Selenenylations of alkenes with styrene nucleophiles

Article abstract of DOI:10.1016/j.tet.2012.08.034

Iodine-mediated addition reactions to alkenes with diphenyl diselenide using the same alkenes as nucleophiles are presented. The transformation proceeds under mild reaction conditions and the addition products were isolated in moderate to good yields.

Full text of DOI:10.1016/j.tet.2012.08.034

Tetrahedron 68 (2012) 10573e10576
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Selenenylations of alkenes with styrene nucleophiles
*
Elena Gabriele, Fateh V. Singh, Diana M. Freudendahl, Thomas Wirth
School of Chemistry, Cardiff University, Park Place, Main Building, Cardiff CF10 3AT, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 5 July 2012
Received in revised form 7 August 2012
Accepted 10 August 2012
Available online 17 August 2012
Iodine-mediated addition reactions to alkenes with diphenyl diselenide using the same alkenes as nu-
cleophiles are presented. The transformation proceeds under mild reaction conditions and the addition
products were isolated in moderate to good yields.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Alkenes
Diselenides
Selenenylation
Styrenes
1. Introduction
2. Results and discussion
Organoselenium chemistry has been developed as an important
synthetic tool1 after the discovery of the selenoxide elimination in
the early 1970s.2 Organoselenium reagents have been used for the
synthesis of various biologically important synthetic and naturally
occurring compounds.3 In the past two decades, addition reactions
of selenium electrophiles to alkenes have been received particular
attention.4 These addition reactions usually consist of two steps
involving the formation of seleniranium ion intermediates 3 from
alkenes 1 and the selenium electrophile RSeX 2 followed by the
attack of nucleophile (Nuꢀ) (Scheme 1). Addition reactions of var-
ious selenium electrophiles with alkenes have been explored in
detail by using internal and external nucleophiles.5,6 The addition
products 4 of these reactions have been identified as valuable
synthetic intermediates also for the synthesis of various natural
products.
Herein, we report an iodine-mediated addition reaction of sty-
renes using the same styrenes as nucleophiles under mild reaction
conditions. Intramolecular versions of alkenes as nucleophiles in
such reactions have already been reported.7 Initially, optimal re-
action conditions for the selenenylation of styrenes were estab-
lished using styrene 5a as model substrate (Scheme 2). The addition
reaction was performed in 1,2-dichloroethane using 1 equiv of
diphenyl diselenide and 4 equiv of styrene in the presence of
20 mol % iodine at 70 ꢁC for 16 h. The isolated product was char-
acterized as (E)-(2,4-diphenylbut-3-enyl)(phenyl)selane 6a as
shown in Scheme 2.
Ph
I2 (20 mol%)
Se
Ph
(PhSe)2
+
Ph
5a
Ph
1,2-dichloroethane
6a (55%)
70°C , 16 h
X–
R4
R
Scheme 2. Selenenylation of styrene 5a with styrene as nucleophile.
R4
R3
R2
R1
R4
R3
Nu–
RSe
R2
Se+
RSeX
+
R2
In order to optimize the reaction conditions, different solvents
have been investigated as shown in Table 1. Initially, the reaction
was performed in dichloroethane at room temperature but no re-
action took place (Table 1, entry 1). On heating the reaction mixture
to 70 ꢁC for 16 h, addition product 6a was isolated in 55% yield
(Table 1, entry 2) while the remaining compound was identified to
be styrene starting material. The same reaction was also performed
for 24 h but the addition product was obtained in identical yields
(Table 1, entry 3). Other chlorinated solvents such as dichloro-
methane and chloroform were also used but the product 6a was
Nu
R1 R3
R1
1
2
3
4
Scheme 1. Selenenylation of alkenes 1.
* Corresponding author. Tel./fax: þ44 29 2087 6968; e-mail address: wirth@
cf.ac.uk (T. Wirth).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.08.034

10574
E. Gabriele et al. / Tetrahedron 68 (2012) 10573e10576
ꢀ78 ꢁC and the addition product 6i was obtained in 30% yield, trace
Table 1
Different solvents for the addition reaction of 5a
amounts of a benzoselenothiine-1-oxide have also been observed
as reported earlier (Table 2, entry 9).6
Ph
I2 (20 mol%)
Se
Ph
(PhSe)2
Styrenes with electron-withdrawing substituents at the aro-
matic ring were also used, but the addition reaction was un-
successful. This is probably due to the fact that electron-
withdrawing groups decrease the nucleophilicity of the styrene,
which is then unable to react as a nucleophile. Furthermore, we
performed the same addition reaction using a 1:1 mixture of sty-
rene 5a and 4-chlorostyrene 5g and a mixture of both addition
products 6a and 6g was obtained in a combined yield of 68% (Table
2, entry 7). Interestingly, 4-chlorostyrene as a single substrate did
not produce any product.
+
Ph
5a
Ph
solvent
70 ºC, 12-24 h
6a
Entry
1a
2
Solvent
Reaction time (h)
6a Yield (%)
1,2-Dichloroethane
1,2-Dichloroethane
1,2-Dichloroethane
CH2Cl2
CHCl3
THF
12
16
24
24
24
24
24
d
55
55
22
15
29
31
3
4b
5
6b
7
H2O
Furthermore, the same reaction was performed with a-meth-
a
Reaction performed at 20 ꢁC.
Reaction performed at reflux.
ylstyrene 9 and the isolated product was characterized as phenyl(2-
phenylallyl)selane 10 in 87% yield while the expected addition
product was not observed (Scheme 3). All reaction products were
fully characterized by spectroscopic analysis.
b
isolated in 22% and 15% yields, respectively (Table 1, entries 4 and
5). The reaction also proceeded in tetrahydrofuran and water, but
product 6a was obtained in lower yields (Table 1, entries 6 and 7).
After the solvent optimization, the reaction was performed with
smaller amounts of iodine (5 and 10 mol %) but the addition
product was obtained in only 18% and 41% yields, respectively. With
the optimal reaction conditions, a series of addition reaction of
different alkenes 5beg were successfully performed and addition
products 6beg were isolated in moderate to good yields as shown
in Table 2. The addition reactions were working smoothly with
styrene systems 5 having electron donating functionality at aro-
matic ring and the products were isolated in moderate to good
yields (Table 2, entries 2e4).
I2 (20 mol%)
SePh
(PhSe)2
+
1,2-dichloroethane
70 ºC, 15 h
9
10 (87%)
a-methylstyrene 9.
Scheme 3. Selenenylation of
We propose a catalytic cycle for the iodine-mediated selene-
nylation of alkenes using styrene as nucleophile as shown in
Scheme 4. The catalytic cycle is initiated by the formation of phe-
nylselenenyl iodide 11 by the reaction of diphenyl diselenide and
iodine. Phenylselenenyl iodide 11 then adds to styrene to form the
seleniranium intermediate 12, which could be attacked by the
styrene nucleophile to form addition product 13. The reaction in-
termediate 13 forms the final reaction product 6 by HI elimination.
Finally, HI could further react with diphenyl diselenide to phenyl-
selenenyl iodide 11 to continue the catalytic cycle.
Table 2
Different alkenes 5 in the selenenylation reaction
R
I2 (20 mol%)
R
Ar
+
Ar
6
8
Se
Ar
Ar
+
1,2-dichloroethane
70 ºC
Se)2
5
7
Ar
Entry
R
Ar
6 Yield (%)
8 Yield (%)
(PhSe)2
I2
Ar
1
2
3
4
5
6
7a
7a: H
7a: H
7a: H
7a: H
7a: H
7a: H
7a: H
5a: Ph
6a: 55
6b: 62
6c: 62
6d: 51
6e: 31
6f: 33
6a and 6g:
68 (1:1)
6h: 0
d
5b: 2-MeC6H4
5c: 3-MeC6H4
5d: 4-MeC6H4
5e: 4-PhC6H4
5f: 2-Naphthyl
5a: Ph and 5g:
4-ClC6H4 (1:1)
5h: 4-MeOC6H4
5a: Ph
d
d
HI
Se
PhSeI
11
d
Ar
Ph
H
8e: 27
8f: 26
d
6
Ar
Ar
5
8
7a: H
7b: SO-t-Bu
d
d
I
9b
6i: 30
Se
Ar
a
Ph
The reaction was performed with the mixture of styrene and 4-chlorostyrene in
Ph
Se+
13
a 1:1 ratio.
b
The reaction was performed in THF at ꢀ78 ꢁC using equimolar amounts of
Ar
bromine instead of iodine.
12
Ar
5
The reaction was successfully performed using methyl-
substituted styrenes and the addition products were isolated in
good yields (Table 2, entries 2e4). When the same reaction was
performed with 4-vinyl-1,10-biphenyl 5e, the addition product 6e
was isolated in 31% yield together with the deselenylated product
8e (Table 2, entry 5). The course of the reaction was similar with 2-
vinylnaphthalene and the products 6f along with 8f were isolated
(Table 2, entry 6). The addition reaction was unsuccessful with 4-
methoxystyrene 5h (Table 2, entry 8). The addition reaction of
styrene was performed with diselenide 7b (R¼SO-t-Bu) in THF at
Scheme 4. Proposed mechanism for the selenenylation sequence.
3. Conclusion
In summary, we have demonstrated that iodine-mediated re-
actions of different styrene derivatives with diaryl diselenides lead
to novel addition products. The interesting feature of this reaction is
that styrenes are used as nucleophiles. Research studies about the
wider scope of this approach are currently in progress.

E. Gabriele et al. / Tetrahedron 68 (2012) 10573e10576
10575
4. Experimental section
4.1. General
1073, 1022, 960, 913, 879, 776, 737 cmꢀ1; HRMS (ESþ): m/z [MþH]þ
calculated for C24H2580Se: 393.1121; found 393.1134.
4.2.4. (E)-(2,4-Di-p-tolylbut-3-enyl)(phenyl)selane (6d). Yellow oil;
Melting points were obtained in open capillary tubes. 1H NMR
and 13C NMR spectra were recorded on an AV-400 Bruker using the
solvents indicated with 400 and 100 MHz, respectively, also a DRX-
500 Bruker was used in the some cases for 1H (500 MHz) and 13C
(125 MHz). Mass spectra (m/z) and HRMS were recorded under the
conditions of electron impact (EI) and electrospray (ES) and
chemical ionization (CI). Infrared spectra were recorded on an ASCO
FT/IR-660 Plus spectrophotometer. All reactions were monitored by
thin-layer chromatography that was performed on pre-coated
sheets of silica gel 60, and flash column chromatography was per-
formed with silica gel 60 (Merck, 230e400 mesh). Eluting solvents
are indicated in the text. All experiments were performed under
open atmosphere. Dichloroethane was purchased from Sigma-
eAldrich Chemicals Limited while THF was used from a solvent
purification system. All other purchased chemicals were used
without further purification.
yield: 51% (100 mg, 0.255 mmol); 1H NMR (400 MHz, CDCl3):
d
¼2.24 (s, 3H, Me), 2.25 (s, 3H, Me), 3.26 (d, J¼6.8 Hz, 2H, CH2), 3.65
(q, J¼6.8 Hz,1H, CH), 6.17e6.34 (m, 2H, CH), 6.94e7.06 (m, 6H, ArH),
7.12e7.17 (m, 5H, ArH), 7.38e7.42 (m, 2H, ArH) ppm; 13C NMR
(100 MHz, CDCl3):
(2C), 129.1 (2C), 129.2 (129.2), 129.4 (2C), 130.5, 130.8, 131.4, 132.7
(2C), 134.4, 136.5, 137.1, 140.2 ppm; IR (film):
¼3019, 2919, 2860,
d¼21.1, 21.2, 34.3, 48.9, 126.2 (2C), 126.8, 127.5
n
1578, 1511, 1478, 1437, 1180, 1073, 1021, 963, 913, 815, 797 cmꢀ1
;
HRMS (ESþ): m/z [MþH]þ calculated for C24H2580Se: 393.1121;
found 393.1121.
4.2.5. (E)-(2,4-Di(biphenyl-4-yl)but-3-enyl)(phenyl)selane
(6e). Yellow oil; yield: 31% (79 mg, 0.155 mmol); 1H NMR
(400 MHz, CDCl3):
d
¼3.34 (d, J¼7.6 Hz, 2H, CH2), 3.79 (q, J¼7.6 Hz,
1H, CH), 6.38e6.45 (m, 2H, CH), 7.34e7.38 (m, 7H, ArH), 7.42e7.46
(m, 5H, ArH), 7.47e7.53 (m, 11H, ArH) ppm; 13C NMR (125 MHz,
CDCl3):
d
¼34.1, 49.2, 126.2 (2C), 126.9 (3C), 127.1 (2C), 127.2 (2C),
4.2. General procedure for the synthesis of (E)-(2,4-diarylbut-
3-enyl)(phenyl)selanes 6aeg and 10
127.3, 127.5 (2C), 128.1 (2C), 128.79 (3C), 128.81 (2C), 129.1 (2C),
130.6, 130.7, 132.3, 132.9 (2C), 136.2, 139.9, 140.2, 140.8, 140.9,
142.3 ppm; IR (film):
n
¼1653, 1635, 1485, 913, 743 cmꢀ1; HRMS
The mixture of styrene derivative (1.0 mmol), diphenyl dis-
elenide (78 mg, 0.25 mmol), and iodine (12.7 mg, 0.05 mmol) in
1,2-dichloroethane (2 mL) was stirred at 70 ꢁC for 16e20 h. The
reaction was monitored by thin-layer chromatography. After the
completion of reaction, the solvent was removed under vacuum
and the reaction was quenched by the addition of 10% aq Na2S2O3
solution. The reaction mixture was extracted with dichloromethane
(3ꢂ10 mL). The combined organic layers were dried over MgSO4,
filtered, and evaporated under vacuum. Finally, the crude product
was purified by column chromatography using hexane as eluent.
(ESþ): m/z [MþH]þ calculated for C34H2876Se: 513.1456; found
513.1445.
4.2.6. (E)-(2,4-Di(naphthalen-2-yl)but-3-enyl)(phenyl)selane
(6f). Yellow oil; yield: 33% (76 mg, 0.165 mmol); 1H NMR
(400 MHz, CDCl3):
d
¼3.42 (d, J¼7.6 Hz, 2H, CH2), 3.93 (q, J¼7.6 Hz,
1H, CH), 6.47e6.56 (m, 2H, CH), 7.38e7.41 (m, 3H, ArH), 7.45e7.50
(m, 4H, ArH), 7.53e7.61 (m, 7H, ArH) ppm; 13C NMR (125 MHz,
CDCl3):
d
¼34.4, 50.1, 124.0, 126.1 (2c), 126.2, 126.4 (2C), 126.59 (2C),
128.61, 126.64, 127.4, 128.06, 128.11, 128.2, 128.4 (2C), 128.5, 128.9,
129.5 (2C), 131.6, 132.6, 133.0 (2C), 133.3, 134.0, 134.9, 140.9 ppm; IR
4.2.1. (E)-(2,4-Diphenylbut-3-enyl)(phenyl)selane (6a). Yellow oil;
(film):
n
¼3054, 2961, 2924, 1599, 1507, 1271, 1022, 913, 855, 816,
yield: 55% (100 mg, 0.27 mmol); 1H NMR (400 MHz, CDCl3):
743 cmꢀ1; HRMS (ESþ): m/z [MþH]þ calculated for C30H2580Se:
d
¼3.30e3.38 (m, 2H, CH2), 3.76 (q, J¼6 Hz, 1H, CH), 6.33e6.42 (m,
2H, CH]CH), 7.17e7.28 (m, 9H, ArH), 7.29e7.32 (m, 4H, ArH),
7.45e7.47 (m, 2H, ArH) ppm; 13C NMR (100 MHz, CDCl3):
465.1121; found 466.1117.
d¼34.2,
4.2.7. (E)-(2,4-Bis(4-chlorophenyl)but-3-enyl)(phenyl)selane
(6g). This compound was isolated as inseparable mixture with
compound 6a in 1:1 ratio in overall 68% yield. Orange oil; 1H NMR
49.4, 126.4 (2C), 126.9, 127.0, 127.4, 127.6 (2C), 128.5 (2C), 128.7 (2C),
129.1 (2C),130.8,130.9, 132.2,132.8 (2C),137.2,143.2 ppm; IR (film):
n
¼3027, 2360, 1635, 1557, 1494, 1477, 1452, 1073, 1022, 963,
(400 MHz, CDCl3):
d
¼3.17e3.28 (m, 4H, 2ꢂCH2), 3.63e3.70 (m, 2H,
734 cmꢀ1; HRMS (ESþ): m/z [MþH]þ calculated for C22H2180Se:
2ꢂCH), 6.20e6.33 (m, 4H, 4ꢂCH), 7.08 (d, J¼8.4 Hz, 2H, ArH),
365.0808; found 365.0824.
7.12e7.25 (m, 22H, ArH), 7.36e7.40 (m, 4H, ArH) ppm; 13C NMR
(100 MHz, CDCl3):
d
¼34.3, 34.4, 49.2, 49.9, 126.8 (2C), 127.37,
4.2.2. (E)-(2,4-Di-o-tolylbut-3-enyl)(phenyl)selane (6b). Yellow oil;
127.44, 127.5, 127.96 (3C), 127.99 (2C), 129.0 (2C), 129.1 (2C), 129.19
(2C), 129.22 (2C), 129.5 (2C), 125.5 (2C), 129.6 (2C), 130.1, 130.8,
131.0, 131.5, 132.1, 133.0, 133.2 (2C), 133.32, 133.34 (2C), 133.4, 136.0,
yield: 62% (120 mg, 0.30 mmol); 1H NMR (400 MHz, CDCl3):
d
¼2.18
(s, 3H, Me), 2.21 (s, 3H, Me), 3.25 (d, J¼7.6 Hz, 2H, CH2), 3.92 (q,
J¼7.6 Hz, 1H, CH), 6.10 (dd, J1¼7.6 Hz, J2¼15.6 Hz, 1H, CH), 6.50 (d,
J¼15.6 Hz, 1H, CH), 7.02e7.19 (m, 10H, ArH), 7.25e7.28 (m, 1H, ArH),
137.3, 141.9, 143.4 ppm; IR (film):
n
¼3057, 3026, 2918, 2849, 1578,
1490, 1477, 1451, 1437, 1403, 1091, 1073, 1012, 820, 734 cmꢀ1; HRMS
(ESþ): m/z [M]þ calculated for C22H18Cl276Se: 427.9972; found
427.9971.
7.39e7.42 (m, 2H, ArH) ppm; 13C NMR (100 MHz, CDCl3):
d
¼19.6,
19.9, 33.6, 45.0, 125.8, 126.1, 126.5 (2C), 126.7, 127.0, 127.3, 128.9,
129.2 (2C), 130.2, 130.7 (2C), 133.0 (2C), 133.3, 135.3, 135.9, 136.5,
141.4 ppm; IR (film):
n
¼3058, 3018, 2968, 2925, 2738, 1799, 1601,
4.3. Procedure for the synthesis of (rac)-2-(tert-butylsulfinyl)
phenyl-(E)-2,4-diphenylbut-3-enyl selenide (6i)
1578, 1486, 1478, 1460, 1436, 1379, 1022, 964 cmꢀ1; HRMS (ESþ):
m/z [MþH]þ calculated for C24H2580Se: 393.1121; found 393.1115.
Bis[2-(tert-butylsulfinyl)phenyl]diselenide (520 mg, 1.0 mmol)
was dissolved in dry tetrahydrofuran (40 mL) under argon, cooled
to ꢀ78 ꢁC, and treated with bromine (1.0 mmol, 1.0 mL of a 1 M
solution in CCl4). After 20 min silver triflate (540 mg, 2.1 mmol) was
added and the mixture was stirred for 25 min at ꢀ78 ꢁC. The re-
action mixture was treated with styrene (229 mg, 2.20 mmol). The
mixture was further stirred at ꢀ78 ꢁC and warmed to ꢀ10 ꢁC
overnight. Then MeOH (1 mL) was added and the mixture was
stirred for additional 60 min at 0 ꢁC. Then 2,4,6-collidine (1 mL)
4.2.3. (E)-(2,4-Di-m-tolylbut-3-enyl)(phenyl)selane (6c). Yellow oil;
yield: 62% (120 mg, 0.30 mmol); 1H NMR (400 MHz, CDCl3):
d¼2.25
(s, 3H, Me), 2.26 (s, 3H, Me), 3.27 (d, J¼7.2 Hz, 2H, CH2), 3.66 (q,
J¼7.2 Hz, 1H, CH), 6.29e6.34 (m, 2H, CH), 6.94e7.19 (m, 11H, ArH),
7.39e7.42 (m, 2H, ArH) ppm; 13C NMR (100 MHz, CDCl3):
20.1, 34.1, 49.4, 123.5, 124.6, 126.8 (2C), 127.0, 127.6, 128.1, 128.3,
128.4, 128.6, 129.1 (2C), 130.8 (2C), 132.1, 132.7 (2C), 137.1, 138.0,
d¼19.9,
143.2 ppm; IR (film):
n
¼2918, 2849, 1605, 1579, 1477, 1436, 1377,

10576
E. Gabriele et al. / Tetrahedron 68 (2012) 10573e10576
was added, followed by water (40 mL). After extraction of the re-
action mixture with dichloromethane (3ꢂ50 mL), drying of the
combined organic phases with MgSO4, and removal of the solvent
under reduced pressure; the residue was purified by flash column
chromatography on silica gel, yielding the addition products as pale
yellow oils. The diastereomers could not be separated by flash
chromatography (ethyl acetate/hexanes, 1:5); yield 30% (309 mg,
0.30 mmol), pale yellow oil.
CH2), 4.93 (d, J¼1.6 Hz, 1H, CH), 5.20 (d, J¼1.6 Hz, 1H, CH), 7.14e7.29
(m, 6H, ArH), 7.35e7.42 (m, 4H, ArH) ppm; 13C NMR (100 MHz,
CDCl3):
d
¼33.0, 115.0, 126.3 (2C), 127.4, 127.9, 128.4 (2C), 129.0 (2C),
130.5, 134.0 (2C), 139.5, 144.2 ppm; IR (film):
n
¼3055, 3030, 2932,
1623, 1577, 1476, 1445, 1436, 1301, 1185, 1072, 1022, 900, 859, 775,
717 cmꢀ1; HRMS (ESþ): m/z [MþH]þ calculated for C15H1474Se:
269.0393; found 269.0390.
Acknowledgements
4.3.1. (rac)-2-(tert-Butylsulfinyl)phenyl-(E)-2,4-diphenylbut-3-enyl
selenide (6i). Yellow oil; yield: 33% (309 mg, 0.66 mmol); 1H NMR
Financial support by the EU, FP7 IIF Marie Curie Grant and the
School of Chemistry, Cardiff University, is gratefully acknowledged.
We thank the EPSRC National Mass Spectrometry Service Centre,
Swansea, for mass spectrometric data.
(500 MHz, CDCl3):
d
¼1.12 (s, 9H, C(CH3)3), 3.30 (m, 2H, CH2), 3.69
(q, J¼7.4 Hz, 1H, CH), 6.27 (ddd, J1¼1.9 Hz, J2¼7.6 Hz, J3¼15.8 Hz, 1H,
CH), 6.37 (dd, J1¼15.9 Hz, J2¼20.4 Hz, 1H, CH), 7.16e7.24 (m, 11H,
ArH), 7.33e7.37 (m,1H, ArH), 7.45 (td, J1¼1.2 Hz, J2¼7.6 Hz,1H, ArH),
7.73 (ddd, J1¼1.4 Hz, J2¼3.7 Hz, J3¼7.8 Hz, 1H, ArH) ppm; 13C NMR
References and notes
(125 MHz, CDCl3):
d
¼23.3, 35.8, 35.9, 49.0, 49.1, 58.1, 58.2, 122.5,
126.3, 126.9, 127.0, 127.4, 127.5, 127.6, 128.4, 128.7, 130.9, 131.1, 131.4,
131.7, 131.8, 133.6, 133.7, 136.8, 136.9, 142.6, 142.7, 143.4 ppm; IR
1. (a) Wirth, T. Tetrahedron 1999, 55, 1; (b) Wirth, T. Angew. Chem. 2000, 112, 3890;
Angew. Chem., Int. Ed. 2000, 39, 3740; (c) Top. Curr. Chem. 2003, 208; (d) Browne,
D. M.; Wirth, T. Curr. Org. Chem. 2006, 10, 1893; (e) Freudendahl, D. M.; Shahzad,
S. A.; Wirth, T. Eur. J. Org. Chem. 2009, 1649; (f) Organoselenium Chemistry; Wirth,
T., Ed.; Wiley-VCH: Weinheim, 2011; (g) Singh, F. V.; Wirth, T. In Organic Selenium
and Tellurium Compounds; Rappoport, Z., Ed.; Wiley: Chichester, 2012; Vol. 3,
p 303.
(film):
n
¼3057, 3026, 2966, 2926, 1599, 1569, 1494, 1443, 1426,
1362, 1326, 1217, 1148, 1091, 965, 749, 699 cmꢀ1; HRMS (ESþ): m/z
[MþH]þ calculated for C26H29OS74Se: 463.1158; found 463.1163.
2. (a) Huguet, J. L. Adv. Chem. Ser. 1967, 76, 345; (b) Jones, D. N.; Mundy, D.;
Whitehouse, R. D. J. Chem. Soc., Chem. Commun. 1970, 86; (c) Walter, R.; Roy, J. J.
Org. Chem. 1971, 36, 2561.
4.3.2. (E)-4,40-(But-1-ene-1,3-diyl)dibiphenyl (8e). Colorless solid;
mp: 105e107 ꢁC; yield: 27% (49 mg, 0.135 mmol); 1H NMR
3. (a) Miyashita, M.; Suzuki, T.; Yoshikoshi, A. J. Am. Chem. Soc. 1989, 111, 3728; (b)
Wirth, T.; Kulicke, K. J.; Fragale, G. J. Org. Chem. 1996, 61, 2686; (c) Wirth, T.
Liebigs Ann./Recueil 1997, 1155; (d) Wirth, T.; Fragale, G. Synthesis 1998, 162; (e)
(400 MHz, CDCl3):
d
¼1.45 (d, J¼6.8 Hz, 3H, Me), 3.64 (q, J¼7.6 Hz,
1H, CH), 6.36e6.45 (m, 2H, CH), 7.24e7.30 (m, 4H, ArH), 7.34e7.38
(m, 6H, ArH), 7.46e7.53 (m, 8H, ArH) ppm; 13C NMR (125 MHz,
ꢀ
Fettes, A.; Carreira, E. M. J. Org. Chem. 2003, 68, 9274; (f) Prange, T.; Rodríguez,
ꢀ
M. S.; Suarez, E. J. Org. Chem. 2003, 68, 4422; (g) Endo, A.; Danishefsky, S. J. J. Am.
CDCl3):
d
¼21.3, 42.4, 126.6 (2C), 126.9 (2C), 127.08 (2C), 127.1, 127.2
Chem. Soc. 2005, 127, 8298; (h) Hong, W.-X.; Chen, L.-J.; Zhong, C.-L.; Yao, Z.-J.
Org. Lett. 2006, 8, 4919; (i) Davoren, J. E.; Martin, S. F. J. Am. Chem. Soc. 2007, 129,
510; (j) Trost, B. M.; Waser, J.; Meyer, A. J. Am. Chem. Soc. 2007, 129, 14556; (k)
Schnabel, C.; Hiersemann, M. Org. Lett. 2009, 11, 2555; (l) Yu, S.-M.; Hong, W.-X.;
Wu, Y.; Zhong, C.-L.; Yao, Z.-J. Org. Lett. 2010, 12, 1124.
(3C), 127.3 (2C), 127.8 (2C), 128.2, 128.7 (2C), 128.8 (2C), 135.3, 136.6,
139.3, 139.9, 140.8, 141.1, 144.7 ppm; IR (film):
n
¼3026, 1485, 1449,
1407, 761 cmꢀ1; HRMS (ESþ): m/z [M]þ calculated for C28H24
:
360.1873; found 360.1868.
4. (a) Tomoda, S.; Iwaoka, M. Chem. Lett. 1988, 1895; (b) Nishibayashi, Y.; Singh, J.
ꢀ
D.; Uemura, S.; Fukuzawa, S. Tetrahedron Lett. 1994, 35, 3115; (c) Deziel, R.;
4.3.3. (E)-2,20-(But-1-ene-1,3-diyl)dinaphthalene (8f). Orange oil;
yield: 26% (40 mg, 0.13 mmol); 1H NMR (400 MHz, CDCl3):
Malenfant, E. J. Org. Chem. 1995, 60, 4660; (d) Fujita, K.; Murata, K.; Iwaoka, M.;
Tomoda, S. Tetrahedron 1997, 53, 2029; (e) Wirth, T.; Fragale, G. Chem.dEur. J.
1997, 3, 1894; (f) Back, T. G.; Moussa, Z. Org. Lett. 2000, 2, 3007; (g) Tiecco, M.;
Testaferri, L.; Santi, C.; Tomassini, C.; Marini, F.; Bagnoli, L.; Temperini, A. Tet-
rahedron: Asymmetry 2000, 11, 4645; (h) Tiecco, M.; Testaferri, L.; Bagnoli, L.;
Marini, F.; Temperini, A.; Tomassini, C.; Santi, C. Tetrahedron Lett. 2000, 41, 3241;
(i) Tiecco, M.; Testaferri, L.; Santi, C.; Tomassini, C.; Marini, F.; Bagnoli, L.; Tem-
perini, A. Chem.dEur. J. 2002, 8, 1118; (j) Scianowski, J.; Rafinski, Z.; Wojtczak, A.
Eur. J. Org. Chem. 2006, 3216.
5. (a) Cox, M.; Wirth, T. Phosphorous Sulfur and Silicon 2005, 180, 659; (b) Browne,
D. M.; Niyomura, O.; Wirth, T. Org. Lett. 2007, 9, 3169; (c) Singh, F. V.; Wirth, T.
Org. Lett. 2011, 13, 6504.
6. Freudendahl, D. M.; Iwaoka, M.; Wirth, T. Eur. J. Org. Chem. 2010, 3934.
7. (a) Clive, D. L. J.; Chittattu, G.; Wong, C. K. J. Chem. Soc., Chem. Commun. 1978, 441;
(b) Kametani, T.; Suzuki, K.; Kurobe, H.; Nemoto, H. J. Chem. Soc., Chem. Commun.
1979, 1128; (c) Toshimitsu, A.; Uemura, S.; Okano, M. J. Chem. Soc., Chem. Com-
mun. 1982, 87.
d¼1.61
(d, J¼6.8 Hz, 3H, Me), 3.88 (q, J¼6.8 Hz, 1H, CH), 6.56e6.66 (m, 2H,
CH), 7.40e7.49 (m, 5H, ArH), 7.60 (d, J¼8.4 Hz, 1H, ArH), 7.71e7.79
(m, 5H, ArH), 7.83 (d, J¼8.0 Hz, 3H, ArH) ppm; 13C NMR (100 MHz,
CDCl3):
d
¼21.2, 42.8, 123.6, 125.3, 125.4, 125.6, 125.8, 126.0, 126.2,
126.4, 127.6 (3C), 127.7, 127.9, 128.1 (2C), 129.0 (2C), 132.8, 133.7,
135.02, 135.6, 143.0 ppm; IR (film):
n
¼3051, 2961, 2864, 1569, 1507,
913, 810, 743 cmꢀ1; HRMS (ESþ): m/z [MþH]þ calculated for C24H19
:
307.1487; found 307.1483.
4.3.4. Phenyl(2-phenylallyl)selane (10). Yellow oil; yield: 87%
(119 mg, 0.435 mmol); 1H NMR (400 MHz, CDCl3):
¼3.88 (s, 2H,
d