New diphenyl diselenides: O -substituted by an O(S,Se)-caranyl skeleton-synthesis and application in asymmetric reactions

Article abstract of DOI:10.1039/c6nj00487c

An efficient methodology for the synthesis of diphenyl diselenides o-substituted by O(S,Se)-caranyl moieties has been presented. 4-Caranyl and 4-isocaranyl groups have been connected to the phenyl ring by an oxygen, sulfur or selenium atom. The influence

Full text of DOI:10.1039/c6nj00487c

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. cianowski, A. J.
Pacua, M. Zieliska-Bajet and A. Wojtczak, New J. Chem., 2016, DOI: 10.1039/C6NJ00487C.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/njc

Page 1 of 19
New Journal of Chemistry
View Article Online
New diphenyl diselenides o-substituted by O(S, Se)-carDO
a
I:
n
10
y
.1039/C6NJ00487C
l
skeleton – synthesis and application in asymmetric reactions
*a
a
b
c
Jacek Ścianowski , Agata J. Pacuła , Mariola Zielińska-Błajet , Andrzej Wojtczak
a
Department of Organic Chemistry, Faculty of Chemistry, Nicolaus Copernicus University in
Torun,7 Gagarin Street, 87-100 Torun, Poland
b
Department of Organic Chemistry, Faculty of Chemistry, Wroclaw University of Technology,
7 Wybrzeze Wyspianskiego Street, 50-370 Wroclaw, Poland
2
c
Department of Crystallochemistry and Biocrystallography, Faculty of Chemistry, Nicolaus
Copernicus University in Torun, 7 Gagarin Street, 87-100 Torun,Poland
E-mail: jsch@chem.umk.pl
Abstract: An efficient methodology for the synthesis of diphenyl diselenides o-substituted by
O(S, Se)-caranyl moieties has been presented. 4-Caranyl and 4-isocaranyl groups have been
connected to the phenyl ring by oxygen, sulfur or selenium atom. The influence of the
selenium-heteroatom interactions on the diastereoselectivity of the methoxyselenenylation of
styrene has been evaluated. The best result was obtained for diselenide with O-caranyl group
substituted in ortho-position. X-ray crystal structure of this compound was determined and the
observed intramolecular interactions were discussed. Additionally diselenides bearing a sulfur
atom were transformed to corresponding methyl o-(S-caranyl) and o-(S-isocaranyl)-
substituted phenyl selenides, and were tested as catalysts in the Tsuji-Trost allylic alkylation
and Henry reaction.
Key words: diselenides, terpenes, methoxyselenenylation reaction, allylic alkylation, Henry
reaction, selenium-heteroatom interactions
Introduction
Organoselenium compounds have been broadly applied in organic synthesis as
reagents and catalysts enabling a wide range of transformations. Se-derivatives can be used as
electrophilic, nucleophilic and radical species with broad application potential providing
simple and efficient methods for generating new carbon-carbon, carbon-nitrogen, carbon-
oxygen and carbon-halogen bonds [1-5]. Due to the unique properties of the selenium atom,
selenofunctionalization can proceed with good chemo- and regioselectivity [6].
Chiral diselenides are efficient precursors of electrophilic reagents commonly applied in the
asymmetric selenenylation of olefins. In the reaction of a selenium electrophile 1 with the

New Journal of Chemistry
Page 2 of 19
View Article Online
unsaturated substrate, the formation of a seleniranium ion 2 is observed, followed by a
DOI: 10.1039/C6NJ00487C
stereospecific anti-addition of the present nucleophile (Scheme 1) [7-9].
Scheme 1. Selenenylation of a double bond.
Stereoselectivity of the reaction can be influenced by several factors: structure of the substrate
and organoselenium reagent, type of the counteranion and non-bonding interactions between
selenium and other heteroatoms. These interactions can be divided into two types. When the
bonding atom acts as a weak electrophile, pulling closer the electron density of the selenium
lone electron pair, it is a Type 1 bonding. Type 2 is observed when the approaching
*
heteroatom is a weak nucleophile in relation to the antibonding σ selenium orbital [10]
(Figure 1).
σ
Figure 1. Schematic representation of different types of Se···Y nonbonded interaction [10].
When a chiral center with a heteroatom is in close proximity to selenium, the exhibited non-
bonding interaction stabilizes the structure and shortens the distance between the chiral
moiety and the reactive center improving the selectivity of the reaction. Examples of
derivatives possessing a chiral moiety in proximity to a heteroatom are showed in Figure 2
[
11-13].
Figure 2. Examples of chiral diselenides applied in methoxyselenenylation of styrene.

Page 3 of 19
New Journal of Chemistry
View Article Online
Compounds 3-5 provided high diastereomeric excess for the asymmetric
DOI: 10.1039/C6NJ00487C
methoxyselenenylation of styrene. The results clearly demonstrate the importance of the non-
bonding Se-heteroatom interaction on the selectivity of the addition reaction. This conclusion
is also supported by the result for compound 6 where the absence of a heteroatom in the side
chain resulted in de 0%.
Recently, several papers and reviews have reported the synthesis and utilization of terpenyl
diselenides in which the selenium atom was directly connected to the chiral moiety [14-22].
However, terpenes have not yet been implemented as chirality sources in the structure of
diaryl diselenides. In this work we present the synthesis and application routes for new
diphenyl diselenides substituted in the ortho position by chiral caranyl and isocaranyl
moieties connected to the aromatic ring through oxygen, sulfur or selenium atom (Figure 3).
The influence of the terpenyl moieties and the type of heteroatom on the diastereoselectivity
of the applied electrophiles in methoxyselenenylation reaction of styrene has been evaluated.
Figure 3. Structure of the synthetized diaryl diselenides.
Additionally derivatives bearing a sulfur atom were transformed to methyl o-substituted
phenyl selenides and used in the allylic alkylation and Henry reaction. Hitherto, only few
examples of S,Se-donating ligands used in the Pd-catalyzed allylic substitution were reported
so far. The bis(chalcogen) ligands 7 and 8 effectively catalyze the asymmetric allylic
alkylation with enantioselectivities of 44% and 34% ee respectively (Figure 4) [23-24]. The
results of these reactions are also demonstrated.
Figure 4. Selenides applied in the Tsuji-Trost reaction.

New Journal of Chemistry
Page 4 of 19
View Article Online
DOI: 10.1039/C6NJ00487C
Results and discussion
First step of our research included the synthesis of (–)-4-isocaranyl tosylate 8 and (+)-4-
caranyl chloride 9 from (–)-4-isocaranol 7 according to the previously reported methodology
(Scheme 2) [16].
Scheme 2. Synthesis of isocaranyl tosylate and caranyl chloride.
Substrates for the synthesis of diselenides, phenyl-caranyl o-bromo ethers 13, 14, sulphides
1
5, 16 and phenyl-caranyl selenides 17, 18 were obtained in the reaction of isocaranyl tosylate
and caranyl chloride with o-bromo phenol 10, o-bromo thiophenol 11 and diphenyl diselenide
2 previously treated with sodium hydride (Scheme 3).
1
Scheme 3. Synthesis of compounds 13-18.

Page 5 of 19
New Journal of Chemistry
View Article Online
Diselenides 19-24 were synthetized by two methods. For substrates 13-16 possessing
DOI: 10.1039/C6NJ00487C
bromium in the aromatic ring magnesium and selenium powders were used to form
selenolate, subsequently hydrolyzed with ammonium chloride and oxidized to diselenides 19-
2
2. In case of diselenides 23 and 24, in the first step of synthesis metalation with butyl lithium
was performed (Scheme 4).
Scheme 4. Synthesis of diselenides 19-24.
Crystallographic analysis was made for diselenide 19. The asymmetric part of the structure
consists of a single molecule. Two o-phenyl-O-caranyl fragments are connected by the
diselenide bridge (Scheme 4). The 1S,3R,4S,6R configuration was found for the first caranyl
moiety and identical 1’S,3’R,4’S,6’R for the second moiety, consistent with the substrate
configuration. The Se1-C16 and Se2-C16’ distances of 1.936(7) and 1.930(7) Å are typical
for such bonds. The C16-Se1-Se2 and C16’-Se2-Se1 angles are 102.6(2) and 103.5(2)º,
respectively. Conformation of the diselenide bridge is anticlinal with the C16-Se1-Se2-C16’
torsion angle of -95.2(3)º. Orientation of two phenyl rings relative to the diselenide bridge is
different, with the torsion angles C11-C16-Se1-Se2 of -162.1(5) and Se1-Se2-C16’-C11’ of
1
56.0(5)º. In such conformation, the dihedral angle between the phenyl ring planes is 71.6(4)º.
Orientation of the caranyl moieties relative to the neighboring phenyl ring is similar, with
torsion angles C11-O1-C4-C3 and C11’-O2-C4’-C3’ being -157.1(7) and -156.9(7)º. The
non-bonded interactions in the organoselenium compounds have been reviewed in the
literature [10]. The structural data reported here revealed the presence of intramolecular

New Journal of Chemistry
Page 6 of 19
View Article Online
contacts Se1…O1 and Se2…O2 of 2.854(6) and 2.877(5) Å, respectively, shorter by 0.5 Å
DOI: 10.1039/C6NJ00487C
than the sum of vdW radii. Since the distance between the O atoms and the adjacent C-Se1-
Se2 planes are 0.708 and -0.980Å for O1 and O2, respectively, and the Se…O interactions are
approximately co-linear with the Se1-Se2 bond, they fulfill the criterion of Type 2
interactions between selenium and the nucleophile. Analysis also revealed the intramolecular
interactions Se1...H15’-C15’ and Se2...H15a-C15 involving the phenyl C-H groups, with the
Se…H distances being 3.04 and 2.87 Å, respectively. These interactions correspond to the
interactions considered as Se…H-C hydrogen bonds. Since distances of H15 and H15’ from
the C-Se-Se plane are -2.689 and 2.526 Å, respectively, these interactions fulfill the criterion
of Type 1 interactions with the weak electrophile interacting with electrons of the selenium
lone-pair. Also the intermolecular Se1…H14’-C14’[-x,-1/2+y,1-z], Se2…H6A’-C6’[-x,-
1
/2+y,-z], Se2…H5A’-C5’[-x,-1/2+y,-z] and Se2…H6A’-C6’[-x,-1/2+y,-z] are found, with
the Se…H distances of 3.29, 3.28, 3.12 and 2.84 Å, respectively.
In the next part of our research diselenides were applied in the methoxyselenenylation of
styrene. Compounds 19-24 were transformed to electrophilic reagents by treatment with 1M
solution of bromine and silver triflate. In the presence of methanol as an external nucleophile
the addition products 25-30 were obtained. Results are presented in Table 1. The best
diastereoselectivity was obtained for diselenide bearing an oxygen atom 25.
Table 1. Results for the asymmetric methoxyselenenylation of styrene.
Diselenide
Product
25
dr
Yield [%]
1
2
2
2
2
2
9
0
1
2
3
4
68:32
61:39
63:37
52:48
53:47
56:44
78
14
47
11
66
19
26
27
28
29
30

Page 7 of 19
New Journal of Chemistry
View Article Online
Diselenides 21 and 22 were additionally transformed to methyl selenides 31 and 32 using
DOI: 10.1039/C6NJ00487C
sodium borohydride and methyl iodide (Scheme 5).
Scheme 5. Synthesis of methyl selenides 31 and 32.
Catalytic efficiency of compounds 31 and 32 was also tested. Tsuji-Trost reaction of dimethyl
malonate with rac-1,3-diphenyl-2-propenyl acetate, was performed using 3 mol% of N,O-
3
bis(trimethylsilyl)acetamide-potassium acetate as a base, 2.5 mol% of [Pd( -C H )Cl] , and
3
5
2
1
0 mol% of tested chiral ligand in acetonitrile solution. Dimethyl(1,3-diphenyl-2-propen-1-
yl)malonate was obtained in high yield and moderate enatioselectivity (Scheme 6).
Scheme 6. Pd-Catalyzed alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl
malonate.
Derivatives 31 and 32 were also tested in the copper-catalyzed Henry reaction (Scheme 7).
Scheme 7. Nitroaldol reaction catalyzed by Ligand/Cu(OAc) .
2
.

New Journal of Chemistry
Page 8 of 19
View Article Online
In case of compound 31 addition of benzaldehyde to nitromethane proceeds with good yield
DOI: 10.1039/C6NJ00487C
but low enantioselectivity. For selenide 32 no enatiomeric excess was observed. The reaction
was run in the presence of base additive such as Et N to accelerate the reaction.
3
Conclusions
In this paper we have presented an efficient methodology for the synthesis of diphenyl
diselenides o-substituted with caranyl and isocaranyl moieties connected to the atromatic ring
by oxygen, sulfur or selenium atom. Diselenides were applied as reagents in
methoxyselenenylation of styrene. The best result was obtained for diselenide bearing O-
caranyl substituent. Crystallographic structure of the most efficient reagent was presented and
the evaluated intramolecular nonbonding Se-H and Se-O interactions were discussed.
Diselenides bearing a sulfur atom were also transformed to corresponding methyl selenides.
These derivatives were applied as ligands in Pd-catalyzed alkylation (Tsuji-Trost reaction)
and Henry reaction with good yield and low to moderate enantioselectivities.
Experimental
General. 1H NMR spectra were obtained at 200 or 300 MHz and chemical shifts were
recorded relative to SiMe (δ 0.00) or solvent resonance (CDCl δ7.26). Multiplicities were
4
3
given as: s (singlet), d (doublet), dd (double doublet), ddd (double double doublet), t (triplet),
dt (double triplet), td (triple doublet) and m (multiplet). The number of protons (n) for a given
resonance was indicated by nH. Coupling constants were reported as a J value in Hz. 13C
NMR spectra were acquired at 50.3Hz and chemical shifts were recorded relative to solvent
resonance (CDCl δ77.25). Commercially available solvents THF, DMF, methanol, diethyl
3
and petroleum ether (Aldrich) and chemicals were used without further purification. Column
chromatography was performed using Merck Kieselgel 60 (0.06-0.2mm). The enantiomeric
composition of nitroaldols was determined by HPLC analysis using a chiral stationary phase
(Chiracel OD-H or Daicel Chiralpak AD-H). The absolute configuration was assigned by
comparison of the retention time and the sign of the specific rotation with literature data.
General procedure for the synthesis of phenyl-terpenyl o-bromoethers 13,14, sulphides
1
5,16 and selenides 17,18.
To a solution of 60% sodium hydride (dispersion in mineral oil) (0.5g, 12.5 mmol) in DMSO
(10 ml) substrate 10, 11, or 12 ( 10 mmol) was added. The mixture was stirred for 1h under
o
argon atmosphere at room temperature (at 50 C for diphenyl diselenide 12). Tosylate 8 or

Page 9 of 19
New Journal of Chemistry
View Article Online
chloride 9 (10 mmol) dissolved in DMSO (10 ml) was added and the mixture was stirred for
DOI: 10.1039/C6NJ00487C
o
5
h at 100 C (4 days at room temperature for compounds 14 and 16). Mixture was poured on 3
M sodium hydroxide solution (100 ml), extracted with diethyl ether (3x50 ml), washed with
water, 3 M sodium hydroxide and water. Combined organic layers were dried with anhydrous
magnesium sulphate and evaporated. Crude product was purified using column
chromathography (silica gel, hexane).
(1S,3R,4S,6R)-4-(2-Bromophenoxy)-3,7,7-trimethylbicyclo[4.1.0]heptane (13).
1
Yield 39%,
= +64.89 (c 1.78, CHCl ). H NMR (200 MHz, CDCl ):  0.47 (dt, 1H, J =
3
3
H
1
3
4
.22, 6.22 Hz), 0.83-0.91 (m, 1H), 0.98 (s, 3H, CH ), 1.00 (s, 3H, CH ), 1.10 (d, 3H, CH , J =
3 3 3
.42 Hz), 1.25-1.85 (m, 4H), 2.23 (ddd, 1H, J = 4.92, 6.18, 10,88 Hz), 4.26 (dd, 1H, J =1.76,
1
3
.82 Hz), 6.73-6.78 (m, 2H), 7.18-7.26 (m, 1H), 7.49-7.52 (dd, 1H, J = 1.14, 5.5 Hz).
C
NMR (CDCl , 75.5 MHz):  15.1 (CH ), 16.9 (CH), 17.6 (C), 17.8 (CH ), 21.7 (CH ), 22.0
3
C
3
3
2
(
CH), 24.1 (CH ), 28.9 (CH ), 33.4 (CH), 74.9 (CH), 112.6 (C), 113.1 (CH), 120.7 (CH),
2 3
1
28.1 (CH), 133.5 (CH), 154.4 (C). Anal. calcd for C H BrO (309.24): C, 62.14; H, 6.84
16 21
Found: C, 62.23; H, 6.87.
(1S,3R,4R,6R)-4-(2-Bromophenoxy)-3,7,7-trimethylbicyclo[4.1.0]heptane (14).
1
Yield 41%,
= -6.18 (c 1.40, CHCl ). H NMR (200 MHz, CDCl ):  0.78-0.98 (m, 2H),
3
3
H
0
1
7
1
3
.98 (d, 3H, CH , J = 2.84 Hz), 0.99 (s, 3H, CH ), 1.01 (s, 3H, CH ), 1.65-1.78 (m, 2H), 1.79-
3 3 3
.90 (m, 1H), 2.05-2.12 (m, 1H), 2.15-2.25 (m, 1H), 3.70-3.83 (m, 1H), 6.74-6.85 (m, 2H),
1
3
.17-7.26 (m, 1H), 7.50-7.54 (dd, 1H, J = 1.64, 6.48 Hz). C NMR (CDCl , 50 MHz): C
3
6.1 (CH ), 17.7 (C), 18.4 (CH ), 20.2 (CH), 21.4 (CH), 27.0 (CH ), 28.4 (CH ), 28.6 (CH ),
3
3
2
2
3
4.7 (CH), 82.9 (CH), 113.0 (C), 114.5 (CH), 121.3 (CH), 128.2 (CH), 133.5 (CH), 155.1 (C).
Anal. calcd for C H BrO (309.24): C, 62.14; H, 6.84 Found: C, 62.10; H, 6.88.
1
6
21
(1S,3R,4S,6R)-4-(2-Bromophenylthio)-3,7,7-trimethylbicyclo[4.1.0]heptane (15).
1
Yield 71%,
= +38.52 (c 1.42, CHCl ). H NMR (200 MHz, CDCl ):  0.57-0.79 (m,
3
3
H
2
1
7
H), 1.00 (s, 3H, CH ), 1.03 (d, 3H, CH , J = 7.0 Hz), 1.06 (s, 3H, CH ), 1.25-1.46 (m, 2H),
3 3 3
.82-2.28 (m, 3H), 3.44-3.58 (dd, 1H, J = 6.2, 8.2 Hz), 6.97-7.05 (m, 1H), 7.20-7.38 (m, 2H),
1
3
.52-7.57 (dd, 1H, J = 1.0, 7.8 Hz). C NMR (CDCl , 50 MHz):  15.7 (CH ), 17.8 (C), 18.8
3
C
3
(
CH ), 21.0 (CH), 21.2 (CH), 24.6 (CH ), 25.6 (CH ), 28.5 (CH ), 30.6 (CH), 45.9 (CH),
3 2 2 3
1
24.9 (C), 126.6 (CH), 127.5 (CH), 130.1 (CH), 133.1 (CH), 138.5 (C). Anal. calcd for
C H BrS (325.31): C, 59.07; H, 6.51 Found: C, 58.89; H, 6.57.
16
21

New Journal of Chemistry
Page 10 of 19
View Article Online
DOI: 10.1039/C6NJ00487C
(
1S,3R,4R,6R)-4-(2-Bromophenylthio)-3,7,7-trimethylbicyclo[4.1.0]heptane (16).
1
Yield 35%,
= –123.20 (c 1.69, CHCl ). H NMR (200 MHz, CDCl ):  0.61-0.92 (m,
3
3
H
2
2
7
H), 0.97 (s, 3H, CH ), 0.98 (s, 3H, CH ), 1.03 (d, 3H, CH , J = 6.29 Hz), 1.25-2.16 (m, 5H),
3 3 3
.81-2.89 (m, 1H), 7.01-7.11 (m, 1H), 7.20-7.30 (m, 1H), 7.37 (dd, 1H, J = 1.49, 6.18 Hz),
13
.56 (dd, 1H, J= 1.4, 8.0 Hz). C NMR (CDCl , 50 MHz):  15.6 (CH ), 17.6 (C), 19.7
3
C
3
(
CH), 20.6 (CH ), 20.7 (CH), 27.8 (CH ), 28.7 (CH ), 29.3 (CH ), 34.6 (CH), 50.6 (CH),
3 2 3 2
1
26.1 (C), 127.2 (CH), 127.4 (CH), 131.8 (CH), 133.1 (CH), 137.4 (C). Anal. calcd for
C H BrS (325.31): C, 59.07; H, 6.51 Found: C, 59.28; H, 6.47.
16
21
(1S,3R,4S,6R)-4-(Phenylseleno)-3,7,7-trimethylbicyclo[4.1.0]heptane (17).
1
Yield 64%,
= +44.16 (c 1.1, CHCl ). H NMR (300 MHz, CDCl ):  0.51-0.59 (m,
3
3
H
1
1
7
2
1
3
H), 0.64-0.72 (m, 1H), 0.97 (s, 3H, CH ), 0.98 (d, 3H, CH , J = 7.05 Hz), 1.02 (s, 3H, CH ),
3 3 3
.26-1.55 (m, 2H), 1.82-2.02 (m, 2H), 2.17-2.27 (m, 1H), 3.58 (dt, 1H, J = 6.66, 8.43 Hz),
1
3
.22- 7.29 (m, 3H), 7.50-7.56 (m, 2H). C NMR (CDCl , 50 MHz):  15.8 (CH ), 17.7 (C),
3
C
3
0.3 (CH ), 21.3 (CH), 21.4 (CH), 25.7 (CH ), 25.9 (CH ), 28.5 (CH ), 31.0 (CH), 47.0 (CH),
3
2
2
3
7
7
26.7 (CH), 128.8 (2 x CH), 131.1 (C), 133.8 (2 x CH). Se NMR (38 MHz, CDCl3): 
Se
46.33. Anal. calcd for C H Se (293.31): C, 65.52; H, 7.56 Found: C, 65.42 H, 7.59.
1
6
22
(1S,3R,4R,6R)-4-(Phenylseleno)-3,7,7-trimethylbicyclo[4.1.0]heptane (18).
1
Yield 36%,
= -102.72 (c 1.88, CHCl ). H NMR (200 MHz, CDCl ):  0.50-0.62 (m,
3
3
H
1
1
H), 0.68-0.87 (m, 1H), 0.93 (s, 3H, CH ), 0.97 (s, 3H, CH ), 1.03 (d, 3H, CH , J = 6.80 Hz),
3 3 3
.24-2.08 (m, 5H), 2.68-2.83 (dt, 1H, J = 8.4, 16.4 Hz), 7.22-7.33 (m, 3H), 7.45-7.64 (m, 2H).
C NMR (CDCl , 50 MHz):  15.6 (CH ), 17.5 (C), 20.6 (CH), 20.7 (CH), 21.8 (CH ), 28.8
1
3
3
C
3
3
(
CH ), 29.7 (CH ), 29.5 (CH ), 34.7 (CH), 48.9 (CH), 127.1 (CH), 128.8 (2 x CH), 129.1 (C),
3 2 2
7
7
1
34.9 (2 x CH). Se NMR (38 MHz, CDCl3):  403.61. Anal. calcd for C H Se (293.31):
Se
16 22
C, 65.52; H, 7.56 Found: C, 65.62; H, 7.54.
General procedure for the synthesis of diselenides 19-22.
To a suspension of magnesium (0.12g, 5.0 mmol) in THF (20 ml) compound 13, 14, 15 or 16
5.0 mmol) dissolved in THF (10ml) was added. Mixture was stirred in reflux for 3h.
(
Selenium (0.39g, 5.0 mmol) was added and the reaction was stirred in reflux for additional 2h.
Mixture was poured on a saturated solution of ammonium chloride (15ml) and oxidized with
air for 3h. Decantated solution was extracted with diethyl ether (3x50ml). Combined organic
layers were washed with water, dried over anhydrous magnesium sulfate and evaporated.
Crude product was purified using column chromatography (silica gel, hexane).

Page 11 of 19
New Journal of Chemistry
View Article Online
bis(2-((1S,3R,4S,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-yloxy)phenyl)diselenide (19)
DOI: 10.1039/C6NJ00487C
1
Yield 74%,
= +36.05 (c 1.43, CHCl ). H NMR (200 MHz, CDCl ):  0.46 (dt, 1H, J =
3
3
H
1
.86, 9.33 Hz), 0.80-0.97 (m, 1H), 1.01 (s, 3H, CH ), 1.05 (d, 3H, CH , J = 6.67 Hz), 1.07 (s,
3 3
3
H, CH ), 1.17-2.00 (m, 4H), 2.16-2.38 (m, 1H), 4.33 (dd, 1H, J = 2.52, 6.84 Hz), 6.63- 6.70
3
(m, 1H), 6.78 (dt, 1H, J = 1.14, 7.53 Hz), 7.09-7.18 (m, 1H), 7.41 (dd, 1H, J = 1.56, 7.74 Hz).
1
3
C NMR (CDCl , 50 MHz):  15.1 (CH ), 16.9 (CH), 17.6 (C), 17.7 (CH ), 21.8 (CH ), 22.1
3
C
3
3
2
(
CH), 24.1 (CH ), 28.9 (CH ), 33.4 (CH), 75.1 (CH), 112.6 (C), 113.1 (CH), 120.7 (CH),
2 3
77
1
28.1 (CH), 133.6 (CH), 154.4 (C). Se NMR (38 MHz, CDCl3):  316.82. Anal. calcd for
Se
C H O Se (616.59): C, 62.33; H, 6.87 Found: C, 62.53; H, 6.82.
32
42
2
2
bis(2-((1S,3R,4R,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-yloxy)phenyl)diselenide (20)
1
Yield 28%,
= –104.83 (c 1.78, CHCl ). H NMR (200 MHz, CDCl ):  0.75-1.00 (m
3
3
H
,
2H), 1.01 (s, 3H, CH ), 1.03 (s, 3H, CH ), 1.04 (d, 3H, CH , J = 9.8 Hz), 1.53-2.29 (m, 4H),
3 3 3
2
1
1
1
.95-2.99 (m, 1H), 3.79-3.91 (m, 1H), 6.71-6.77 (m, 1H), 6.78-6.85 (m, 1H), 7.09-7.19 (m,
1
3
H), 7.49 (dd, 1H, J = 1.6, 7,8 Hz). C NMR (CDCl , 50 MHz):  16.1 (CH ), 17.7 (C),
3
C
3
8.8 (CH ), 20.2 (CH), 21.3 (CH), 27.1 (CH ), 28.3 (CH ), 28.6 (CH ), 34.6 (CH), 82.3 (CH),
3
2
2
3
7
7
12.1 (CH), 119.8 (C), 121.5 (CH), 127.6 (CH), 130.0 (CH), 155.6 (C). Se NMR (38 MHz,
CDCl3):  326.7. Anal. calcd for C H O Se (616.59): C, 62.33; H, 6.87 Found: C, 62.28;
Se
32 42
2
2
H, 6.86.
bis(2-((1S,3R,4S,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-ylthio)phenyl)diselenide
21).
Yield 56%,
(
1
= +81.05 (c 1.68, CHCl ). H NMR (300 MHz, CDCl ):  0.45-0.59 (m,
3
3
H
1
1
1
2
1
3
H), 0.63-0.74 (m, 1H), 0.99 (s, 3H, CH ), 1.09 (d, 3H, CH , J = 7.22 Hz), 1.10 (s, 3H, CH ),
3 3 3
.41-1.60 (m, 2H), 1.79-2.23 (m, 3H), 3.40-3.51 (m, 1H), 7.05-7.20 (m, 2H), 7.33-7.47 (m,
1
3
H), 7.52-7.64 (m, 1H). C NMR (CDCl , 50 MHz):  15.9 (CH ), 17.9 (C), 18.9 (CH ),
3
C
3
3
0.9 (CH ), 21.2 (CH ), 25.0 (CH), 25.6 (CH), 28.5 (CH ), 31.0 (CH), 51.1 (CH), 127.2 (CH),
2
2
3
7
7
28.8 (CH), 128.9 (CH), 134.4 (CH), 134.5 (C), 136.6 (C). Se NMR (38 MHz, CDCl3): 
Se
97.14. Anal. calcd for C H S Se (648.73): C, 59.25; H, 6.53 Found: C, 59.16; H, 6.48.
3
2
42
2
2
bis(2-((1S,3R,4R,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-ylthio)phenyl)diselenide
22).
Yield 30%,
(
1
= -86.09 (c 1.72, CHCl ). H NMR (300 MHz, CDCl ):  0.63-0.90 (m,
3
3
H
2
1
H), 0.93 (s, 3H, CH ), 0.97 (s, 3H, CH ), 1.11 (d, 3H, CH , J = 6.56 Hz), 1.40-1.59 (m, 2H),
3 3 3
.82-2.07 (m, 3H), 2.75-2.86 (m, 1H), 7.09-7.19 (m, 2H), 7.33-7.44 (m, 1H), 7.54-7.61 (m,

New Journal of Chemistry
Page 12 of 19
1
3
View Article Online
DOI: 10.1039/C6NJ00487C
1
2
H). C NMR (CDCl , 50 MHz):  15.6 (CH ), 17.6 (CH ), 20.1 (CH), 20.7 (CH), 20.7 (C),
3
C
3
3
8.1 (CH ), 28.8 (CH ), 29.4 (CH ), 34.7 (CH), 53.4 (CH), 126.7 (CH), 128.5 (CH), 129.3
2
3
2
7
7
(
CH), 133.0 (C), 135.4 (CH), 137.2 (C). Se NMR (38 MHz, CDCl3):  392.92. Anal. calcd
Se
for C H S Se (648.73): C, 59.25; H, 6.53 Found: C, 59.17; H, 6.46.
3
2
42
2
2
General procedure for the synthesis of diselenides 23 and 24.
To a solution of selenide 17 or 18 (5.0 mmol) in penthane (8 ml), under argon atmosphere,
TMEDA (5.5 mmol) was added, followed by addition of 2.5M solution of n-buthyllithium
o
(
2.1ml, 5.25mmol). Mixture was stirred at 0 C for 0.5h and at room temperature for 8h.
Selenium (0.39g, 5.0 mmol) was added and the reaction was stirred at room temperature for
additional 12h. Mixture was poured on a saturated solution of ammonium chloride (15ml) and
oxidized with air for 3h. Decantated solution was extracted with diethyl ether (3x50ml).
Combined organic layers were washed with water, dried over anhydrous magnesium sulfate
and evaporated. Crude product was purified using column chromatography (silica gel,
hexane:ethyl acetate 95:5).
bis(2-((1S,3R,4S,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-ylseleno)phenyl)diselenide
(23).
1
Yield 44%,
= +55.39 (c 1.65, CHCl ). H NMR (200 MHz, CDCl ):  0.47-0.80 (m,
3
3
H
2
2
H), 0.99 (s, 3H, CH ), 1.04 (d, 3H, CH , J = 7.00 Hz), 1.07 (s, 3H, CH ), 1.52-1.73 (m, 4H),
3 3 3
1
3
.17- 2.38 (m, 1H), 3.58-3.75 (m, 1H), 7.03-7.22 (m, 2H), 7.48-7.65 (m, 2H). C NMR
(
CDCl , 50 MHz):  16.0 (CH ), 17.9 (C), 20.3 (CH ), 21.5 (2 x CH), 25.9 (CH ), 26.1
3
C
3
3
2
(
CH ), 28.5 (CH ), 31.4 (CH), 50.1 (CH), 126.8 (CH), 128.6 (CH), 129.4 (CH), 129.6 (C),
2 3
7
7
1
36.7 (CH), 138.1 (C). Se NMR (38 MHz, CDCl3):  324.18, 421.35. Anal. calcd for
Se
C H Se (742.52): C, 51.76; H, 5.70 Found: C, 51.58; H, 5.76.
32
42
4
bis(2-((1S,3R,4R,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-ylseleno)phenyl)diselenide
24).
Yield 36%,
(
1
= –91.48 (c 1.59, CHCl ). H NMR (200 MHz, CDCl ):  0.53-0.90 (m,
3
3
H
2
1
H), 0.95 (s, 3H, CH ), 0.96 (s, 3H, CH ), 1.08 (d, 3H, CH , J = 6.67 Hz), 1.45-1.70 (m, 2H),
3 3 3
13
.90-2.20 (m, 3H), 2.90-3.09 (m, 1H), 7.00-7.25 (m, 2H), 7.47-7.63 (m, 2H). C NMR
(
CDCl , 50 MHz):  15.7 (CH ), 17.6 (C), 20.7 (2 x CH), 21.6 (CH ), 28.8 (CH ), 29.0
3
C
3
3
3
(
CH ), 29.6 (CH ), 35.1 (CH), 50.9 (CH), 126.6 (CH), 128.3 (CH), 129. (C), 129.7 (CH),
2 2
7
7
1
37.4 (CH), 138.5 (C). Se NMR (38 MHz, CDCl3):  372.29, 419.11. Anal. calcd for
Se
C H Se (742.52): C, 51.76; H, 5.70 Found: C, 51.57; H, 5.64.
32
42
4

Page 13 of 19
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ00487C
General procedure for the synthesis of methyl selenides 31 and 32.
To a solution of selenide 21 or 22 (0.6 mmol) in methanol (10 ml) and diethyl ether (10ml),
under argon atmosphere, sodium borohydride (0,6g, 15 mmol) was added. Mixture was stirred
at room temperature until decoloration. Methyl iodide (5.0g, 35mmol) was added and stirring
was continued for 2 days. Solvent was evaporated under reduce pressure, water (50ml) was
added and the obtained mixture was extracted with diethyl ether (3x50ml). Combined organic
layers were dried over anhydrous magnesium sulfate and evaporated. Crude product was
purified using column chromatography (silica gel, hexane).
(1S,3R,4S,6R)-4-(2-(methylseleno)phenylthio)(3,7,7-trimethylbicyclo[4.1.0]heptan) (31).
1
8
3%,
= +59.96 (c 2.55, CHCl ). H NMR (300 MHz, CDCl ):  0.51-0.72 (m, 2H),
3
3
H
0
1
1
6
2
.87-0.96 (m, 1H), 0.97 (s, 3H, CH ), 1.04 (d, 3H, CH , J=6.90 MHz), 1.08 (s, 3H, CH ),
3 3 3
.37-1.47 (m, 1H), 1.84-1.95 (m, 1H), 1.97-2.18 (m, 2H), 2.27 (s, 3H, CH ), 3.32- 3.50 (dt,
3
1
3
H, J = 6.3, 8.1 Hz), 7.13-7.25 (m, 3H), 7.36-7.41 (m, 1H). C NMR (CDCl , 50 MHz): 
3
C
.4 (CH ), 15.9 ( CH ), 17.7 (C), 18.8 (CH ), 20.9 (CH), 21.1 (CH), 24.8 (CH ), 25.5 (CH ),
3
3
3
2
2
8.5 (CH ), 30.8 (CH), 49.0 (CH), 125.4 (CH), 127.3 (CH), 127.6 (CH), 133.0 (CH), 135.9
3
7
7
(
C), 138.1 (C). Se NMR (38 MHz, CDCl3):  200.14. Anal. calcd for C H SSe (339.40):
Se
17 24
C, 60.16; H, 7.13 Found: C, 60.06; H, 7.21.
(1S,3R,4R,6R)-4-(2-(methylseleno)phenylthio)-3,7,7-trimethylbicyclo[4.1.0]heptan (32).
1
Yield 48%,
= –125.75 (c 1.21, CHCl ). H NMR (200 MHz, CDCl ):  0.52-0.93 (m,
3
3
H
2
1
1
2
H), 0.92 (s, 3H, CH ), 0.96 (s, 3H, CH ), 1.07 (d, 3H, CH , J=6.60 Hz), 1.38-1.58 (m, 2H),
3 3 3
.86-2.08 (m, 3H), 2.27 (s, 3H, CH ), 2.71-2.92 (m, 1H), 7.12-7.29 (m, 3H), 7.57-7.64 (m,
3
1
3
H). C NMR (CDCl , 50 MHz):  6.4 (CH ), 15.6 ( CH ), 17.5 (C), 19.9 (CH), 20.7 (CH ),
3
C
3
3
3
0.7 (CH), 27.8 (CH ), 28.7 (CH ), 29.3 (CH ), 34.7 (CH), 51.9 (CH), 125.2 (CH), 127.1
2
3
2
7
7
(
CH), 128.0 (CH), 134.2 (CH), 134.6 (C), 139.2 (C). Se NMR (38 MHz, CDCl3): Se
2
00.83. Anal. calcd for C H SSe (339.397): C, 60.16; H, 7.13 Found: C, 60.12; H, 7.15.
1
7
24
General procedure for the methoxyselenenylation of styrene.
To a solution of diselenide (0.58mmol) dissolved in dry dichloromethane (8ml), cooled to -
o
7
8 C, solution of bromine in tetrachloromethane (0.58ml, 1M, 0.58mmol) was added
dropwise. After 15 min, a 0.70M methanol solution of silver triflate (320 mg, 1.80 mL) was
added at –78 °C and stirred for another 15 min. Styrene (2.9 mmol) was added and the
mixture was stirred at the same temperature for 2h. The reaction was poured on 10%
NaHCO3 solution, diluted with 50 ml of dichloromethane, washed with water and brine, dried

New Journal of Chemistry
Page 14 of 19
View Article Online
over magnesium sulfate and concentrated in vacuum. The crude product was purified by
DOI: 10.1039/C6NJ00487C
column chromatography (silica gel, petroleum ether: ethyl acetate 95:5).
1S,3R,4S,6R-)-4-(2-(2-Methoxy-2-phenylethylseleno)phenoxy)-3,7,7-
(
trimethylbicyclo[4.1.0]heptan (25).
1
Yield 78%, dr 68:32. H NMR (300 MHz, CDCl ):  0.43 (dt, 2H, J = 2.1, 9.3 Hz), 0.81-
3
H
0
1
.93 (m, 4H), 0.96 (d, 6H, 2 x CH , J = 7.5 Hz), 0.98 (s, 6H, 2 x CH ), 0.99 (s, 6H, 2 x CH ),
3 3 3
.24-1.43 (m, 4H), 1.51-1.88 (m, 4H), 2.18-2.30 (m, 2H), 2.98-3.06 (m, 2H), 3.25 (s, 6H, 2 x
CH ), 4.23-4.30 (m, 2H), 4.33-4.41 (m, 2H), 6.65-6.67 (m, 2H), 6.78-6.85 (m, 2H), 7.08-7.16
3
13
(
m, 2H), 7.21-7.28 (m, 2H), 7.29-7.42 (m, 10H). C NMR (CDCl , 50 MHz):  15.4 (2 x C),
3
C
1
2
1
7.0 (2 x CH ), 17.5 (2 x CH), 17.8 (2 x CH ), 21.9 (2 x CH ), 22.1 (2 x CH), 24.2 (2 x CH ),
3 3 2 2
8.8 (2 x CH ), 31.9 (2 x CH ), 33.4 (2 x CH), 57.0 (2 x CH ),74.7 (2 x CH), 83.2 (2 x CH),
3
2
3
11.3 (2 x CH),120.5 (2 x CH), 121.4 (2 x C), 126.6 (2 x CH), 126.6 (4 x CH), 127.9 (2 x
77
CH), 128.4 (4 x CH), 129.6 (2 x CH), 141.3 (2 x C), 155.6 (2 x C). Se NMR (38 MHz,
CDCl3): Se 223.96. Anal. calcd for C H O Se (443.480): C, 67.71; H, 7.27 Found: C,
25
32
2
6
7.58; H, 7.25.
(1S,3R,4R,6R)-4-(2-(2-Methoxy-2-phenylethylseleno)phenoxy)-3,7,7-
trimethylbicyclo[4.1.0]heptan (26).
1
Yield 14%, dr 61:39. H NMR (200 MHz, CDCl ):  0.67-0.96 (m, 6H), 0.96-1.02 (m, 12H,
3
H
4
3
1
x CH ), 0.99 (s, 6H, 2 x CH ), 1.23-1.46 (m, 6H), 1.98- 2.30 (m, 4H), 3.00-3.12 (m, 2H),
3 3
.24 (s, 6H, 2 x CH ), 3.71-3.74 (m,2H), 4.30-4.45 (m, 2H), 6.70-6.89 (m, 6H), 7.06-7.38 (m,
3
1
3
0H), 7.40-7.50 (m, 2H). C NMR (CDCl , 50 MHz):  16.1 (2 x CH ), 17.6 (2 x C), 18.6
3
C
3
(
2 x CH ), 20.2 (2 x CH), 21.3 (2 x CH), 26.9 (2 x CH ), 28.3 (2 x CH ), 28.6 (2 x CH ), 32.1
3 2 2 3
(
2 x CH ), 34.7 (2 x CH), 57.0 (2 x CH ), 81.5 (2 x CH), 83.2 (2 x CH), 112.4 (2 x CH), 120.9
2
3
(2 x CH), 121.4 (2 x C), 126.7 (4 x CH), 127.9 (2 x CH), 128.5 (4 x CH), 130.3 (2 x CH),
7
7
1
3
30.4 (2 x CH), 141.3 (2 x C), 156.4 (2 x C). Se NMR (38 MHz, CDCl3):  272.13,
Se
28.68. Anal. calcd for C H O Se (443.48): C, 67.71; H, 7.27 Found: C, 67.52; H, 7.23.
2
5
32
2
(1S,3R,4S,6R-)-4-(2-(2-methoxy-2-phenylethylseleno)phenylthio)-3,7,7-
trimethylbicyclo[4.1.0]heptan (27).
1
Yield 47%, dr 63:37. H NMR (200 MHz, CDCl ):  0.50-0.77 (m, 4H), 0.99 (d, 6H, 2 x
3
H
CH , J = 6.0 Hz), 0.99 (s, 6H, 2 x CH ), 1.02 (s, 6H, 2 x CH ), 1.25-1.48 (m, 4H), 1.80-2.22
3
3
3
(
m, 6H), 3.03-3.14 (m, 2H,), 3.27 (s, 6H, 2 x CH ), 3.30-3.49 (m, 4H), 4.25 (ddd, 2H, J = 0.8,
3
1
3
5
.0, 8.6 Hz), 7.04-7.19 (m, 4H), 7.23-7.43 (m, 14H). C NMR (CDCl , 50 MHz):  15.8 (2 x
3
C
CH ), 17.8 (2 x C), 18.8 (2 x CH ), 21.1 (2 x CH), 24.7 (2 x CH ), 25.6 (2 x CH ), 28.5 (2 x
3
3
2
2

Page 15 of 19
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ00487C
CH ), 30.6 (2 x CH), 33.9 (2 x CH ), 48.3 (2 x CH), 48.4 (2 x CH), 57.0 (2 x CH ), 82.9 (2 x
3
2
3
CH), 126.2 (2 x CH), 126.6 (4 x CH), 126.8 (2 x CH), 128.0 (2 x CH), 128.5 (4 x CH), 130.1
7
7
(
2 x CH), 131.7 (2 x CH), 135.7 (2 x C), 137.7 (2 x C), 141.1 (2 x C). Se NMR (38 MHz,
CDCl3):  275.76, 275.55. Anal. calcd for C H OSSe (459.55): C, 65.64; H, 7.02 Found:
Se
25 32
C, 65.33; H, 7.08.
(1S,3R,4R,6R-)-4-(2-(2-methoxy-2-phenylethylseleno)phenylthio)-3,7,7-
trimethylbicyclo[4.1.0]heptan (28).
1
Yield 11%, dr 52:48. H NMR (300 MHz, CDCl ):  0.69-0.91 (m, 4H), 0.94 (s, 6H, 2 x
3
H
CH ), 0.96 (s, 6H, 2 x CH ), 1.05 (dd, 6H, 2 x CH , J = 4.96 Hz, J = 1.30 Hz), 1.10-1.36 (m,
3
3
3
4
H), 1.37-1.51 (m, 2H), 1.83-2.07 (m, 6H), 2.73-2.85 (m, 2H), 3.06 (d, 1H, J = 5.1 Hz), 3.09
(
(
(
(
d, 1H, J = 4.8 Hz), 3.26 (s, 6H, 2 x CH ), 4.38-4.46 (m, 2H), 7.07-7.18 (m, 4H), 7.25- 7.40
3
1
3
m, 14H). C NMR (CDCl , 50 MHz):  15.6 (2 x CH ), 17.5 (2 x C), 19.9 (2 x CH ), 20.8
3
C
3
3
4 x CH), 27.8 (2 x CH ), 28.7 (2 x CH ), 29.3 (2 x CH ), 33.9 (2 x CH ), 34.7 (2 x CH), 51.6
2
3
2
2
2 x CH), 57.0 (2 x CH ), 83.0 (2 x CH), 125.9 (2 x CH), 126.6 (4 x CH) 127.4 (2 x CH),
3
1
1
27.5 (2 x C), 128.1 (2 x CH), 128.6 (4 x CH), 129.7 (2 x CH), 133.2 (2 x CH), 137.2 (2 x C),
7
7
41.2 (2 x C). Se NMR (38 MHz, CDCl3):  268.42, 268.83. Anal. calcd for C H OSSe
Se
25 32
(459.55): C, 65.34; H, 7.02 Found: C, 65.22; H, 6.97.
(1S,3R,4S,6R-)-4-(2-(2-methoxy-2-phenylethylseleno)phenylseleno)-3,7,7-
trimethylbicyclo[4.1.0]heptan (29).
1
Yield 66%, dr 53:47. H NMR (200 MHz, CDCl ):  0.49-0.78 (m, 4H), 0.98 (s, 6H, 2 x
3
H
CH ), 1.00 (d, 6H, 2 x CH , J = 6.0 Hz), 1.04 (s, 6H, 2 x CH ), 1.23-1.62 (m, 6H), 1.80-2.09
3
3
3
(
m, 4H), 2.13-2.33 (m, 2H), 3.00-3.14 (m, 2H), 3.26 (s, 6H, 2 x CH ), 3.55-3.68 (m, 2H),
3
1
3
4
1
2
8
.38-4.48 (m, 2H), 7.04-7.19 (m, 2H), 7.20-7.54 (m, 16H). C NMR (CDCl , 50 MHz): 
3
C
5.8 (2 x C), 17.7 (2 x CH ), 20.3 (2 x CH ), 21.3 (2 x CH), 21.6 (2 x CH), 25.6 (2 x CH ),
3
3
2
6.1 (2 x CH ), 28.4 (2 x CH ), 30.9 (2 x CH), 34.8 (2 x CH ), 47.1 (2 x CH), 56.9 (2 x CH ),
2
3
2
3
2.9 (2 x CH), 126.4 (2 x CH), 126.6 (4 x CH), 127.4 (2 x CH), 127.9 (2 x CH), 128.5 (4 x
77
CH), 130.3 (2 x CH), 133.8 (2 x C), 133.9 (2 x CH), 137.4 (2 x C), 141.1 (2 x C). Se NMR
38 MHz, CDCl3):  282.77, 283.14, 338.95, 339.45. Anal. calcd for C H OSe (506.44):
(
Se
25 32
2
C, 59.29; H, 6.37 Found: C, 59.18; H, 6.38.
1S,3R,4S,6R-)-4-(2-(2-methoxy-2-phenylethylseleno)phenylseleno)-3,7,7-
(
trimethylbicyclo[4.1.0]heptan (30).
1
Yield 19%, dr 56:44. H NMR (200 MHz, CDCl ):  0.55-0.92 (m, 6H), 0.96 (s, 12H, 4 x
3
H
CH ), 1.03-1.05 (m, 6H, 2 x CH ), 1.22-1.63 (m, 6H), 1.90-2.09 (m, 6H), 3.00-3.15 (m, 2H),
3
3

New Journal of Chemistry
Page 16 of 19
View Article Online
3
.26 (s, 6H , 2 x CH ), 4.38-4.47 (m, 2H), 7.00-7.20 (m, 4H), 7.21-7.40 (m, 12H), 7.40-7.50
3
DOI: 10.1039/C6NJ00487C
1
3
(
m, 2H). C NMR (CDCl , 50 MHz):  15.6 (2 x CH ), 17.5 (2 x C), 20.5 (2 x CH ), 20.8 (2
3
C
3
3
x CH), 21.5 (2 x CH), 28.6 (2 x CH ), 28.8 (2 x CH ), 29.5 (2 x CH ), 34.7 (2 x CH ), 35.0 (2
2
3
2
2
x CH), 48.9 (2 x CH), 57.0 (2 x CH ), 83.0 (2 x CH), 126.1 (2 x CH), 126.6 (4 x CH), 127.8
3
(2 x CH), 128.1 (2 x CH), 128.5 (4 x CH), 129.8 (2 x CH), 132.7 (2 x C), 135.1 (2 x CH),
7
7
1
3
38.2 (2 x C), 141.2 (2 x C). Se NMR (38 MHz, CDCl3):  285.16, 285.52, 389.53,
Se
90.86. Anal. calcd for C H OSe (506.44): C, 59.29; H, 6.37 Found: C, 59.37; H, 6.31.
2
5
32
2
General procedure for palladium-catalyzed allylic alkylation.
The Pd-catalyzed allylic substitution reaction (Trost-Tsuji reaction) of dimethyl malonate
with rac-1,3-diphenyl-2-propenyl acetate, was performed using 3 mol% of N,O-
3
bis(trimethylsilyl)acetamide-potassium acetate as a base, 2.5 mol% of [Pd( -C H )Cl] , and
3
5
2
1
2
5
0 mol% of tested chiral ligand in acetonitrile solution. The product (dimethyl(1,3-diphenyl-
-propen-1-yl)malonate) was purified by column chromatography (n-hexane/ethyl acetate,
1
:1), analyzed by H NMR, and specific rotation in CH Cl ware measured. Stereochemical
2
2
effect of the catalytic reaction was determined by HPLC (Chiracel AD-H), n-hexane/i-PrOH,
5:5, flow rate: 1.0 mL/min, λ=225 nm, enantiomer (R) t = 16.3 min, enantiomer (S) t = 23.7
9
r
r
min. The absolute configuration was assigned by comparison of the retention times in HPLC
and optical rotation signs with literature data [25-26].
General procedure for copper-catalyzed Henry reaction.
Ligand (0.06 mmol, 12 mol%) and Cu(OAc) ∙H O (10.0 mg, 0.05 mmol, 10 mol%) were
2
2
dissolved in i-PrOH ( 1 mL) and the mixture was stirred for 3 h at rt to give a blue or dark
green solution. Then benzaldehyde (0.5 mmol, 1 eq), nitromethane (5.0 mmol, 10 eq) and
Et N (1.0 mol%) were added with additional 1 mL of i-PrOH. The reaction mixture was
3
cooled to 0 °C. After 3 days, the crude product was isolated by column chromatography
(hexane/AcOEt 6:1) to give β-nitroalcohol (2-nitro-1-phenylethan-1-ol) as a mixture of
1
diastereomers. Product was analyzed by H NMR, and the enantiomeric excess was
determined using chiral HPLC (Chiracel OD-H), n-hexane/i-PrOH, 90:10, flow rate: 1.0
mL/min, λ=254 nm, enantiomer (R) t = 13.2 min, enantiomer (S) t = 16.3 min). The absolute
r
r
configuration was assigned by comparison of the retention times in HPLC and optical rotation
signs with literature data [27-29].

Page 17 of 19
New Journal of Chemistry
View Article Online
Crystallographic data for bis(2-((1S,3R,4S,6R)-3,7,7-Trimethyl-bicyclo[4.1.0]heptan-4-
DOI: 10.1039/C6NJ00487C
yloxy)phenyl)diselenide (19).
Crystals of diselenide 19 were grown from the methanol solution. The X-ray intensities were
collected with an Oxford Sapphire CCD diffractometer using MoKα radiation λ =0.71073 Å,
at 292(2) K, by ω-2θ method. Structure was solved by direct methods and refined with the
2
full-matrix least-squares method on F with the use of SHELX97 and SHELX2014 program
packages [30]. Analytical absorption corrections were applied (RED171 package of programs
[
31] Oxford Diffraction, 2000), the maximum and minimum transmission of 0.2026 and
.4609. Hydrogen atoms were located from the electron density maps and their positions were
constrained in the refinement. The absolute structure was determined with the Flack method
32], the Flack x being -0.045(17). The structural data have been deposited with Cambridge
0
[
Crystallographic Data Centre, the CCDC number 1453055.
References
1
. Organoselenium Chemistry: A Practical Approach, Back, T.G. Ed.; Oxford University
Press: Oxford, 1999.
2
3
. Organoselenium Chemistry, Wirth, T. Ed.; Top. Curr. Chem., 2000.
. Wirth, T. Comprehensive Organometallic Chemistry III; Crabtree, R.H.; Mingos, D.M.P.
Eds.; Elsevier: Oxford, 2007, Vol. 9, p.p. 457–500.
. Organoselenium Chemistry: Synthesis and Reactions, Wirth, T. Ed.; Wiley-VCH:
Weincheim, 2012.
4
5
2
6
. Organoselenium Chemistry: Between Synthesis and Biochemistry; Santi, C., Ed.; Bentham,
014.
. McGarrigle, E. M.; Myers, E. L.; Illa, O.; Shaw, M. A.; Riches, S. L.; Aggarwal, V. K.
Chem. Rev. 2007, 107, 5841.
. Santi, C.; Santoro, S. Electrophilic selenium reagents. In: Organoselenium Chemistry:
Synthesis and Reactions; Wirth, T., Ed.; Wiley-VCH, 2012; pp. 1-51.
. Ścianowski, J.; Rafiński, Z. Electrophilic selenium reagents: Addition reactions to double
7
8
bonds and selenocyclizations. In: Organoselenium Chemistry: Between Synthesis and
Biochemistry; Santi, C., Ed.; Bentham, 2014; pp. 8-60.
9
2
1
. Sancineto, L.; Palombaa, M.; Bagnolia, L.; Marinia, F.; Santi, C. Curr. Org. Chem. 2015,
0, 122.
0. Coles, M. P. Curr. Org. Chem. 2006, 10, 1993.

New Journal of Chemistry
Page 18 of 19
View Article Online
1
3
1
1
1. Déziel, R.; Malenfant, E.; Thibault, C.; Fréchette, S.; Gravel, M. Tetrahedron Lett. 1997,
DOI: 10.1039/C6NJ00487C
8, 4753.
2. Fragale, G.; Neuburgerb, M.; Wirth, T., Chem. Commun., 1998, 1867.
3. Tiecco, M.; Testaferri, L.;Santi, C.; Tomassini, C.; Marini, F.; Bagnoli, L.; Temperini, A.
Chem. Eur. J. 2002, 8, 1118.
1
1
1
1
1
1
2
2
2
4. Ścianowski, J. Tetrahedron Lett., 2005, 46, 3331.
5. Ścianowski, J.; Rafiński, Z.; Wojtczak, A. Eur. J. Org. Chem., 2006, 3216.
6. Rafiński, Z.; Ścianowski, J.; Wojtczak, A. Tetrahedron: Asymmetry, 2008, 19, 223.
7. Rafiński, Z.; Ścianowski, J. Tetrahedron:Asymmetry, 2008, 19, 1237.
8. Rafiński, Z.; Ścianowski, J.; Wojtczak, A. Lett. Org. Chem., 2009, 6, 321.
9. Ścianowski, J.; Rafiński, Z.; Szuniewicz, A.; Wojtczak, A. Tetrahedron, 2009, 65, 10162.
0. Ścianowski, J.; Rafiński, Z.; Wojtczak, A.; Burczyński, K. Tetrahedron:Asymmetry, 2009,
0, 2871.
1. Ścianowski, J.; Rafalski, J.; Banach, A.; Czaplewska, J.; Komoszyńska, A. Tetrahedron:
Asymmetry, 2013, 24, 1089.
2
2. Pacuła, A. J.; Ścianowski, J. Curr. Green Chem., 2016, 3, 36.
2
3. Enders, D.; Peters, R.; Lochtman, R.; Raabe, G.; Runsink, J.; Bats, J. W. Eur. J. Org.
Chem. 2000, 3399.
2
2
2
4. Wojaczyńska, E.; Skarżewski, J. Tetrahedron Asymmetry 2008, 19, 594.
5. Zhang, W.; Xu, Q.; Shi, M. Tetrahedron: Asymmetry 2004, 15, 3161.
6. Mino, T.; Wakui, K.; Oishi, S.; Hattori, Y.; Sakamoto, M.; Fujita, T. Tetrahedron:
Asymmetry 2008, 19, 2711.
2
4
2
2
3
3
3
7. Blay, G.; Domingo, L. R.; Hernandez-Olmos, V.; Pedro, J. R. Chem. Eur. J. 2008, 14,
725.
8 Liu, S.; Wolf, C. Org. Lett. 2008, 10, 1831.
9. Zielińska-Błajet, M.; Skarżewski, J. Tetrahedron : Asymmetry 2009, 20, 1992.
0. Sheldrick, G. Acta Cryst., Sect. 2008, A 64, 112.
1. CrysAlis CCD171 and RED171 package of programs, Oxford Diffraction, 2000.
2. Flack, H.D. Acta Cryst., 1983, A39, 876.

Page 19 of 19
New Journal of Chemistry
View Article Online
Convenient methodology for the synthesis of optically active diselenides and selenides
DOI: 10.1039/C6NJ00487C
functionalized with terpenyl moieties and their applications in selenenylation of alkenes,
and Tsuji-Trost, and Henry reactions are presented.