions of aldehydes with diselenides is depicted in Scheme 1.
The DTBP under heating can generate t-BuO radical which can
react with aldehyde and diselenide to generate aldehydic radical
A and selenide radical B respectively. The coupling of radical A
and B can provide the selenoester.
Entry
1
Product
Yieldb (%)
91 (38)c
2
84
3
4
5
92
67
78
Experimental section
General information
All chemicals were purchased from commercial suppliers and
used without further purication. NMR spectra were recorded
on a Varian Unity Inova-600 or a Varian Mercury-400 instrument
using CDCl3 as solvent. Chemical shis are reported in parts
per million (ppm) and referenced to the residual solvent reso-
nance. Coupling constant (J) are reported in hertz (Hz). Stan-
dard abbreviations indicating multiplicity were used as follows:
s ¼ singlet, d ¼ doublet, t ¼ triplet, dd ¼ double doublet, q ¼
quartet, m ¼ multiplet. High resolution mass spectra (HRMS)
were performed on an electron ionization time-of-ight (EI-
TOF) mass spectrometer at the National Chung Hsing
University.
6
7
8
69
58
51
General procedure for Table 1
9
25
A Schlenk tube equipped with a magnetic stirrer bar was
charged with diphenyl diselenide (78.8 mg, 0.25 mmol), 4-
a
Reaction conditions unless otherwise stated: aldehyde (1.0 mL), methoxybenzaldehyde (1.0 mL) and oxidant (2.0 mmol) under a
ꢀ
dialkyl diselenide (0.25 mmol) and DTBP (2.0 mmol) were reacted at
nitrogen-lled balloon and heated at 120 C for 24 h in an oil
b
120 ꢀC for 24
h using sealed tube. Isolated yields based on
c
bath. Aer the reaction was complete (monitored by TLC), the
diselenides. Reactions were carried out using Schlenk tube.
reaction mixture was cooled to ambient temperature. The
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resulting residue was puried by column chromatography
(SiO2, hexanes–EtOAc: 100 : 1) to provide 3a.
Se-4-bromophenyl 4-methoxybenzoselenoate (3e). The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-bromophenyl)diselane (118 mg, 0.25
mmol), 4-methoxybenzaldehyde (1.0 mL) and DTBP (2.0 mmol),
then puried by column chromatography (SiO2, hexanes–
EtOAc: 100 : 1) to provide 3e as a white solid (115 mg, 62%
yield). M.P.: 81–82 ꢀC; 1H NMR (400 MHz, CDCl3): d 3.86 (s, 3H),
6.94 (d, J ¼ 8.8 Hz, 2H), 7.43 (d, J ¼ 8.8 Hz, 2H), 7.51 (d, J ¼ 8.4
Hz, 2H), 7.87 (d, J ¼ 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): d
59.5, 114.1, 123.6, 124.7, 129.6, 130.8, 132.3, 137.8, 164.2, 190.4;
HRMS-EI calcd for C14H11BrO2Se: 369.9108, found: 369.9110.
Se-4-bromophenyl thiophene-2-carboselenoate (3f). The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-bromophenyl)diselane (118 mg, 0.25
mmol), thiophene-2-carbaldehyde (1.0 mL) and DTBP (2.0
mmol), then puried by column chromatography (SiO2,
hexanes–EtOAc: 100 : 1) to provide 3f as a white solid (152 mg,
Se-phenyl 4-methoxybenzoselenoate (3a) (Table 1, entry 7).17a
The title compound was prepared following the general proce-
dure for Table 1, using diphenyl diselenide (78.8 mg, 0.25
mmol), 4-methoxybenzaldehyde (1.0 mL) and DTBP (2.0 mmol),
which on purication by column chromatography (SiO2,
hexanes–EtOAc: 100 : 1), provided 3a as a white solid (135 mg,
93% yield). M.P.: 59–60 ꢀC; 1H NMR (400 MHz, CDCl3): d 3.83 (s,
3H), 6.93 (dd, J ¼ 2.0 & 6.8 Hz, 2H), 7.40 (dd, J ¼ 2.0 & 4.8 Hz,
3H), 7.57–7.59 (m, 2H), 7.90 (dd, J ¼ 2.0 & 6.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d 55.4, 114.0, 125.8, 128.8, 129.2, 129.5,
131.1, 136.3, 164.0, 191.2.
General procedure for Table 2
1
ꢀ
A Schlenk tube equipped with a magnetic stirrer bar was
charged with diselenide (0.25 mmol), aldehyde (1.0 mL) and
DTBꢀP (2.0 mmol) under a nitrogen-lled balloon and heated at
120 C for 24 h in an oil bath. Aer the reaction was complete
(monitored by TLC), the reaction mixture was cooled to ambient
temperature. The resulting residue was puried by column
chromatography (SiO2, hexanes–EtOAc: 100 : 1) to provide 3.
Se-4-bromophenyl 3-methylbenzoselenoate (3b). The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-bromophenyl)diselane (118 mg, 0.25
mmol), 3-methylbenzaldehyde (1.0 mL) and DTBP (2.0 mmol),
then puried by column chromatography (SiO2, hexanes–
EtOAc: 100 : 1) to provide 3b as a white solid (166 mg, 94%
yield). M.P.: 64–65 ꢀC; 1H NMR (400 MHz, CDCl3): d 2.40 (s, 3H),
7.35 (d, J ¼ 7.2 Hz, 1H), 7.39–7.41 (m, 3H), 7.50–7.52 (m, 2H),
7.69–7.71 (m, 2H); 13C NMR (100 MHz, CDCl3): d 21.2, 123.6,
124.5, 124.6, 127.6, 128.7, 132.3, 134.7, 137.7, 138.0, 138.8,
192.5; HRMS-EI calcd for C14H11BrOSe: 353.9158, found:
353.9162.
88% yield). M.P.: 77–78 C; H NMR (400 MHz, CDCl3): d 7.14
(dd, J ¼ 0.8 & 4.0 Hz, 1H), 7.43–7.45 (m, 2H), 7.50–7.52 (m, 2H),
7.69 (dd, J ¼ 1.2 & 4.8 Hz, 1H), 7.84 (dd, J ¼ 1.2 & 4.0 Hz, 1H); 13
C
NMR (100 MHz, CDCl3): d 123.8, 124.2, 128.0, 132.1, 132.4,
133.9, 137.6, 142.5, 182.6; HRMS-EI calcd for C11H7BrOSSe:
345.8566, found: 345.8564.
Se-4-(triuoromethyl)phenyl benzoselenoate (3g). The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)diselane (112
mg, 0.25 mmol), benzaldehyde (1.0 mL) and DTBP (2.0 mmol),
then puried by column chromatography (SiO2, hexanes–
EtOAc: 100 : 1) to provide 3g as a white solid (127 mg, 78%
1
ꢀ
yield). M.P.: 96–97 C; H NMR (400 MHz, CDCl3): d 7.46–7.50
(m, 2H), 7.60–7.72 (m, 5H), 7.90–7.92 (m, 2H); 13C NMR (100
MHz, CDCl3): d 123.9 (d, J ¼ 271.3 Hz), 125.9 (d, J ¼ 3.7 Hz),
127.3, 129.0, 130.4, 131.0 (d, J ¼ 32.8 Hz), 134.2, 136.4, 138.0,
192.0; 19F NMR (376 MHz, CDCl3): d ¼ ꢁ64.2 (s); HRMS-EI calcd
for C14H9F3OSe: 329.9771, found: 329.9776.
Se-4-(triuoromethyl)phenyl
thiophene-2-carboselenoate
Se-4-bromophenyl 2-methylbenzoselenoate (3c). The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-bromophenyl)diselane (118 mg, 0.25
mmol), 2-methylbenzaldehyde (1.0 mL) and DTBP (2.0 mmol),
then puried by column chromatography (SiO2, hexanes–
EtOAc: 100 : 1) to provide 3c as a white solid (156 mg, 88%
yield). M.P.: 87–88 ꢀC; 1H NMR (400 MHz, CDCl3): d 2.46 (s, 6H),
7.25 (d, J ¼ 7.6 Hz, 1H), 7.32 (d, J ¼ 7.6 Hz, 1H), 7.39–7.42 (m,
3H), 7.52–7.54 (m, 2H), 7.87 (d, J ¼ 7.6 Hz, 1H); 13C NMR (100
MHz, CDCl3): d 20.8, 123.7, 125.7, 126.0, 128.8, 131.9, 132.42,
(3h). The title compound was prepared following the general
procedure for Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)
diselane (112 mg, 0.25 mmol), thiophene-2-carbaldehyde (1.0
mL) and DTBP (2.0 mmol), then puried by column chroma-
tography (SiO2, hexanes–EtOAc: 100 : 1) to provide 3h as yellow
solid (144 mg, 86% yield). M.P.: 71–72 C; H NMR (400 MHz,
CDCl3): d 7.14–7.17 (m, 1H), 7.62–7.70 (m, 2H), 7.71–7.72 (m,
3H), 7.85–7.87 (m, 1H); 13C NMR (100 MHz, CDCl3): d 123.8 (d, J
¼ 270.3 Hz), 125.9 (d, J ¼ 3.7 Hz), 128.1, 130.1, 131.0 (d, J ¼ 32.8
Hz), 132.3, 134.1, 136.2, 142.4, 182.0; 19F NMR (376 MHz,
CDCl3): d ¼ ꢁ64.2 (s). HRMS-EI calcd for C12H7F3OSSe:
335.9335, found: 335.9340.
1
ꢀ
132.48, 136.6, 137.6, 137.8, 194.2; HRMS-EI calcd for C14H11
BrOSe: 353.9158, found: 353.9156.
-
Se-4-bromophenyl benzoselenoate (3d).17b The title
compound was prepared following the general procedure for
Table 2, using 1,2-bis(4-bromophenyl)diselane (118 mg, 0.25
mmol), benzaldehyde (1.0 mL) and DTBP (2.0 mmol), then
puried by column chromatography (SiO2, hexane) to provide
3d as a white solid (129 mg, 76% yield). M.P.: 71 C; H NMR
(400 MHz, CDCl3): d 7.42–7.63 (m, 7H), 7.89–7.91 (m, 2H); 13C
NMR (100 MHz, CDCl3): d 123.8, 124.5, 127.3, 128.9, 132.4,
134.0, 137.7, 138.1, 192.5.
Se-4-(triuoromethyl)phenyl furan-2-carboselenoate (3i).
The title compound was prepared following the general proce-
dure for Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)dis-
elane (112 mg, 0.25 mmol), furan-2-carbaldehyde (1.0 mL) and
DTBP (2.0 mmol), then puried by column chromatography
(SiO2, hexanes–EtOAc: 100 : 1) to provide 3i as a yellow oil (118
mg, 74% yield). 1H NMR (400 MHz, CDCl3): d 6.60 (dd, J ¼ 1.6,
1
ꢀ
3.6 Hz, 1H), 7.23 (dd, J ¼ 0.8, 3.6 Hz, 1H), 7.63–7.72 (m, 5H); 13
C
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NMR (100 MHz, CDCl3): d 113.0, 115.7, 123.8 (d, J ¼ 270.3 Hz), which on purication by column chromatography (SiO2,
125.9 (d, J ¼ 3.7 Hz), 129.4, 131.0 (d, J ¼ 32.8 Hz), 136.3, 146.9, hexanes–EtOAc: 100 : 1), provided 3n as a yellow solid (91 mg,
151.2, 179.4; 19F NMR (376 MHz, CDCl3): d ¼ ꢁ64.2 (s); HRMS- 60% yield). M.P.: 162–163 ꢀC; 1H NMR (400 MHz, CDCl3): d 2.97
EI calcd for C12H7F3O2Se: 319.9563, found: 319.9561.
(s, 6H), 6.55 (d, J ¼ 9.2 Hz, 2H), 7.30–7.32 (m, 3H), 7.50–7.53 (m,
Se-4-(triuoromethyl)phenyl 4-chlorobenzoselenoate (3j). 2H), 7.74 (d, J ¼ 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): d 39.9,
The title compound was prepared following the general proce- 110.7, 125.5, 126.4, 128.5, 129.0, 129.7, 136.4, 153.9, 189.7;
dure for Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)dis- HRMS-EI calcd for C15H15NOSe: 305.0319, found: 305.0310.
elane (112 mg, 0.25 mmol), 4-chlorobenzaldehyde (1.0 g) and
Se-phenyl thiophene-2-carboselenoate (3o).17c The title
DTBP (2.0 mmol), then puried by column chromatography compound was prepared following the general procedure for
(SiO2, hexane) to provide 3j as a white solid (140 mg, 77% yield). Table 2, using diphenyl diselenide (78.8 mg, 0.25 mmol), thio-
1
ꢀ
M.P.: 69–70 C; H NMR (400 MHz, CDCl3): d 7.46 (dd, J ¼ 0.8, phene-2-carbaldehyde (1.0 mL) and DTBP (2.0 mmol), which on
8.4 Hz, 2H), 7.64–7.71 (m, 4H), 7.84 (dd, J ¼ 0.8, 8.0 Hz, 2H); 13
C
purication by column chromatography (SiO2, hexanes–EtOAc:
NMR (100 MHz, CDCl3): d 123.8 (d, J ¼ 270.3 Hz), 125.9, 126.0 (d, 100 : 1), provided 3o as a brown oil (86 mg, 65% yield). 1H NMR
J ¼ 3.6 Hz), 128.6, 129.3, 130.0, 131.1 (d, J ¼ 31.8 Hz), 136.3, (400 MHz, CDCl3): d 7.14 (t, J ¼ 4.8 Hz, 1H), 7.39–7.41 (m, 3H),
140.6, 190.8; 19F NMR (376 MHz, CDCl3): d ¼ ꢁ64.2 (s). HRMS- 7.58–7.60 (m, 2H), 7.67 (d, J ¼ 5.2 Hz, 1H), 7.86 (d, J ¼ 4.0 Hz,
EI calcd for C14H8ClF3OSe: 363.9381, found: 363.9386.
1H); 13C NMR (100 MHz, CDCl3): d 125.4, 127.9, 129.1, 129.3,
Se-4-(triuoromethyl)phenyl 4-methoxybenzoselenoate (3k). 131.9, 133.16, 136.1, 142.9, 183.4.
The title compound was prepared following the general proce-
Se-phenyl 3-methylbenzoselenoate (3p).17c The title
dure for Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)dis- compound was prepared following the general procedure for
elane (112 mg, 0.25 mmol), 4-methoxybenzaldehyde (1.0 mL) Table 2, using diphenyl diselenide (78.8 mg, 0.25 mmol), 3-
and DTBP (2.0 mmol), then puried by column chromatography methylbenzaldehyde (1.0 mL) and DTBP (2.0 mmol), then
(SiO2, hexanes–EtOAc: 100 : 1) to provide 3k as a white solid puried by column chromatography (SiO2, hexane) to provide
(106 mg, 59% yield). M.P.: 90–91 ꢀC; 1H NMR (400 MHz, CDCl3): 3p as a yellow oil (127 mg, 92% yield). 1H NMR (400 MHz,
d 3.86 (s, 3H), 6.95 (dd, J ¼ 2.0, 7.2 Hz, 2H), 7.63 (d, J ¼ 8.0 Hz, CDCl3): d 2.40 (s, 3H), 7.31–7.39 (m, 5H), 7.57–7.59 (m, 2H),
2H), 7.70 (d, J ¼ 8.0 Hz, 2H), 7.89 (dd, J ¼ 2.0, 6.8 Hz, 2H); 13C 7.71–7.73 (m, 2H); 13C NMR (100 MHz, CDCl3): d 21.2, 124.5,
NMR (100 MHz, CDCl3): d 55.5, 114.2, 123.9 (d, J ¼ 270.3 Hz), 125.8, 127.6, 128.7, 128.9, 129.2, 134.5, 136.2, 138.4, 138.8,
125.8 (d, J ¼ 3.6 Hz), 129.7, 130.6, 130.7, 131.0 (d, J ¼ 23.7 Hz), 193.3.
136.4, 164.4, 189.8; 19F NMR (376 MHz, CDCl3): d ¼ ꢁ64.1 (s).
Se-4-methoxyphenyl thiophene-2-carboselenoate (3q). The
title compound was prepared following the general procedure
HRMS-EI calcd for C15H11F3O2Se: 359.9876, found: 359.9872.
Se-4-(triuoromethyl)phenyl 3-methylbenzoselenoate (3l). for Table 2, using 1,2-bis(4-methoxyphenyl)diselane (93.0 mg,
The title compound was prepared following the general proce- 0.25 mmol), thiophene-2-carbaldehyde (1.0 mL) and DTBP (2.0
dure for Table 2, using 1,2-bis(4-(triuoromethyl)phenyl)dis- mmol), then puried by column chromatography (SiO2,
elane (112 mg, 0.25 mmol), 3-methylbenzaldehyde (1.0 mL) and hexanes–EtOAc: 100 : 1) to provide 3q as a brown solid (131 mg,
DTBP (2.0 mmol), then puried by column chromatography 88% yield). M.P.: 101–102 ꢀC; 1H NMR (400 MHz, CDCl3): d 3.81
(SiO2, hexane) to provide 3l as a white solid (89.2 mg, 52% yield). (s, 3H), 6.91–6.94 (m, 2H), 7.12–7.14 (m, 1H), 7.47–7.49 (m, 2H),
M.P.: 78–79 ꢀC; 1H NMR (400 MHz, CDCl3): d 2.41 (s, 3H), 7.33– 7.66 (dd, J ¼ 1.2, 4.8 Hz, 1H), 7.85 (dd, J ¼ 1.2, 4.0 Hz, 1H); 13
C
7.7.43 (m, 2H), 7.62–7.72 (m, 6H); 13C NMR (100 MHz, CDCl3): d NMR (100 MHz, CDCl3): d 55.2, 115.0, 115.7, 127.9, 131.8, 133.4,
21.1, 122.5, 123.9 (d, J ¼ 270.3 Hz), 125.9 (d, J ¼ 3.6 Hz), 127.7, 137.7, 143.0, 160.4, 184.3; HRMS-EI calcd for C12H10O2SSe:
128.8, 130.6, 130.9 (d, J ¼ 32.8 Hz), 134.9, 136.3, 138.0, 139.0, 297.9567, found: 297.9572.
191.8; 19F NMR (376 MHz, CDCl3): d ¼ ꢁ64.2 (s); HRMS-EI calcd
Se-4-methoxyphenyl furan-2-carboselenoate (3r). The title
compound was prepared following the general procedure for
for C15H11F3OSe: 343.9927, found: 343.9936.
Se-phenyl 4-(diethylamino)benzoselenoate (3m). The title Table 2, using 1,2-bis(4-methoxyphenyl)diselane (93.0 mg, 0.25
compound was prepared following the general procedure for mmol), furan-2-carbaldehyde (1.0 mL) and DTBP (2.0 mmol),
Table 2, using diphenyl diselenide (78.8 mg, 0.25 mmol), 4- then puried by column chromatography (SiO2, hexanes–
(diethylamino)benzaldehyde (1.0 g) and DTBP (2.0 mmol), EtOAc: 100 : 1) to provide 3r as a brown solid (101 mg, 72%
which on purication by column chromatography (SiO2, yield). M.P.: 51–52 ꢀC; 1H NMR (400 MHz, CDCl3): d 3.82 (s, 3H),
hexanes–EtOAc: 100 : 1), provided 3m as a yellow solid (131 mg, 6.56 (dd, J ¼ 1.6, 3.6 Hz, 1H), 6.92–6.95 (m, 2H), 7.19 (d, J ¼ 3.6
79% yield). M.P.: 104–106 ꢀC; 1H NMR (400 MHz, CDCl3): d 1.09 Hz, 1H), 7.47 (dd, J ¼ 2.0, 6.8 Hz, 2H), 7.62 (d, J ¼ 1.6 Hz, 1H);
(t, J ¼ 7.2 Hz, 6H), 3.30 (q, J ¼ 7.2 Hz, 4H), 6.52 (d, J ¼ 9.2 Hz, 13C NMR (100 MHz, CDCl3): d 55.21, 112.7, 114.9, 115.0, 115.3,
2H), 7.28–7.29 (m, 2H), 7.50–7.52 (m, 3H), 7.71 (d, J ¼ 8.8 Hz, 137.8, 146.5, 151.7, 160.4, 181.6; HRMS-EI calcd for C12H10O3Se:
2H); 13C NMR (100 MHz, CDCl3): d 12.3, 44.5, 110.2, 124.8, 281.9795, found: 281.9801.
126.5, 128.4, 128.9, 130.0, 136.4, 151.8, 189.2; HRMS-EI calcd for
C
17H19NOSe: 333.0632, found: 333.0640.
Se-phenyl 4-(dimethylamino)benzoselenoate (3n). The title
General procedure for Table 3
compound was prepared following the general procedure for A sealed tube equipped with a magnetic stirrer bar was charged
Table 2, using diphenyl diselenide (78.8 mg, 0.25 mmol), 4- with diselenide (0.25 mmol), aldehyde (1.0 mL) and DTBP (2.0
(dimethylamino)benzaldehyde (1.0 g) and DTBP (2.0 mmol), mmol) under a nitrogen-lled balloon and heated at 120 ꢀC for
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24 h in an oil bath. Aer the reaction was complete (monitored CDCl3): d 0.88 (t, J ¼ 6.8 Hz, 3H), 1.26–1.43 (m, 17H), 1.71–1.76
by TLC), the reaction mixture was cooled to ambient tempera- (m, 2H), 7.45 (d, J ¼ 8.4 Hz, 2H), 7.85 (d, J ¼ 8.8 Hz, 2H); 13C
ture. The resulting residue was puried by column chroma- NMR (100 MHz, CDCl3): d 14.0, 22.5, 25.5, 28.7, 29.6, 29.9, 30.5,
tography (SiO2, hexanes–EtOAc: 100 : 1) to provide 4. 31.0, 31.7, 35.1, 125.6, 127.0, 136.6, 157.2, 194.3; HRMS-EI calcd
Se-methyl 4-(diethylamino)benzoselenoate (4a). The title for C18H28OSe: 340.1305, found: 340.1307.
compound was prepared following the general procedure for
Se-(n-heptyl) 3-methylbenzoselenoate (4f). The title
Table 3, using dimethyl diselenide (0.024 mL, 0.25 mmol), 4- compound was prepared following the general procedure for
(diethylamino)benzaldehyde (1.0 g) and DTBP (2.0 mmol),- Table 3, using 1,2-diheptyldiselane (89.1 mg, 0.25 mmol), 3-
which on purication by column chromatography (SiO2, methylbenzaldehyde (1.0 mL) and DTBP (2.0 mmol), then
hexanes–EtOAc: 100 : 1), provided 4a as a white solid (123 mg, puried by column chromatography (SiO2, hexane) to provide 4f
91% yield). M.P.: 79–81 ꢀC; 1H NMR (400 MHz, CDCl3): d 1.17 (t, as a yellow oil (103 mg, 69% yield). 1H NMR (400 MHz, CDCl3): d
J ¼ 7.2 Hz, 6H), 2.31 (s, 3H), 3.38 (q, J ¼ 7.2 Hz, 4H), 6.58 (d, J ¼ 0.88 (t, J ¼ 7.2 Hz, 3H), 1.25–1.43 (m, 8H), 1.70–1.76 (m, 2H),
9.2 Hz, 2H), 7.78 (d, J ¼ 9.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): 2.39 (s, 3H), 3.07 (t, J ¼ 7.2 Hz, 2H), 7.28–7.37 (m, 2H), 7.69–7.71
d 4.2, 12.3, 44.4, 110.1, 125.6, 129.6, 151.4, 191.0; HRMS-EI calcd (m, 2H); 13C NMR (100 MHz, CDCl3): d 14.0, 21.1, 22.5, 25.6,
for C12H17NOSe: 271.0475, found: 271.0472.
28.7, 29.6, 29.9, 30.4, 31.6, 124.3, 127.4, 128.5, 134.1, 138.5,
Se-methyl 4-(dimethylamino)benzoselenoate (4b). The title 139.2, 195.0; HRMS-EI calcd for C15H22OSe: 298.0836, found:
compound was prepared following the general procedure for 298.0831.
Table 3, using dimethyl diselenide (0.024 mL, 0.25 mmol), 4-
Se-(n-heptyl) benzoselenoate (4g). The title compound was
(dimethylamino)benzaldehyde (1.0 g) and DTBP (2.0 mmol),- prepared following the general procedure for Table 3, using 1,2-
which on purication by column chromatography (SiO2, diheptyldiselane (89.1 mg, 0.25 mmol), benzaldehyde (1.0 mL)
hexanes–EtOAc: 100 : 1), provided 4b as a white solid (102 mg, and DTBP (2.0 mmol), then puried by column chromatography
84% yield). M.P.: 87–89 ꢀC; 1H NMR (400 MHz, CDCl3): d 2.31 (s, (SiO2, hexane) to provide 4g as a colorless oil (82 mg, 58% yield).
3H), 3.01 (s, 6H), 6.59 (d, J ¼ 9.2 Hz, 2H), 7.79 (d, J ¼ 8.4 Hz, 2H); 1H NMR (400 MHz, CDCl3): d 0.88 (t, J ¼ 6.8 Hz, 3H), 1.25–1.43
13C NMR (100 MHz, CDCl3): d 4.3, 39.9, 110.5, 126.4, 129.2, (m, 8H), 1.71–1.76 (m, 2H), 3.09 (t, J ¼ 7.6 Hz, 2H), 7.41–7.56 (m,
153.7, 191.4; HRMS-EI calcd for C10H13NOSe: 243.0162, found: 3H), 7.89–7.91 (m, 2H); 13C NMR (100 MHz, CDCl3): d 14.0, 22.5,
243.0160.
Se-(n-heptyl) thiophene-2-carboselenoate (4c). The title HRMS-EI calcd for C14H20OSe: 284.0679, found: 284.0672.
compound was prepared following the general procedure for Se-(n-heptyl) 4-chlorobenzoselenoate (4h). The title
25.7, 28.7, 29.9, 30.4, 31.6, 127.0, 128.6, 133.4, 139.2, 195.0;
Table 3, using 1,2-diheptyldiselane (89.1 mg, 0.25 mmol), compound was prepared following the general procedure for
thiophene-2-carbaldehyde (1.0 mL) and DTBP (2.0 mmol), then Table 3, using 1,2-diheptyldiselane (89.1 mg, 0.25 mmol), 4-
puried by column chromatography (SiO2, hexane) to provide chlorobenzaldehyde (1.0 g) and DTBP (2.0 mmol), then puried
1
4c as a colorless oil (133 mg, 92% yield). H NMR (400 MHz, by column chromatography (SiO2, hexane) to provide 4h as a
1
CDCl3): d 0.88 (t, J ¼ 7.2 Hz, 3H), 1.25–1.42 (m, 8H), 1.75 (t, J ¼ yellow oil (81.0 mg, 51% yield). H NMR (400 MHz, CDCl3): d
7.6 Hz, 2H), 3.09 (t, J ¼ 7.6 Hz, 2H), 7.11 (dd, J ¼ 4.0, 5.2 Hz, 1H), 0.86–0.89 (m, 3H), 1.28–1.42 (m, 8H), 1.72–1.76 (m, 2H), 3.07–
7.63 (dd, J ¼ 1.2, 4.8 Hz, 1H), 7.11 (dd, J ¼ 1.2, 4.0 Hz, 1H); 13
C
3.11 (m, 2H), 7.39–7.42 (m, 2H), 7.82–7.85 (m, 2H); 13C NMR
NMR (100 MHz, CDCl3): d 14.0, 22.5, 26.0, 28.7, 29.8, 30.5, 31.6, (100 MHz, CDCl3): d 14.0, 22.5, 26.0, 28.7, 29.9, 30.3, 31.6, 128.3,
127.7, 131.3, 132.7, 144.2, 185.1; HRMS-EI calcd for C12H18OSSe: 128.9, 137.5, 139.7, 193.7; HRMS-EI calcd for C14H19ClOSe:
290.0244, found: 290.0246.
318.0290, found: 318.0281.
Se-(n-heptyl) 4-(triuoromethyl)benzoselenoate (4d). The
Se-benzyl 4-methoxybenzoselenoate (4i). The title compound
title compound was prepared following the general procedure was prepared following the general procedure for Table 2, using
for Table 3, using 1,2-diheptyldiselane (89.1 mg, 0.25 mmol), 4- 1,2-dibenzyldiselane (85.0 mg, 0.25 mmol), 4-methox-
(triuoromethyl)benzaldehyde (1.0 mL) and DTBP (2.0 mmol), ybenzaldehyde (1.0 mL) and DTBP (2.0 mmol), then puried by
then puried by column chromatography (SiO2, hexane) to column chromatography (SiO2, hexanes–EtOAc: 100 : 1) to
1
provide 4d as a colorless oil (118 mg, 67% yield). 1H NMR (400 provide 4i as a yellow oil (38.2 mg, 25% yield). H NMR (400
MHz, CDCl3): d 0.88 (t, J ¼ 6.4 Hz, 3H), 1.25–1.44 (m, 8H), 1.76 (t, MHz, CDCl3): d 3.85 (s, 3H), 4.32 (s, 2H), 6.90 (dd, J ¼ 2.0, 6.8 Hz,
J ¼ 7.2 Hz, 2H), 3.13 (t, J ¼ 7.2 Hz, 2H), 7.72 (d, J ¼ 8.0 Hz, 2H), 2H), 7.20–7.37 (m, 5H), 7.86 (dd, J ¼ 2.0, 6.8 Hz, 2H); 13C NMR
8.00 (d, J ¼ 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): d 14.0, 22.5, (100 MHz, CDCl3): d 28.8, 55.5, 113.9, 126.8, 128.5, 128.9, 129.5,
26.3, 28.7, 29.9, 30.2, 31.6, 123.9 (d, J ¼ 270.3 Hz), 125.8 (d, J ¼ 131.6, 139.2, 164.0, 192.4; HRMS-EI calcd for C15H14O2Se:
3.7 Hz), 127.3, 134.6 (d, J ¼ 32.8 Hz), 141.9, 194.3; 19F NMR (376 306.0159, found: 306.0153.
MHz, CDCl3): d ¼ ꢁ64.7 (s); HRMS-EI calcd for C15H19F3OSe:
352.0553, found: 352.0556.
Conclusions
Se-(n-heptyl) 4-tert-butylbenzoselenoate (4e). The title
compound was prepared following the general procedure for In conclusion, we have developed a general and efficient
Table 3, using 1,2-diheptyldiselane (89.1 mg, 0.25 mmol), 4- approach for the preparation of selenoesters using DTBP as an
(tert-butyl)benzaldehyde (1.0 mL) and DTBP (2.0 mmol), then oxidant under metal-free and solvent-free conditions. This
puried by column chromatography (SiO2, hexane) to provide system shows good functional group compatibility, giving
4e as a yellow oil (132 mg, 78% yield). 1H NMR (400 MHz, selenoesters in good to excellent yields.
41242 | RSC Adv., 2014, 4, 41237–41244
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Acknowledgements
The National Science Council, Taiwan (NSC 101-2113-M-005-
008-MY3), the National Chung Hsing University and the Center
of Nanoscience and Nanotechnology (NCHU) are gratefully
acknowledged for nancial support. We also thank Prof. Fung-E
Hong (NCHU) for sharing his GC-MS instruments. C.F.L. is a
Golden-Jade Fellow of Kenda Foundation, Taiwan.
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41244 | RSC Adv., 2014, 4, 41237–41244
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