The use of sulfides derived from carane, p -menthane, pinane, and bornane in the synthesis of optically active epoxides

Article abstract of DOI:10.1080/10426507.2013.819867

Convenient routes for the synthesis of optically active methyl, phenyl, and dimonoterpenyl sulfides derived from carane, p-menthane, pinane, and bornane were developed. Methyl and dimonoterpenyl sulfides have been obtained by the reaction of the corresponding monoterpene thiolates with methyl iodide or monoterpene tosylates. The reactions of monoterpene tosylates with sodium benzenethiolate gave the corresponding phenyl monoterpenyl sulfides. These sulfides were used for the sulfur ylide-mediated reaction to yield epoxides. Good diastereoselectivities up to 99:1 and low to moderate enantioselectivities were observed for the enantioselective synthesis of chiral epoxides.

Full text of DOI:10.1080/10426507.2013.819867

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Phosphorus, Sulfur, and Silicon and the
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The Use of Sulfides Derived from Carane,
P-Menthane, Pinane, and Bornane in the
Synthesis of Optically Active Epoxides
Anna Banach a , Jacek Ścianowski a & Piotr Ozimek a
a Department of Organic Chemistry , Nicolaus Copernicus
University , 7 Gagarin Street, 87-100 , Torun , Poland
Accepted author version posted online: 20 Aug 2013.Published
online: 03 Dec 2013.
To cite this article: Anna Banach , Jacek Ścianowski & Piotr Ozimek (2014) The Use of Sulfides
Derived from Carane, P-Menthane, Pinane, and Bornane in the Synthesis of Optically Active
Epoxides, Phosphorus, Sulfur, and Silicon and the Related Elements, 189:2, 274-284, DOI:
10.1080/10426507.2013.819867
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Phosphorus, Sulfur, and Silicon, 189:274–284, 2014
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2013.819867
THE USE OF SULFIDES DERIVED FROM CARANE,
P-MENTHANE, PINANE, AND BORNANE IN THE
SYNTHESIS OF OPTICALLY ACTIVE EPOXIDES
´
Anna Banach, Jacek Scianowski, and Piotr Ozimek
Department of Organic Chemistry, Nicolaus Copernicus University, 7 Gagarin
Street 87-100, Torun, Poland
GRAPHICAL ABSTRACT
Abstract Convenient routes for the synthesis of optically active methyl, phenyl, and dimonoter-
penyl sulfides derived from carane, p-menthane, pinane, and bornane were developed. Methyl
and dimonoterpenyl sulfides have been obtained by the reaction of the corresponding monoter-
pene thiolates with methyl iodide or monoterpene tosylates. The reactions of monoterpene
tosylates with sodium benzenethiolate gave the corresponding phenyl monoterpenyl sulfides.
These sulfides were used for the sulfur ylide-mediated reaction to yield epoxides. Good di-
astereoselectivities up to 99:1 and low to moderate enantioselectivities were observed for the
enantioselective synthesis of chiral epoxides.
Keywords Sulfides; monoterpenes; stereoselective synthesis of epoxides; sulfur ylides
INTRODUCTION
In recent years, an increasing role of chalcogenides in organic synthesis is observed.
The specific reactivity of these compounds makes them potential reagents and catalysts
for the formation of new carbon–carbon, carbon—nitrogen, and carbon–oxygen bonds.1
Applications of organosulfur and organoselenium compounds in asymmetric synthesis are
particularly interesting, for example, chiral sulfur ylides were used for the synthesis of
optically active epoxides aziridines and cyclopropanes.2,3
Although the first successful example of using chiral sulfonium ylides for the syn-
thesis of optically active epoxides was reported by Furukawa and coworkers in 1989,4
Received 18 March 2013; accepted 24 June 2013.
The present work was supported by a Grant of the Dean of Department of Chemistry, Nicolaus Copernicus
University, (Nr.2/2012).
´
Address correspondence to Jacek Scianowski, Department of Organic Chemistry, Nicolaus Copernicus
University, 7 Gagarin Street, 87-100, Torun, Poland. E-mail: jsch@chem.umk.pl
274

SULFIDES DERIVED FROM CARANE, P-MENTHANE, PINANE, BORNANE
275
Figure 1 Structures of sulfides 1 and 2.
searching for new reagents for the synthesis of asymmetric epoxides is still the current di-
rection of modern developments.5,6 The aim of our investigation was to develop a synthesis
of optically active sulfides derived from commercially available monoterpenes [(+)-3-
carene, (–)-menthol, (–)-β-pinene, and (–)-borneol] and test them as auxiliaries for the
stereoselective synthesis of epoxides. Previous studies on the use of sulfur ylides contain-
ing a monoterpene substructure in the sulfide structures were presented for camphor,4,7–13
pulegone,14 α-pinene,15 limonene,16 and carvone17 derivatives. Particularly interesting was
the use of sulfides 1 and 2 (Figure 1) for the synthesis of quinine and quinidine.16,18
In our previous investigations, we have shown that monoterpene tosylates are conve-
nient substrates for the synthesis of selenium monoterpene derivatives.19–23 In this work,
we present the use of monoterpene tosylates for the synthesis of monoterpene thiols24,25
and their transformation into methyl, phenyl, and dimonoterpenyl sulfides, precursors for
chiral sulfur ylides. We wanted to compare the influence of the methyl and the phenyl group
or the additional monoterpene group on the diastereoselectivity and enantioselectivity of
the epoxide formation.
RESULTS AND DISCUSSION
The synthesis of monoterpene thiols 6, 9, 12, 15 was the first step of our investigation.
Two methods for the preparation of thiols have been compared: the reaction of monoter-
pene tosylates with potassium thioacetate and subsequent reduction with lithium alanate
(method a),24 and the one pot reaction of monoterpene tosylate with thiourea and hydrolysis
with sodium hydroxide (method b).25 Monoterpene thioacetates 5, 8, 11 were isolated by
distillation under reduced pressure. Tosylates 4, 7, 10, 13 were prepared by the reaction of
monoterpene alcohols with tosyl chloride in pyridine.19,20 As an example, the synthesis of
the caranyl thiol 6 from (+)-3-carene 3 is presented in Scheme 2.
Scheme 1

276
A. BANACH ET AL.
Scheme 2
Figure 2 Optically active monoterpene sulfides.
Summaries of the syntheses of thioacetates and monoterpene thiols from derivatives
of p-menthane, carane, pinane, and bornane are included in Table 1. We could not isolate
isobornyl thioacetate 14 by the adopted methodology.
The reaction of thiols 6, 9, 12, and 15 with sodium hydride gave the corresponding
thiolates, which upon reaction with methyl iodide or monoterpenyl tosylates were converted
into methyl monoterpenyl sulfides 16, 19, 22, 25 and dimonoterpenyl sulfides 17, 20, 23.
Using this method, we could not get diisobornyl sulfide 26. Additionally, the reaction
of monoterpene tosylates with sodium benzenethiolate gave the corresponding phenyl
monoterpenyl sulfides 18, 21, 24, 27. Examples for syntheses of methyl-, phenyl-, and
dimonoterpenyl sulfides from carane are presented in Scheme 3. Structures of the obtained
sulfides and yields are summarized in Figure 2.
The sulfides 16–27 were used for the sulfur ylide-mediated enantioselective synthe-
sis of chiral epoxides. The model reaction of benzyl bromide with benzaldehyde yielding
epoxystilbene was studied. The reaction was carried out in acetonitrile as a one-pot synthe-
sis, without isolation of the corresponding sulfonium salt (Scheme 4). Yields, enantio- and
diastereoselectivities of the epoxide formations are presented in Table 2.

SULFIDES DERIVED FROM CARANE, P-MENTHANE, PINANE, BORNANE
277
Table 1 Syntheses of monoterpene thioacetates and thiols
Yield
[%]
Method a Method b
yield [%]a yield [%]
Entry
1
Tosylate
Thioacetate
Thiol
70
48
37
2
48
33
39
3
63
37
40
4
—
—
61
aoverall yield after two steps.
The best diastereoselectivities were obtained for the reactions of sulfides 16, 25,
and 27, while the best enantioselectivity was obtained with sulfide 18. According to our
knowledge, phenyl monoterpenyl sulfides have not yet been tested in this type of reaction.
CONCLUSIONS
We have found that tosylates derived from p-menthane, carane, pinane, and bornane
can be conveniently used as precursors for the synthesis of optically active monoterpene
thiols and sulfides. We have developed and compared two methods for the synthesis of

278
A. BANACH ET AL.
Scheme 3
Table 2 Formation of asymmetric stilbene epoxides by use of monoterpene sulfides
Entry
Sulfide
Yield [%]
Ratio cis/transa
ee trans (%)b
1
2
3
4
5
6
7
8
16
19
22
25
17
20
23
18
21
24
27
53
30
74
50
14
—
73
13
11
40
23
3/97
5/95
5/95
1/99
71/29
—
11/89
55/45
33/67
24/76
3/97
8 (S,S)
2 (R,R)
6 (R,R)
0
8 (S,S)
—
10 (R,R)
44 (S,S)
20 (S,S)
14 (R,R)
34 (S,S)
9
10
11
adetermined on the basis of the 1H NMR spectra.
bdetermined on the basis of HPLC using a Chiralcel Daicel OD-H column.
Scheme 4
monoterpene thiols. The results are similar, but we regard the method involving thiourea
more convenient because of the simplicity of the one pot synthesis. The resulting monoter-
pene sulfides provided the target epoxides, but low to moderate enantioselectivities were
obtained. This is probably caused by the formation of diastereomeric mixtures of sulfo-
nium salts in the first step of the epoxide formation process. We have observed that the
introduction of the phenyl group into the structure of sulfides resulted in an increase of the
enantioselectivity of the produced epoxides.

SULFIDES DERIVED FROM CARANE, P-MENTHANE, PINANE, BORNANE
279
EXPERIMENTAL
Melting points were measured with a Bu¨chi Tottoli SPM-20 heating unit and are un-
corrected. NMR spectra (solvent CDCl3, chemical shifts δ in /ppm) were recorded on Bruker
AM-300, Varian 200, Bruker Avance III/400, or Bruker Avance III/700. Optical rotations
were measured in 10-mm cells with a polAAr 3000 polarimeter. Elemental analyses were
performed on a Vario MACRO CHN analyzer. TLC was conducted on precoated silica gel
plates (Merck 60F254), and the spots were visualized under UV light. Column chromatog-
raphy was carried out by use of Silica Gel 60 Merck (70–230 mesh) with petroleum ether
as eluent. All reactions requiring anhydrous conditions were conducted in a flame-dried
apparatus.
GENERAL PROCEDURE FOR THE PREPARATION OF MONOTERPENE
THIOACETATES
A monoterpene tosylate (65.4 mmol) was carefully added to the potassium thioacetate
(8.27 g, 72.5 mmol) in anhydrous DMSO (75 mL). The solution was kept at 45◦C under Ar
for 36 h, subsequently poured into water (100 mL) and extracted with CHCl3 (3 × 50 mL).
The combined organic layers were dried over MgSO4, the solvent was evaporated, and the
residue was purified by distillation at reduced pressure.
(1S,3R,4S,6R)-(+)-4-Caranyl Thioacetate (5). Bp: 98–100◦C/1.0 mm Hg.
22
1
Yield 70%; [α]D = +30.10 (c 4.80, CHCl3); H NMR (200 MHz): 0.48–0.79 (m, 3H),
0.85 (d, 3H, CH3, J = 6.8 Hz), 0.96 (s, 3H, CH3), 0.98 (s, 3H, CH3), 1.37–1.56 (m, 1H),
1.67–1.91 (m, 2H), 2.30 (s, 3H, CH3CO), 2.32–2.48 (m, 1H), 3.77–3.88 (m, 1H); 13C
NMR (50.3 MHz): 15.8 (CH3), 17.6 (C), 18.9 (CH3), 19.0 (CH3), 19.1 (CH), 22.0 (CH),
25.3 (CH2), 26.2 (CH2), 28.6 (CH3), 30.8 (CH), 43.3 (CH), 195.8 (C). Elemental Anal.
Calcd (%) for C12H20OS (212.36): C, 67.87; H, 9.49. Found: C, 68.09; H, 9.45.
(1S,2S,5R)-(+)-Neomenthyl Thioacetate (8). Bp.: 76–78◦C/0.5 mm Hg. Yield
48%; [α]D = +72.00 (c 5.22, CHCl3); Lit.24 [α]D = +64.00 (c 2.66, CHCl3); 1H NMR
(300 MHz): 0.83 (d, 3H, CH3, J = 6.6 Hz), 0.86 (d, 3H, CH3, J = 6.3 Hz), 0.88 (d, 3H,
CH3, J = 6.6 Hz), 0.89–0.94 (m, 2H), 1.04–1.16 (m, 1H), 1.27–1.45 (m, 2H), 1.68–1.75
(m, 2H), 1.82 (dq, 2H, J = 3.3, 13.2 Hz), 2.32 (s, 3H, CH3CO), 4.05–4.09 (m, 1H); 13C
NMR (75.5 MHz): 20.7 (CH3), 20.9 (CH3), 22.1 (CH3), 27.7 (CH2), 28.1 (CH), 30.5 (CH),
31.1 (CH3), 35.0 (CH2), 41.9 (CH2), 45.2 (CH), 47.6 (CH), 195.4 (C). Elemental Anal.
Calcd (%) for C12H22OS (214.37): C, 67.23; H, 10.34. Found: C, 67.58; H, 10.37.
(1S,2R,5S)-(–)-cis-Myrtanyl Thioacetate (11). Bp.: 106–108◦C/0.8 mm Hg.
20
20
Yield 63%; [α]D = –75.25 (c 5.27, CHCl3); 1H NMR (300 MHz): 0.87 (d, 1H, J =
20
9.6 Hz), 1.04 (s, 3H, CH3), 1.19 (s, 3H, CH3), 1.43–1.53 (m, 2H), 1.80–2.20 (m, 6H), 2.32
(s, 3H, CH3CO), 2.96 (dd, 2H, CH2, J = 1.8, 8.1 Hz); 13C NMR (75.5 MHz): 21.8 (CH2),
23.1 (CH3), 26.0 (CH2), 27.9 (CH3), 30.6 (CH3), 33.3 (CH2), 35.7 (CH2), 38.6 (C), 41.1
(CH), 41.2 (CH), 45.4 (CH), 196.0 (C). Elemental Anal. Calcd (%) for C12H20OS (212.36):
C, 67.87; H, 9.49. Found: C, 67.52; H, 9.55.
General Procedure for the Preparation of Thiols
Method a. To the suspension of LiAlH4 (4.00 g, 105.0 mmol) in anhydrous diethyl
ether (80 mL), the thioacetate (52 mmol) dissolved in anhydrous diethyl ether (30 mL)
was carefully added. The solution was stirred 2 h at reflux under an argon atmosphere,

280
A. BANACH ET AL.
allowed to cool, and diluted with water (60 mL). The precipitate was dissolved by adding
10% H2SO4 (50 mL) and extracted with diethyl ether (3 × 40 mL). The combined ethereal
layers were dried over MgSO4, the solvent was evaporated, and the residue was purified by
distillation.
Method b. The tosylate (16.0 mmol) and thiourea (32.0 mmol) in propane-2-ol
(50 mL) were kept 15 h at 100◦C. The mixture was allowed to cool, and 0.5 M NaOH
(50 mL) were added. The mixture was kept 2 h at 100◦C. The mixture was acidified and
extracted with dichloromethane (3 × 50 mL). The combined organic layers were dried
over MgSO4, and the solvent was evaporated. The crude products were purified by column
chromatography.
(1S,3R,4S,6R)-(+)-4-Caranyl Thiol (6). Method a: bp: 44–46◦C/0.3 mm Hg.
Yield 48%; Method b: Yield 37%; colorless liquid; [α]D = +41.01 (c 5.02, CHCl3); 1H
25
NMR (200 MHz): 0.47–0.57 (m, 1H), 0.68–0.90 (m, 2H,), 0.92 (d, 3H, CH3, J = 6.6 Hz),
0.98 (s, 3H, CH3), 1.01 (s, 3H, CH3), 1.23 (d, 1H, J = 5.6 Hz), 1.27–1.36 (m, 1H), 1.60–1.80
(m, 2H), 2.22–2.49 (m, 1H), 3.20–3.32 (m, 1H); 13C NMR (50.3 MHz): 15.8 (CH3), 17.7
(CH3), 18.8 (CH), 19.7 (CH), 22.7 (CH2), 23.6 (C), 28.5 (CH3), 28.5 (CH2), 31.6 (CH),
38.8 (CH). Elemental Anal. Calcd (%) for C10H18S (170.31): C, 70.52; H, 10.65. Found:
C, 70.13; H, 10.59.
(1S,2S,5R)-(+)-Neomenthyl Thiol (9). Method a: bp: 48–50◦C/0.7 mm Hg.
Yield 33%; Method b: Yield 39%; colorless liquid; [α]D = +37.99 (c 5.3, CHCl3); Lit.24
25
20
1
[α]D = +53.9 (c 1.85, CHCl3); H NMR (200 MHz) 0.87 (d, 3H, CH3, J = 6.2 Hz),
0.90 (d, 3H, CH3, J = 6.6 Hz), 0.91 (d, 3H, CH3, J = 6.8 Hz), 0.98–1.09 (m, 2H), 1.22
(d, 1H, J = 6.8 Hz), 1.29–1.56 (m, 3H), 1.62–1.98 (m, 3H), 3.45–3.53 (m, 1H); 13C NMR
(50.3 MHz): 20.3 (CH3), 20.8 (CH3), 22.1 (CH3), 24.2 (CH2), 25.9 (CH), 30.2 (CH), 35.29
(CH2), 40.1 (CH), 44.0 (CH2), 48.2 (CH). Elemental Anal. Calcd (%) for C10H20S (172.33):
C, 69.69; H, 11.70. Found: C, 69.99; H, 11.79.
(1S,2R,5S)-(–)-cis-Myrtanyl Thiol (12). Method a: bp: 79–81◦C/0.3 mm Hg.
Yield 37%; Method b: Yield 40%; colorless liquid; [α]D = –75.87 (c 5.18, CHCl3); 1H
25
NMR (200 MHz): 0.89 (d, 1H, J = 9.4 Hz), 0.97 (s, 3H, CH3), 1.19 (s, 3H, CH3), 1.29 (t,
1H, J = 7.8 Hz), 1.43–1.54 (m, 1H), 1.84–2.21 (m, 6H), 2.29–2.41 (m, 1H), 2.57 (t, 2H, J
= 7.6 Hz); 13C NMR (50.3 MHz): 21.8 (CH2), 23.2 (CH3), 26.1 (CH2), 27.9 (CH3), 31.4
(CH2), 32.5 (CH), 33.3 (CH2), 38.6 (C), 41.3 (CH), 45.3 (CH). Elemental Anal. Calcd (%)
for C10H18S (170.31): C, 70.52; H, 10.65. Found: C, 70.77; H, 10.64.
(1R,2R,4R)-(+)-Isobornyl Thiol (15). Method b: Yield 61%; colorless liquid;
[α]D = +50.00 (c 4.52, CHCl3); Lit.26 [α]D = +47.50 (c 5.06, CHCl3); H NMR
(700 MHz): 0.83 (s, 3H, CH3), 0.97 (s, 3H, CH3), 1.01 (s, 3H, CH3), 1.08–1.15 (m, 2H),
1.64–1.74 (m, 3H), 1,78 (d, 1H, J = 6.3 Hz), 1.79–1.83 (m, 1H), 1.89 (dd, 1H, J = 9.1,
13.3 Hz), 2.96–2.99 (m, 1H); 13C NMR (176.1 MHz): 13.9 (CH3), 20.3 (CH3), 20.6 (CH3),
27.3 (CH2), 38.2 (CH2), 41.3 (CH2), 45.9 (CH), 46.2 (CH), 47.6 (C), 48.4 (C). Elemental
Anal. Calcd (%) for C11H18S (170.31): C, 70.52; H, 10.65. Found: C, 70.59; H, 10.68.
22
22
1
General Procedure for the Preparation of Alkyl Methyl Sulfides
The solution of the thiol (5.9 mmol) in anhydrous petroleum ether (15 mL) was
carefully added to the suspension of NaH (0.570 g, 23.8 mmol) in anhydrous petroleum ether
(15 mL). The mixture was kept 0.5 h at ambient temperature under an argon atmosphere.
Methyl iodide (1.70 g, 11.9 mmol) was added and the mixture was stirred for 24 h. The
solution was poured into water (75 mL) and extracted with petroleum ether (3 × 50 mL).

SULFIDES DERIVED FROM CARANE, P-MENTHANE, PINANE, BORNANE
281
The combined organic layers were dried over MgSO4, and the solvent was evaporated. The
crude products were purified by column chromatography.
(1S,3R,4S,6R)-(+)-4-Caranyl Methyl Sulfide (16). Yield 80%; yellow oil;
[α]D = +21.42 (c 7.75, CHCl3); 1H NMR (700 MHz): 0.55 (ddd, 1H, J = 6.3, 9.1,
22
9.1 Hz), 0.62 (ddd, 1H, J = 7.0, 9.1, 9.1 Hz), 0.83 (ddd, 1H, J = 7.0, 9.1, 16.1 Hz), 0.92 (d,
3H, CH3, J = 7.0 Hz), 0.96 (s, 3H, CH3), 0.98 (s, 3H, CH3), 1.24 (ddd, 1H, J = 6.3, 8.4,
15.4 Hz), 1.79 (ddd, 1H, J = 5.6, 8.4, 14.7 Hz), 1.85–1.91 (m, 1H), 2.05 (s, 3H, CH3), 2.14
(ddd, 1H, J = 6.3, 8.4, 14.7 Hz), 2.74 (dt, 1H, J = 6.3, 7.7 Hz); 13C NMR (100.6 MHz): 15.7
(CH3), 15.7 (CH3), 17.6 ©, 18.6 (CH3), 21.1 (CH), 21.2 (CH), 24.4 (CH2), 25.2 (CH2),
28.6 (CH3), 30.7 (CH), 47.7 (CH). Elemental Anal. Calcd (%) for C11H20S (184.34): C,
71.67; H, 10.94. Found: C, 71.76; H, 10.91.
(1S,2S,5R)-(+)-Methyl Neomenthyl Sulfide (19). Yield 29%; yellow oil;
[α]D = +93.10 (c 7.25, CHCl3); Lit.24 [α]D = +90.30 (c 3.85, CDCl3); H NMR
(700 MHz): 0.83–0.86 (m, 1H), 0.85 (d, 3H, CH3, J = 7.0 Hz), 0.87 (d, 3H, CH3, J =
6.3 Hz), 0.92 (d, 3H, CH3, J = 7.0 Hz), 1.03–1.23 (m, 3H), 1.59–1.72 (m, 3H), 1.85–1.92
(m, 1H), 1.93 (dq, 1H, J = 2.8, 14.0 Hz), 2.04 (s, 3H, CH3), 2.99 (m, 1H); 13C NMR
(176.1 MHz): 15.2 (CH3), 20.7 (CH3), 21.1 (CH3), 22.2 (CH3), 26.0 (CH2), 26.4 (CH),
30.1 (CH), 35.4 (CH2), 39.8 (CH2), 48.8 (CH), 49.9 (CH). Elemental Anal. Calcd (%) for
23
20
1
C11H22S (186.36): C, 70.89; H, 11.90. Found: C, 71.11; H, 11.84.
24
(1S,2R,5S)-(–)-Methyl Myrtanyl Sulfide (22). Yield 51%; yellow oil; [α]D
=
–30.00 (c 5.21, CHCl3); 1H NMR (700 MHz): 0.87 (d, 1H, J = 9 .1 Hz), 0.97 (s, 3H, CH3),
1.16 (s, 3H, CH3), 1.47–1.53 (m, 1H), 1.80–2.10 (m, 5H), 2.04 (s, 3H, CH3), 2.18–2.23 (m,
1H), 2.30–3.24 (m, 1H), 2.53 (ddd, 2H, J = 7.0, 12.6, 24.5 Hz); 13C NMR (176.1 MHz):
15.8 (CH3), 22.1 (CH2), 23.3 (CH3), 26.2 (CH2), 28.0 (CH3), 33.4 (CH2), 38.7 (C), 40.6
(CH), 41.4 (CH), 41.8 (CH2), 45.6 (CH). Elemental Anal. Calcd (%) for C11H20S (184.34):
C, 71.67; H, 10.94. Found: C, 71.99; H, 10.87.
28
(1R,2R,4R)-(+)-Isobornyl Methyl Sulfide (25). Yield 60%; yellow oil; [α]D
1
= +72.17 (c 5.75, CHCl3); H NMR (700 MHz): 0.80 (s, 3H, CH3), 0.96 (s, 3H, CH3),
0,98 (s, 3H, CH3), 1.10–1.14 (m, 2H), 1.63–1.78 (m, 4H), 1.86 (dd, 1 H, J = 9.1, 12.6 Hz),
2.09 (s, 3H, CH3), 2.56 (dd, 1H, J = 5.6, 9.1 Hz); 13C NMR (176.1 MHz): 13.6 (CH3),
18.2 (CH3), 20.3 (CH3), 20.4 (CH3), 27.4 (CH2), 38.5 (CH2), 40.0 (CH2), 45.8 (CH), 47.3
(C), 49.5 (C), 56.7 (CH). Elemental Anal. Calcd (%) for C11H20S (184.34): C, 71.67; H,
10.94. Found: C, 72.01; H, 10.90.
General Procedure for the Preparation of Dialkyl Sulfides
To a suspension of NaH (0.660 g, 27.5 mmol) in anhydrous petroleum ether (15 mL)
was carefully added a thiol solution (6.6 mmol) in anhydrous petroleum ether (15 mL).
The solution was stirred 0.5 h at ambient temperature under an argon atmosphere. The
respective tosylate (6.8 mmol) was added, and the mixture was stirred under reflux for
24 h. The solution was poured into water (75 mL) and extracted with petroleum ether (3 ×
50 mL). The combined organic layers were dried with anhydrous MgSO4 and the solvent
was evaporated. The crude product was purified by column chromatography.
20
(1S,3R,4S,6R)-(+)-4-Dicaranyl Sulfide (17). Yield 23%; yellow oil; [α]D
=
+48.00 (c 4.84, CHCl3); 1H NMR (400 MHz): 0.57 (ddd, 2H, J = 5.2, 8.8, 14.0 Hz), 0.66
(ddd, 2H, J = 4.6, 8.4, 15.2 Hz), 0.85 (ddd, 2H, J = 5.2, 8.8, 14.0 Hz), 0.96 (d, 6H, 2
CH3, J = 6.8 Hz), 0.99 (s, 6H, 2 CH3), 1.04 (s, 6H, 2 CH3), 1.38 (ddd, 2H, J = 5.2, 7.2,
14.8 Hz), 1.79–1.91 (m, 4H), 2.17 (ddd, 2H, J = 6.8, 8.8, 15.6 Hz), 2.80 (dd, 2H, J = 5.2,

282
A. BANACH ET AL.
8.8 Hz); 13C NMR (100.6 MHz): 15.9 (2 CH3), 17.7 (2 C), 19.0 (2 CH3), 21.0 (2 CH), 21.3
(2 CH), 25.2 (2 CH2), 25.4 (2 CH2), 28.7 (2 CH3), 31.2 (2 CH), 44.8 (2 CH). Elemental
Anal. Calcd (%) for C20H34S (306.55): C, 78.36; H, 11.18. Found: C, 78.15; H, 11.12.
24
(1S,2S,5R)-(+)-Dineomenthyl Sulfide (20). Yield 10%; yellow oil; [α]D
=
+141.83 (c 6.04, CHCl3); 1H NMR (400 MHz): 0.83–0.95 (m, 12H), 0.87 (d, 6H, 2 CH3,
J = 6.4 Hz), 0.90 (d, 6H, 2 CH3, J = 6.4 Hz), 0.93 (d, 6H, 2 CH3, J = 6.8 Hz), 1.06–1.26
(m, 6H), 1.67–1.77 (m, 6H), 1.93 (dq, 2H, J = 2.4, 13.6 Hz), 2.03–2.18 (m, 2H), 3.10 (d,
2H, J = 2.8 Hz); 13C NMR (100.6 MHz): 20.4 (2 CH3), 21.2 (2 CH3), 22.1 (2 CH3), 26.2
(2 CH2), 26.3 (2 CH), 29.8 (2 CH), 35.6 (2 CH2), 39.9 (2 CH2), 43.5 (2 CH), 49.0 (2 CH).
Elemental Anal. Calcd (%) for C20H38S (310.58): C, 77.34; H, 11.69. Found: C, 77.47; H,
11.70.
23
(1S,2R,5S)-(–)-Dimyrtanyl Sulfide (23). Yield 93%; yellow oil; [α]D = –67.99
(c 4.11, CHCl3); 1H NMR (700 MHz): 0.87 (d, 2H, J = 9.8 Hz), 0.97 (s, 6H, 2 CH3), 1.17
(s, 6H, 2 CH3), 1.47–1.53 (m, 2H), 1.80–2.10 (m, 10H), 2.15–2.20 (m, 2H), 2.30–3.24 (m,
2H), 2.53 (ddd, 4H, J = 7.7, 12.6, 23.8 Hz); 13C NMR (176.1 MHz): 22.2 (2 CH2), 23.3
(2 CH3), 26.2 (2 CH2), 28.0 (2 CH3), 33.4 (2 CH2), 38.7 (2 C), 39.7 (2 CH2), 41.2 (2 CH),
41.4 (2 CH), 45.6 (2 CH). Elemental Anal. Calcd (%) for C20H34S (306.55): C, 78.36; H,
11.18. Found: C, 78.72; H, 11.15.
General Procedure for the Preparation of Alkyl Phenyl Sulfides
To a suspension of NaH (1.12 g, 46.5 mmol) in anhydrous DMSO (10 mL) was
carefully added thiophenol solution (1.131 g, 6.6 mmol) in DMSO (10 mL). The solution
was stirred 0.5 h at ambient temperature under an argon atmosphere. The respective tosylate
(11.9 mmol) was added and the mixture was mixed in 90◦C for 10 h. The solution was
poured into 10% solution NaOH (100 ml) and extracted with diethyl ether (3 × 50 mL).
The combined ethereal layers were dried with anhydrous MgSO4, and the solvent was
evaporated. The crude product was purified by column chromatography.
(1S,3R,4S,6R)-(+)-4-Caranyl Phenyl Sulfide (18). Yield 81%; yellow oil;
22
1
[α]D = +36.03 (c 5.78, CHCl3); H NMR (700 MHz): 0.56 (ddd, 1H, J = 5.6, 9.1,
14.7 Hz), 0.67 (ddd, 1H, J = 7.0, 9.1, 16.1 Hz), 0.90 (ddd, 1H, J = 7.0, 9.8, 16.8 Hz), 0.97
(s, 3H, CH3), 0.98 (d, 3H, CH3, J = 7.0 Hz), 1.03 (s, 3H, CH3), 1.34 (ddd, 1H, J = 6.3,
8.4, 15.4 Hz), 1.85 (ddd, 1H, J = 6.3, 9.1, 14.7 Hz), 1.96–2.00 (m, 1H), 2.17 (ddd, 1H, J
= 6.8, 8.8, 15.6 Hz), 3.45 (dt, 1H, J = 6.3, 7.7 Hz), 7.14–7.17 (m, 1Harom), 7.23–7.26 (m,
2Harom), 7.34–7.36 (m, 2Harom); 13C NMR (100.6 MHz): 15.9 (CH3), 17.8 (C), 19.0 (CH3),
21.0 (CH), 21.3 (CH), 24.8 (CH2), 25.4 (CH2), 28.6 (CH3), 30.8 (CH), 47.9 (CH), 125.9
(CHarom), 128.8 (2 CHarom), 130.5 (2 CHarom), 137.2 (Carom). Elemental Anal. Calcd (%)
for C16H22S (246.41): C, 77.99; H, 9.00. Found: C, 77.81; H, 9.01.
(1S,2S,5R)-(+)-Neomenthyl Phenyl Sulfide (21). Yield 60%; yellow oil;
[α]D = +82.21 (c 6.79, CHCl3); 1H NMR (400 MHz): 0.86 (d, 3H, CH3, J = 6.4 Hz),
24
0.90–0.92 (m, 1H), 0.95 (d, 3H, CH3, J = 2.4 Hz), 0.96 (d, 3H, CH3, J = 2.8 Hz), 1.15–1.33
(m, 3H), 1.72–1.82 (m, 3H), 1.92 (dq, 1H, J = 2.0, 13.6 Hz), 2.01–2.09 (m, 1H), 3.65 (d,
1H, J = 2.0 Hz), 7.18–7.23 (m, 1Harom), 7.27–7.31 (m, 2Harom), 7.40–7.43 (m, 2Harom); 13
C
NMR (100.6 MHz): 20.7 (CH3), 21.2 (CH3), 22.2 (CH3), 26.2 (CH2), 26.5 (CH), 30.2 (CH),
35.4 (CH2), 40.6 (CH2), 48.9 (CH), 49.8 (CH), 126.1 (CHarom), 128.8 (2 CHarom), 131.1
(2 CHarom), 136.9 (Carom). Elemental Anal. Calcd (%) for C16H24S (248.43): C, 77.36; H,
9.72. Found: C, 77.35; H, 9.70.

SULFIDES DERIVED FROM CARANE, P-MENTHANE, PINANE, BORNANE
283
21
(1S,2R,5S)-(–)-Myrtanyl Phenyl Sulfide (24). Yield 76%; yellow oil; [α]D
=
–29.71 (c 6.83, CHCl3); 1H NMR (400 MHz): 0.85–0.89 (m, 1H), 0.90 (d, 1H, J = 9.6 Hz),
1.05 (s, 3H, CH3), 1.21 (s, 3H, CH3), 1.60–1.64 (m, 1H), 1.81–2.10 (m, 4H), 2.26–2.39 (m,
2H), 3.02 (ddd, 2H, J = 7.2, 12.4, 26.4 Hz), 7.14–7.19 (m, 1Harom), 7.25–7.30 (m, 2Harom),
7.35–7.40 (m, 2Harom); 13C NMR (100.6 MHz): 22.1 (CH2), 23.3 (CH3), 26.2 (CH2), 28.0
(CH3), 33.3 (CH2), 38.7 ©, 40.6 (CH), 40.8 (CH2), 41.3 (CH), 45.6 (CH), 125.6 (CHarom),
128.8 (2 CHarom), 128.9 (2 CHarom), 137.3 (Carom). Elemental Anal. Calcd (%) for C16H22S
(246.41): C, 77.99; H, 9.00. Found: C, 78.25; H, 8.97.
28
(1R,2R,4R)-(+)-Isobornyl Phenyl Sulfide (27). Yield 9%; yellow oil; [α]D
=
+82.88 (c 5.92, CHCl3); 1H NMR (700 MHz): 0.89 (s, 3H, CH3), 1.05 (s, 3H, CH3), 1.07
(s, 3H, CH3), 1.20–1.32 (m, 2H), 1.70–1.80 (m, 3H), 2.05 (dt, 2H, J = 2.0, 7.6 Hz), 3.25
(t, 1H, J = 7.6 Hz), 7.14–7.19 (m, 1Harom), 7.25–7.30 (m, 2Harom), 7.35–7.40 (m, 2Harom);
13C NMR (100.6 MHz): 14.9 (CH3), 21.2 (CH3), 21.5 (CH3), 28.4 (CH2), 39.5 (CH2), 42.0
(CH2), 46.9 (CH), 48.6 (C), 50.9 (C), 57.2 (CH), 126.5 (CHarom), 129.7 (2 CHarom), 130.3
(2 CHarom), 140.3 (Carom). Elemental Anal. Calcd (%) for C16H22S (246.41): C, 77.99; H,
9.00. Found: C, 78.44; H, 8.92.
Stilbene Epoxide. A mixture of a sulfide (2.18 mmol), benzyl bromide (0.749 g,
4.38 mmol), sodium hydroxide (0.088 g, 2.20 mmol) and benzaldehyde (0.231 g,
2.18 mmol) in 10 mL of acetonitrile was stirred for 3 d. Acetonitrile was evaporated, and
water (50 mL) was added. The mixture was extracted with petroleum ether (3 × 50 mL)
and the combined organic layers were dried with anhydrous magnesium sulfate. The
solvent was evaporated. The crude products were purified by column chromatography.
Using petroleum ether:ethyl acetate 95:5 as the mobile phase gave pure trans-stilbene
oxide. For the detailed results see Table 2.
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