Stereoselective synthesis of (Z)-1,2-dithio-1-alkenes via copper-catalyzed thiolation of (Z)-2-bromovinyl sulfides

DOI: 10.1055/s-0031-1290067

Source and publish data:

Synthesis p. 380 - 388 (2012)

Update date:2022-08-05

Topics:

Authors:

Xu, Hui Xu, Hui

Chen, Wanzhi

Chen, Jiuxi

Wu, Huayue

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Article abstract of DOI:10.1055/s-0031-1290067

We describe a new method for the stereoselective synthesis of (Z)-1,2-dithio-1-alkenes via copper-catalyzed cross-coupling of (Z)-2-bromovinyl sulfides and thiols. The desired products are obtained in good to excellent yields. The double bond geometry of the starting (Z)-2-bromovinyl sulfides is retained under these reaction conditions. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0031-1290067

380

PAPER

Stereoselective Synthesis of (Z)-1,2-Dithio-1-alkenes via Copper-Catalyzed

Thiolation of (Z)-2-Bromovinyl Sulfides

Hui Xu,^aWanzhi Chen,*^aJiuxi Chen,^bHuayue Wu*^b

Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, P. R. of China

Fax +86(571)88273314; E-mail: chenwzz@zju.edu.cn

College of Chemistry & Material Engineering, Wenzhou University, Wenzhou 325035, P. R. of China

E-mail: hywu3@163.com

Received 31 October 2011; revised 4 December 2011

tives.^29–31The copper-catalyzed coupling of thiols with

Abstract: We describe a new method for the stereoselective syn-

alkyl vinyl bromides has not been well-documented.³²Re-

thesis of (Z)-1,2-dithio-1-alkenes via copper-catalyzed cross-cou-

cently, we reported the regio- and stereoselective synthe-

sis of N-fused heterocycles and 1,2-hetero-disubstituted

pling of (Z)-2-bromovinyl sulfides and thiols. The desired products

are obtained in good to excellent yields. The double bond geometry

of the starting (Z)-2-bromovinyl sulfides is retained under these re- alkenes from 1,1-dibromo-1-alkenes using a copper cata-

lyst.^33,34(Z)-2-Bromovinyl sulfides were readily available

action conditions.

by the reactions of 1,1-dibromo-1-alkenes with thiols me-

diated by tetrabutylammonium fluoride (Scheme 1).³³

These bromovinyl sulfides bearing a bromine atom at the

double bond offer opportunities for the introduction of an-

other sulfide group through metal-catalyzed C(sp²)–S

coupling reactions. Herein, we describe a stereoselective

synthesis of (Z)-1,2-dithio-1-alkenes via the copper-cata-

lyzed cross-coupling of thiols with bromovinyl sulfides.

Key words: copper catalyst, cross-coupling, thiolation, (Z)-2-bro-

movinyl sulfide, (Z)-1,2-dithio-1-alkene

1,2-Dithio-1-alkenes are important intermediates in or-

ganic synthesis, useful precursors for optoelectronic ma-

terials, and chelate ligands in coordination chemistry.^1–4

Thus, the development of regio- and stereoselective syn-

theses of 1,2-dithio-1-alkenes is of practical interest. Var-

ious synthetic methods have been reported for these

compounds.^5–18Metal-catalyzed addition of a disulfide to

a terminal alkyne is so far the most efficient method for

the synthesis of 1,2-dithio-1-alkenes. The first example of

the reaction involving terminal alkynes and a diaryl disul-

fide (Ar₂S₂) was reported by Sonoda in 1991.¹⁴The

reaction was catalyzed by tetrakis(triphenylphos-

phine)palladium(0) [Pd(PPh₃)₄] giving the expected (Z)-

1,2-bis(arylthio)-1-alkenes in good yields and stereose-

lectivity. Metal catalysts such as palladium,^6–8,11rhodi-

um,⁹and nickel⁵have been widely studied in the

disulfidation of various alkynes normally leading to Z-

configured products. Both aromatic disulfides and ali-

phatic disulfides can be used as the starting thio com-

pounds. Gallium(III) chloride (GaCl₃) also promotes the

disulfidation of alkynes, but leads to E-configured prod-

ucts selectively when a stoichiometric amount of the cat-

alyst was used.¹⁶All these known methods are restricted

to the synthesis of symmetric 1,2-dithio-1-alkenes having

two identical thio groups.

R²

TBAF⋅3H₂O

R²SH

DMF, 65 °C, 12 h

R¹

R¹= alkyl

R²= aryl, heteroaryl

Scheme 1 Tetrabutylammonium fluoride mediated reactions of 1,1-

dibromo-1-alkenes with thiols

As shown in Table 1, the thiolation of (Z)-2-bromovinyl

sulfide 1a and 4-toluenethiol (2a) could be carried out by

using copper(I) oxide (Cu₂O) (10 mol%), N,N¢-dimethyl-

ethylenediamine (DMEDA) (15 mol%) and two equiva-

lents of cesium carbonate in N,N-dimethylformamide.

(Z)-1,2-Dithio-1-alkene 3a was obtained in 82% yield and

the Z-configuration of the double bond was confirmed by

NOESY measurements. To explore the scope of the reac-

tion, we examined the cross-coupling of a number of sub-

stituted (Z)-2-bromovinyl sulfides with various aromatic

thiols under the same catalytic conditions. The results are

listed in Table 1.

In general, we were able to obtain (Z)-1,2-diarylthio-1-

alkenes bearing two identical or two different arylthio

groups in up to 91% yield at 120 °C. The carbon–sulfur

coupling of 1a with various substituted thiophenols gave

high conversions and 75–85% isolated yields of products

(Table 1, entries 1–4). Naphthalene-2-thiol (2e) coupled

with 1a smoothly giving the desired (Z)-1,2-dithio-1-alk-

ene 3e in 81% isolated yield (Table 1, entry 5). Sulfur-

containing heterocycles occur in many compounds of bio-

logical interest, thus we attempted to broaden the scope of

our methodology to heterocyclic thiols. 2-Mercaptopyri-

Copper-catalyzed C–S coupling reactions have been dem-

onstrated to be powerful tools for the formation of aryl C–

S bonds^19–24and vinyl C–S bonds.^25–32Compared to vinyl

iodides, vinyl bromides are less reactive. Examples of the

coupling reactions of vinyl bromides with thiols in the lit-

erature are limited to 1-(2-bromovinyl)benzene deriva-

SYNTHESIS 2012, 44, 380–388

Advanced online publication: 03.01.2012

DOI: 10.1055/s-0031-1290067; Art ID: H102311SS

PAPER

Stereoselective Synthesis of (Z)-1,2-Dithio-1-alkenes

381

dine (2f) and 2-mercaptothiophene (2g) were coupled unsymmetric diaryl disulfides (Ar¹SSAr²) would afford

with 1a affording the desired products in 70% and 88% product mixtures without any selectivity. When vinyl bro-

isolated yields, respectively (Table 1, entries 6 and 7). Un- mides possessing different alkyl substituents such as 1-

fortunately, no product was obtained when the coupling of hexyl, isopropyl, isobutyl, tert-butyl, and cyclohexyl were

1a was attempted with 4-nitrobenzenethiol (2h) even at reacted with 4-toluenethiol (2a), good to excellent yields

higher temperatures, probably due to the low nucleophi- of the corresponding products were obtained (Table 1, en-

licity of 4-nitrobenzenethiolate (Table 1, entry 8). The thi- tries 15–19). It would appear that the bulkiness of the

olation of vinyl bromides bearing different aryl and alkyl group had no effect on the reactions. Aromatic bro-

heteroaryl sulfide substituents with 4-toluenethiol (2a) movinyl sulfides could not be generated according to our

was also evaluated (Table 1, entries 9–14). All the reac- reported methodology,³³thus we did not extend the reac-

tions proceeded smoothly, affording the corresponding tion to these substrates. Although symmetric (Z)-1,2-

products 3i–n in 77–89% isolated yields. Compounds 3i– dithio-1-alkenes such as 3a and 3o–s could also be synthe-

n are structural isomers of 3b–g. Thus both isomeric (Z)- sized by metal-catalyzed disulfidation of alkynes, these

1,2-dithio-1-alkenes could be easily prepared by appropri- reactions usually require expensive palladium or rhodium

ate choice of the bromovinyl sulfides and thiols. In con- as catalysts in combination with environmentally un-

trast, unsymmetric (Z)-1,2-dithio-1-alkenes could not be friendly phosphines as ligands.^5–9,11

prepared via disulfidation of alkynes since disulfidation of

Table 1 Thiolation of (Z)-2-Bromovinyl Sulfides with Aromatic Thiols^a

Entry

(Z)-2-Bromovinyl sulfide

Aromatic thiol

Product

Yield (%)

C₈H₁₇

75^b

C₈H₁₇

OMe

MeO

C₈H₁₇

–

C₈H₁₇

NO₂

O₂N

C₈H₁₇

Synthesis 2012, 44, 380–388

382

H. Xu et al.

PAPER

Table 1 Thiolation of (Z)-2-Bromovinyl Sulfides with Aromatic Thiols^a(continued)

Entry

(Z)-2-Bromovinyl sulfide

Aromatic thiol

Product

Yield (%)

C₈H₁₇

MeO

77^b

C₈H₁₇

C₆H₁₃

^aReaction conditions: (Z)-2-bromovinyl sulfide (0.5 mmol), aromatic thiol (0.75 mmol), Cu₂O (10 mol%), DMEDA (15 mol%), Cs₂CO₃

(2 equiv), DMF (1.5 mL), 120 °C, 24 h.

^bReaction at 80 °C, 36 h.

Using the reaction conditions described above, we were the case of cyclohexane thiol, a 94% yield of the desired

also able to prepare (Z)-1,2-alkylthio/arylthio-1-alkenes product 3u was obtained. The thiolation with aliphatic thi-

in excellent yields from (Z)-2-bromovinyl sulfides and ols also showed excellent stereoselectivity, and as with

alkyl thiols. The results are summarized in Table 2. (Z)-2- aromatic thiols, we did not observe the formation of

Bromovinyl sulfide (1a) reacted with benzyl thiol (2i), cy- (E)-1,2-dithio-1-alkenes.

clohexane thiol (2j), and linear aliphatic chain thiols 2k,l

To examine the substituent compatibility of (Z)-2-bro-

at 120 °C in the presence of two equivalents of cesium

movinyl sulfides in the thiolation reaction, a number of

carbonate to afford the corresponding (Z)-1,2-dithio-1-

(Z)-2-bromovinyl sulfides 1b–l were reacted with octane-

alkenes 3t–w in excellent yields (Table 2, entries 1–4). In

1-thiol (2k) in the presence of copper(II) oxide (10 mol%)

Synthesis 2012, 44, 380–388

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Stereoselective Synthesis of (Z)-1,2-Dithio-1-alkenes

383

and N,N¢-dimethylethylenediamine (15 mol%) at 120 °C. tries 12–14). The Z-configuration of the products was

In general, the alkyl thiols were more reactive than aryl confirmed by NOESY experiments. In the NOESY spec-

thiols as was demonstrated by the higher isolated yields tra of 3t and 3y, the alkene protons exhibited cross peaks

obtained. This was to be expected since alkyl thiolates are with the adjacent methylene protons of the octyl groups

more nucleophilic than aryl thiolates. The reactions of (see Supporting Information).^9,35The reaction of a 1,2-di-

1b–l and 2k proceeded with complete conversion into the bromoalkene with aliphatic thiols often gave a mixture of

desired disulfides in excellent yields. Both electron-rich an alkynyl sulfide and a bromovinyl sulfide which could

and electron-poor substituents on the aryl and heteroaryl not be separated by column chromatography.³³Therefore,

groups were well tolerated. In addition, steric hindrance we did not study the synthesis of 1,2-dialkylthioalkenes.

had little influence on the thiolation reaction (Table 2, en-

Table 2 Thiolation of (Z)-2-Bromovinyl Sulfides with Alkyl Thiols^a

Entry

(Z)-2-Bromovinyl sulfide

Alkyl thiol

Product

Yield (%)

C₈H₁₇

SC₈H₁₇

SC₄H₉

H₁₇C₈SH

C₈H₁₇

H₉C₄SH

C₈H₁₇

SC₈H₁₇

C₈H₁₇

SC₈H₁₇

C₈H₁₇

MeO

SC₈H₁₇

87^b

C₈H₁₇

3aa

SC₈H₁₇

C₈H₁₇

SC₈H₁₇

3bb

3cc

C₈H₁₇

SC₈C₁₇

C₈H₁₇

C₆H₁₃

C₈H₁₇

SC₈H₁₇

3dd

C₆H₁₃

Synthesis 2012, 44, 380–388

384

H. Xu et al.

PAPER

Table 2 Thiolation of (Z)-2-Bromovinyl Sulfides with Alkyl Thiols^a(continued)

Entry

(Z)-2-Bromovinyl sulfide

Alkyl thiol

Product

Yield (%)

SC₈H₁₇

3ee

SC₈H₁₇

3ff

SC₈H₁₇

3gg

SC₈H₁₇

3hh

^aReaction conditions: (Z)-2-bromovinyl sulfide (0.5 mmol), alkyl thiol (0.75 mmol), Cu₂O (10 mol%), DMEDA (15 mol%), Cs₂CO₃(2 equiv),

DMF (1.5 mL), 120 °C, 24 h.

^bReaction at 80 °C, 36 h.

(Z)-(1-Bromodec-1-en-2-yl)(4-methoxyphenyl)sulfane (1d)

Light yellow oil; yield: 157 mg (88%).

dithio-1-alkenes. Both symmetric and unsymmetric (Z)- ¹H NMR (400 MHz, CDCl₃): d = 7.41 (d, J = 8.0 Hz, 2 H), 6.88 (d,

In conclusion, we have described a concise synthetic

methodology for the stereoselective synthesis of (Z)-1,2-

J = 8.0 Hz, 2 H), 6.13 (s, 1 H), 3.83 (s, 3 H), 2.04 (t, J = 7.6 Hz, 2

H), 1.38–1.35 (m, 2 H), 1.28–1.13 (m, 10 H), 0.88 (t, J = 7.0 Hz, 3

H).

¹³C NMR (100 MHz, CDCl₃): d = 160.0, 143.5, 136.1, 121.8, 114.5,

100.5, 55.2, 35.5, 31.7, 29.0, 28.9, 28.6, 28.1, 22.5, 14.0.

1,2-dithio-1-alkenes have been obtained via copper-cata-

lyzed thiolation of (Z)-2-bromovinyl sulfides in very good

to excellent yields. The copper-catalyzed C–S coupling

offers a novel route to (Z)-1,2-dithio-1-alkenes using an

inexpensive catalyst and readily available starting materi-

als. Further investigation of the utility of this method and

of the obtained products is currently in progress.

HRMS (TOF): m/z calcd for C₁₇H₂₅BrOS: 356.0809; found:

356.0808.

(Z)-(1-Bromodec-1-en-2-yl)(naphthalen-2-yl)sulfane (1e)

Light yellow oil; yield: 170 mg (90%).

¹H NMR (400 MHz) and ¹³C NMR (100 MHz) spectra were record-

ed in CDCl₃using a Bruker Avance 400 spectrometer. Chemical

shifts (d) are expressed in ppm downfield relative to TMS (0 ppm)

and coupling constants (J) are given in Hz. The following abbrevi-

ations are used to describe the signal patterns where appropriate:

br = broad, s = singlet, d = doublet, t = triplet, td = triplet of dou-

blets, m = multiplet. HRMS were obtained using a Waters GCT

Premier TOF mass spectrometer with EI source. Column chroma-

tography was performed using high purity silica gel (60 Å, 200–300

mesh). Petroleum ether (PE) refers to the fraction boiling in the 60–

90 °C range. (Z)-2-Bromovinyl sulfides were prepared according to

our previously reported method.³³

¹H NMR (400 MHz, CDCl₃): d = 8.00 (s, 1 H), 7.87–7.81 (m, 3 H),

7.55–7.49 (m, 3 H), 6.40 (s, 1 H), 2.20 (t, J = 7.4 Hz, 2 H), 1.48–

1.45 (m, 2 H), 1.29–1.14 (m, 10 H), 0.89 (t, J = 7.0 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 142.4, 133.5, 132.5, 132.0, 129.9,

129.4, 128.6, 127.7, 127.5, 126.6, 126.5, 104.4, 36.3, 31.7, 29.1,

29.0, 28.6, 28.1, 22.5, 14.1.

HRMS (TOF): m/z calcd for C₂₀H₂₅BrS: 376.0860; found:

376.0864.

(Z)-2-[(1-Bromodec-1-en-2-yl)thio]thiophene (1g)

Light yellow oil; yield: 148 mg (89%).

(Z)-(1-Bromodec-1-en-2-yl)(o-tolyl)sulfane (1c)

¹H NMR (400 MHz, CDCl₃): d = 7.47 (d, J = 5.2 Hz, 1 H), 7.25 (d,

J = 3.6 Hz, 1 H), 7.04 (t, J = 4.4 Hz, 1 H), 6.11 (s, 1 H), 2.09 (t,

J = 7.4 Hz, 2 H), 1.48–1.41 (m, 2 H), 1.32–1.18 (m, 10 H), 0.89 (t,

J = 6.8 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 143.3, 136.9, 131.5, 128.8, 127.6,

100.0, 35.1, 31.7, 29.1, 29.0, 28.7, 28.3, 22.6, 14.0.

Light yellow oil; yield: 155 mg (91%).

¹H NMR (400 MHz, CDCl₃): d = 7.42 (d, J = 7.2 Hz, 1 H), 7.24–

7.23 (m, 2 H), 7.17–7.13 (m, 1 H), 6.29 (s, 1 H), 2.40 (s, 3 H), 2.00

(t, J = 7.4 Hz, 2 H), 1.40–1.33 (m, 2 H), 1.27–1.12 (m, 10 H), 0.87

(t, J = 7.4 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 142.3, 141.3, 134.3, 130.9, 130.4,

128.5, 126.3, 103.3, 35.8, 31.7, 29.1, 29.0, 28.6, 28.0, 22.5, 20.6,

14.0.

HRMS (TOF): m/z calcd for C₁₄H₂₁BrS₂: 332.0268; found:

332.0265.

HRMS (TOF): m/z calcd for C₁₇H₂₅BrS: 340.0860; found:

340.0858.

(Z)-(1-Bromo-3,3-dimethylbut-1-en-2-yl)(p-tolyl)sulfane (1k)

Light yellow oil; yield: 133 mg (93%).

Synthesis 2012, 44, 380–388

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Stereoselective Synthesis of (Z)-1,2-Dithio-1-alkenes

385

¹H NMR (400 MHz, CDCl₃): d = 7.21 (d, J = 8.0 Hz, 2 H), 7.14 (d,

J = 8.0 Hz, 2 H), 7.06 (s, 1 H), 2.37 (s, 3 H), 1.32 (s, 9 H).

(Z)-Naphthalen-2-yl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3e)

Light yellow oil; yield: 170 mg (81%).

¹³C NMR (100 MHz, CDCl₃): d = 149.2, 135.0, 132.2, 129.6, 126.9,

¹H NMR (400 MHz, CDCl₃): d = 7.88 (s, 1 H), 7.84–7.79 (m, 3 H),

7.53–7.46 (m, 3 H), 7.35 (d, J = 8.0 Hz, 2 H), 7.16 (d, J = 8.4 Hz, 2

H), 6.60 (s, 1 H), 2.37 (s, 3 H), 2.27 (t, J = 7.4 Hz, 2 H), 1.55–1.52

(m, 2 H), 1.33–1.25 (m, 10 H), 0.90 (t, J = 6.6 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.1, 136.4, 133.7, 133.4, 132.0,

131.4, 129.8, 129.7, 128.6, 127.7, 127.5, 127.4, 127.2, 126.6, 126.4,

125.9, 36.8, 31.8, 29.2, 29.1, 28.8, 28.5, 22.6, 21.1, 14.1.

115.7, 41.3, 29.2, 21.0.

HRMS (TOF): m/z calcd for C₁₃H₁₇BrS: 284.0234; found:

284.0239.

(Z)-Dec-1-ene-1,2-diylbis(p-tolylsulfane) (3a);³³Typical Proce-

dure

(Z)-(1-Bromodec-1-en-2-yl)(p-tolyl)sulfane (1a) (171 mg, 0.5

mmol) was added to a stirred solution of 4-toluenethiol (2a) (70 mg,

0.75 mmol), Cu₂O (7 mg, 0.05 mmol), DMEDA (8 mL, 0.075

mmol), Cs₂CO₃(326 mg, 1 mmol) in DMF (2 mL) under N₂. The

resulting mixture was stirred at 120 °C for 24 h. After being cooled

to r.t., the mixture was diluted with H₂O (15 mL) and extracted with

EtOAc (3 × 15 mL). The combined organic layer was dried over

Na₂SO₄and concentrated. The crude residue was purified by flash

column chromatography (eluent: PE–EtOAc, 50:1).

HRMS (TOF): m/z calcd for C₂₇H₃₂S₂: 420.1945; found: 420.1951.

(Z)-2-{[2-(p-Tolylthio)dec-1-en-1-yl]thio}pyridine (3f)

Light yellow oil; yield: 130 mg (70%).

¹H NMR (400 MHz, CDCl₃): d = 8.44 (d, J = 4.0 Hz, 1 H), 7.53 (td,

J = 8.0, 1.6 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.16–7.12 (m, 3 H),

7.05–7.02 (m, 1 H), 6.73 (s, 1 H), 2.40 (t, J = 7.6 Hz, 2 H), 2.36 (s,

3 H), 1.61–1.55 (m, 2 H), 1.29–1.26 (m, 10 H), 0.89 (t, J = 7.2 Hz,

3 H).

¹³C NMR (100 MHz, CDCl₃): d = 158.2, 149.6, 140.3, 137.7, 136.4,

132.4, 129.9, 129.7, 121.5, 120.0, 117.7, 33.1, 31.8, 29.3, 29.1,

29.0, 28.1, 22.6, 21.1, 14.1.

Light yellow oil; yield: 157 mg (82%).

¹H NMR (400 MHz, CDCl₃): d = 7.32–7.27 (m, 4 H), 7.13–7.08 (m,

4 H), 6.45 (s, 1 H), 2.32 (s, 3 H), 2.31 (s, 3 H), 2.20 (t, J = 7.2 Hz, 2

H), 1.49–1.46 (m, 2 H), 1.29–1.20 (m, 10 H), 0.87 (t, J = 6.8 Hz, 3

H).

¹³C NMR (100 MHz, CDCl₃): d = 137.12, 137.11, 134.7, 132.8,

131.5, 130.4, 130.3, 130.1, 130.0, 128.8, 37.2, 32.1, 29.6, 29.5,

29.1, 28.8, 22.9, 21.4, 21.3, 14.4.

HRMS (TOF): m/z calcd for C₂₂H₂₉NS₂: 371.1741; found:

371.1747.

(Z)-2-{[2-(p-Tolylthio)dec-1-en-1-yl]thio}thiophene (3g)

Light yellow oil; yield: 165 mg (88%).

¹H NMR (400 MHz, CDCl₃): d = 7.38 (d, J = 5.6 Hz, 1 H), 7.30 (d,

J = 8.0 Hz, 2 H), 7.19 (d, J = 3.2 Hz, 1 H), 7.13 (d, J = 8.0 Hz, 2 H),

7.02–7.00 (m, 1 H), 6.40 (s, 1 H), 2.35 (s, 3 H), 2.17 (t, J = 7.6 Hz,

2 H), 1.49–1.45 (m, 2 H), 1.31–1.22 (m, 10 H), 0.89 (t, J = 7.0 Hz,

3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.9, 133.5, 132.8, 132.7, 131.1,

130.9, 129.8, 129.7, 129.2, 127.6, 36.6, 31.8, 29.2, 29.1, 28.7, 28.3,

22.6, 21.1, 14.1.

(Z)-Phenyl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3b)

Light yellow oil; yield: 157 mg (85%).

¹H NMR (400 MHz, CDCl₃): d = 7.41 (d, J = 7.2 Hz, 2 H), 7.33–

7.28 (m, 4 H), 7.22 (t, J = 7.2 Hz, 1 H), 7.11 (d, J = 8.0 Hz, 2 H),

6.48 (s, 1 H), 2.32 (s, 3 H), 2.21 (t, J = 7.2 Hz, 2 H), 1.50–1.46 (m,

2 H), 1.30–1.20 (m, 10 H), 0.87 (t, J = 6.8 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.0, 136.1, 135.7, 131.3, 129.9,

129.7, 129.5, 129.0, 126.9, 126.6, 36.8, 31.8, 29.2, 29.1, 28.8, 28.5,

22.6, 21.1, 14.1.

HRMS (TOF): m/z calcd for C₂₁H₂₈S₃: 376.1353; found: 376.1354.

HRMS (TOF): m/z calcd for C₂₃H₃₀S₂: 370.1789; found: 370.1799.

(Z)-Phenyl[1-(p-tolylthio)dec-1-en-2-yl]sulfane (3i)

Light yellow oil; yield: 156 mg (84%).

(Z)-p-Tolyl[1-(o-tolylthio)dec-1-en-2-yl]sulfane (3c)

Light yellow oil; yield: 161 mg (84%).

¹H NMR (400 MHz, CDCl₃): d = 7.40 (d, J = 8.0 Hz, 2 H), 7.35 (d,

J = 8.0 Hz, 2 H), 7.32 (t, J = 8.0 Hz, 2 H), 7.24 (t, J = 7.2 Hz, 1 H),

7.16 (d, J = 8.0 Hz, 2 H), 6.57 (s, 1 H), 2.36 (s, 3 H), 2.26 (t, J = 7.2

Hz, 2 H), 1.53–1.50 (m, 2 H), 1.32–1.24 (m, 10 H), 0.90 (t, J = 6.8

Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.0, 133.9, 133.0, 132.1, 130.5,

130.3, 130.2, 129.8, 128.9, 126.6, 37.1, 31.8, 29.2, 29.1, 28.8, 28.5,

22.6, 21.0, 14.1.

¹H NMR (400 MHz, CDCl₃): d = 7.45–7.43 (m, 1 H), 7.33 (d,

J = 8.0 Hz, 2 H), 7.24–7.18 (m, 3 H), 7.14 (d, J = 8.4 Hz, 2 H), 6.39

(s, 1 H), 2.45 (s, 3 H), 2.36 (s, 3 H), 2.23 (t, J = 7.4 Hz, 2 H), 1.52–

1.49 (m, 2 H), 1.33–1.23 (m, 10 H), 0.90 (t, J = 7.0 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 138.2, 137.0, 136.1, 135.0, 131.4,

130.3, 130.0, 129.9, 129.7, 126.9, 126.6, 126.5, 36.7, 31.8, 29.2,

29.1, 28.7, 28.5, 22.6, 21.1, 20.6, 14.1.

HRMS (TOF): m/z calcd for C₂₃H₃₀S₂: 370.1789; found: 370.1785.

HRMS (TOF): m/z calcd for C₂₄H₃₂S₂: 384.1945; found: 384.1949.

(Z)-o-Tolyl[1-(p-tolylthio)dec-1-en-2-yl]sulfane (3j)

Light yellow oil; yield: 167 mg (87%).

(Z)-(4-Methoxyphenyl)[2-(p-tolylthio)dec-1-en-1-yl]sulfane

(3d)

Light yellow oil; yield: 150 mg (75%).

¹H NMR (400 MHz, CDCl₃): d = 7.40–7.35 (m, 3 H), 7.24–7.22 (m,

1 H), 7.21–7.16 (m, 4 H), 6.55 (s, 1 H), 2.46 (s, 3 H), 2.38 (s, 3 H),

2.19 (t, J = 7.4 Hz, 2 H), 1.53–1.49 (m, 2 H), 1.34–1.25 (m, 10 H),

0.92 (t, J = 7.0 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 139.3, 136.8, 133.6, 132.6, 132.4,

131.2, 130.3, 130.1, 129.8, 128.8, 127.0, 126.3, 36.8, 31.8, 29.3,

29.2, 28.8, 28.5, 22.6, 21.0, 20.5, 14.1.

¹H NMR (400 MHz, CDCl₃): d = 7.41 (d, J = 8.8 Hz, 2 H), 7.31 (d,

J = 8.0 Hz, 2 H), 7.13 (d, J = 8.0 Hz, 2 H), 6.89 (d, J = 9.2 Hz, 2 H),

6.43 (s, 1 H), 3.81 (s, 3 H), 2.35 (s, 3 H), 2.20 (t, J = 7.2 Hz, 2 H),

1.50–1.47 (m, 2 H), 1.31–1.22 (m, 10 H), 0.89 (t, J = 6.8 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 159.2, 136.7, 133.0, 132.5, 130.9,

130.1, 130.0, 129.6, 126.3, 114.7, 55.3, 36.8, 31.8, 29.2, 29.1, 28.7,

28.5, 22.6, 21.0, 14.1.

HRMS (TOF): m/z calcd for C₂₄H₃₂S₂: 384.1945; found: 384.1956.

HRMS (TOF): m/z calcd for C₂₄H₃₂OS₂: 400.1895; found:

400.1900.

(Z)-(4-Methoxyphenyl)[1-(p-tolylthio)dec-1-en-2-yl]sulfane

(3k)

Light yellow oil; yield: 154 mg (77%).

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¹H NMR (400 MHz, CDCl₃): d = 7.38 (d, J = 7.2 Hz, 2 H), 7.33 (d,

J = 7.2 Hz, 2 H), 7.15 (d, J = 7.6 Hz, 2 H), 6.87 (d, J = 7.2 Hz, 2 H),

6.36 (s, 1 H), 3.81 (s, 3 H), 2.35 (s, 3 H), 2.16 (t, J = 7.2 Hz, 2 H),

1.49–1.46 (m, 2 H), 1.29–1.22 (m, 10 H), 0.89 (t, J = 6.6 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.8, 133.2, 132.4, 131.2, 130.1,

130.0, 129.8, 129.7, 129.4, 46.0, 26.9, 22.0, 21.1, 21.0.

HRMS (TOF): m/z calcd for C₂₀H₂₄S₂: 328.1319; found: 328.1328.

¹³C NMR (100 MHz, CDCl₃): d = 159.3, 136.7, 136.0, 133.9, 132.5,

129.9, 129.8, 125.8, 123.8, 114.4, 55.2, 36.4, 31.8, 29.2, 29.1, 28.7,

28.4, 22.6, 21.0, 14.1.

(Z)-(3-Methylbut-1-ene-1,2-diyl)bis(p-tolylsulfane) (3q)

Light yellow oil; yield: 143 mg (91%).

¹H NMR (400 MHz, CDCl₃): d = 7.31 (d, J = 8.0 Hz, 2 H), 7.23 (d,

J = 8.0 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H), 7.08 (d, J = 8.0 Hz, 2 H),

6.61 (s, 1 H), 2.51–2.44 (m, 1 H), 2.32 (s, 3 H), 2.30 (s, 3 H), 1.12

(s, 3 H), 1.10 (s, 3 H).

HRMS (TOF): m/z calcd for C₂₄H₃₂OS₂: 400.1895; found:

400.1898.

(Z)-Naphthalen-2-yl[1-(p-tolylthio)dec-1-en-2-yl]sulfane (3l)

Light yellow oil; yield: 187 mg (89%).

¹³C NMR (100 MHz, CDCl₃): d = 138.2, 137.0, 136.1, 132.3, 131.1,

130.7, 130.4, 129.8, 129.7, 129.5, 35.6, 22.2, 21.0.

¹H NMR (400 MHz, CDCl₃): d = 7.90 (s, 1 H), 7.85–7.80 (m, 3 H),

7.54–7.47 (m, 3 H), 7.42 (d, J = 8.0 Hz, 2 H), 7.20 (d, J = 8.4 Hz, 2

H), 6.67 (s, 1 H), 2.39 (s, 3 H), 2.33 (t, J = 7.6 Hz, 2 H), 1.61–1.56

(m, 2 H), 1.33–1.25 (m, 10 H), 0.92 (t, J = 6.8 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.0, 133.7, 132.9, 132.2, 132.1,

131.5, 130.8, 130.3, 129.9, 128.7, 128.5, 128.0, 127.7, 127.3, 126.5,

125.9, 37.2, 31.8, 29.3, 29.2, 28.8, 28.5, 22.6, 21.1, 14.1.

HRMS (TOF): m/z calcd for C₁₉H₂₂S₂: 314.1163; found: 314.1160.

(Z)-(3,3-Dimethylbut-1-ene-1,2-diyl)bis(p-tolylsulfane) (3r)³⁶

Light yellow oil; yield: 144 mg (88%).

¹H NMR (400 MHz, CDCl₃): d = 7.28 (d, J = 8.0 Hz, 2 H), 7.17 (d,

J = 7.6 Hz, 2 H), 7.10 (d, J = 8.0 Hz, 2 H), 7.06 (d, J = 8.0 Hz, 2 H),

6.92 (s, 1 H), 2.30 (s, 3 H), 2.28 (s, 3 H), 1.20 (s, 9 H).

HRMS (TOF): m/z calcd for C₂₇H₃₂S₂: 420.1945; found: 420.1948.

¹³C NMR (100 MHz, CDCl₃): d = 138.2, 137.2, 136.2, 134.7, 132.5,

132.2, 130.7, 129.8, 129.6, 126.7, 39.9, 29.5, 21.1, 21.0.

(Z)-2-{[1-(p-Tolylthio)dec-1-en-2-yl]thio}pyridine (3m)

Light yellow oil; yield: 165 mg (89%).

(Z)-(1-Cyclohexylethene-1,2-diyl)bis(p-tolylsulfane) (3s)

Light yellow oil; yield: 152 mg (86%).

¹H NMR (400 MHz, CDCl₃): d = 8.45 (d, J = 4.4 Hz, 1 H), 7.52 (td,

J = 8.0, 1.6 Hz, 1 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.21 (d, J = 8.0 Hz,

1 H), 7.11 (d, J = 8.0 Hz, 2 H), 7.02–6.99 (m, 1 H), 6.77 (s, 1 H),

2.42 (t, J = 7.6 Hz, 2 H), 2.32 (s, 3 H), 1.56–1.51 (m, 2 H), 1.23 (br

m, 10 H), 0.86 (t, J = 6.8 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 158.2, 149.8, 137.2, 136.5, 135.6,

131.6, 130.5, 129.8, 129.2, 121.8, 119.9, 38.3, 31.8, 29.2, 29.1,

28.9, 28.5, 22.6, 21.0, 14.0.

¹H NMR (400 MHz, CDCl₃): d = 7.30 (d, J = 8.0 Hz, 2 H), 7.21 (d,

J = 7.6 Hz, 2 H), 7.11 (d, J = 7.6 Hz, 2 H), 7.08 (d, J = 8.4 Hz, 2 H),

6.62 (s, 1 H), 2.32 (s, 3 H), 2.30 (s, 3 H), 2.09 (t, J = 11.2 Hz, 1 H),

1.91 (d, J = 12.8 Hz, 2 H), 1.71 (d, J = 10.8 Hz, 2 H), 1.61 (d,

J = 8.0 Hz, 1 H), 1.29–1.08 (m, 5 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.0, 136.8, 135.8, 132.4, 131.8,

131.3, 130.3, 129.8, 129.6, 129.0, 45.8, 32.8, 26.4, 26.1, 21.0.

HRMS (TOF): m/z calcd for C₂₂H₂₉NS₂: 371.1741; found:

371.1748.

HRMS (TOF): m/z calcd for C₂₂H₂₆S₂: 354.1476; found: 354.1478.

(Z)-Benzyl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3t)

Light yellow oil; yield: 159 mg (83%).

(Z)-2-{[1-(p-Tolylthio)dec-1-en-2-yl]thio}thiophene (3n)

Light yellow oil; yield: 145 mg (77%).

¹H NMR (400 MHz, CDCl₃): d = 7.40–7.28 (m, 5 H), 7.20 (d,

J = 8.0 Hz, 2 H), 7.09 (d, J = 8.4 Hz, 2 H), 6.27 (s, 1 H), 3.97 (s, 2

H), 2.35 (s, 3 H), 2.13 (t, J = 7.6 Hz, 2 H), 1.46–1.39 (m, 2 H), 1.32–

1.19 (m, 10 H), 0.92 (t, J = 7.2 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 138.0, 136.5, 133.1, 130.7, 130.2,

129.5, 128.8, 128.5, 128.3, 127.1, 38.1, 36.9, 31.8, 29.2, 29.1, 28.6,

28.3, 22.6, 21.0, 14.1.

¹H NMR (400 MHz, CDCl₃): d = 7.41 (d, J = 5.2 Hz, 1 H), 7.33 (d,

J = 7.6 Hz, 2 H), 7.23 (d, J = 3.2 Hz, 1 H), 7.15 (d, J = 8.0 Hz, 2 H),

7.03–7.01 (m, 1 H), 6.28 (s, 1 H), 2.36 (s, 3 H), 2.19 (t, J = 7.4 Hz,

2 H), 1.54–1.51 (m, 2 H), 1.31–1.25 (m, 10 H), 0.90 (t, J = 6.8 Hz,

3 H).

¹³C NMR (100 MHz, CDCl₃): d = 137.0, 136.8, 135.1, 132.3, 130.9,

130.2, 129.8, 129.7, 127.4, 124.3, 36.0, 31.8, 29.2, 29.1, 28.8, 28.5,

22.6, 21.0, 14.1.

HRMS (TOF): m/z calcd for C₂₄H₃₂S₂: 384.1945; found: 384.1938.

HRMS (TOF): m/z calcd for C₂₁H₂₈S₃: 376.1353; found: 376.1357.

(Z)-Cyclohexyl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3u)

Light yellow oil; yield: 177 mg (94%).

(Z)-Oct-1-ene-1,2-diylbis(p-tolylsulfane) (3o)¹¹

Light yellow oil; yield: 150 mg (84%).

¹H NMR (400 MHz, CDCl₃): d = 7.34 (d, J = 8.0 Hz, 2 H), 7.31 (d,

J = 8.0 Hz, 2 H), 7.15 (d, J = 8.0 Hz, 2 H), 7.12 (d, J = 8.0 Hz, 2 H),

6.48 (s, 1 H), 2.35 (s, 3 H), 2.34 (s, 3 H), 2.22 (t, J = 7.8 Hz, 2 H),

1.51–1.46 (m, 2 H), 1.29–1.22 (m, 6 H), 0.87 (t, J = 6.8 Hz, 3 H).

¹H NMR (400 MHz, CDCl₃): d = 7.18 (d, J = 8.0 Hz, 2 H), 7.04 (d,

J = 8.0 Hz, 2 H), 6.31 (s, 1 H), 2.88–2.83 (m, 1 H), 2.27 (s, 3 H),

2.12 (t, J = 7.2 Hz, 2 H), 1.99 (d, J = 11.6 Hz, 2 H), 1.78–1.75 (m,

2 H), 1.61–1.58 (m, 1 H), 1.44–1.16 (m, 17 H), 0.84 (t, J = 7.0 Hz,

3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.3, 131.8, 130.5, 130.4, 129.5,

128.2, 45.9, 36.9, 33.7, 31.8, 29.2, 29.1, 28.7, 28.5, 25.9, 25.6, 22.6,

21.0, 14.0.

¹³C NMR (100 MHz, CDCl₃): d = 136.8, 134.3, 132.4, 131.1, 130.1,

129.8, 129.7, 128.4, 36.8, 31.5, 28.4, 22.5, 21.0, 20.9, 14.0.

HRMS (TOF): m/z calcd for C₂₃H₃₆S₂: 376.2258; found: 376.2260.

(Z)-(4-Methylpent-1-ene-1,2-diyl)bis(p-tolylsulfane) (3p)

Light yellow oil; yield: 143 mg (87%).

(Z)-Octyl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3v)

Light yellow oil; yield: 185 mg (91%).

¹H NMR (400 MHz, CDCl₃): d = 7.19 (d, J = 8.0 Hz, 2 H), 7.04 (d,

J = 8.4 Hz, 2 H), 6.24 (s, 1 H), 2.69 (t, J = 7.4 Hz, 2 H), 2.28 (s, 3

¹H NMR (400 MHz, CDCl₃): d = 7.36 (d, J = 7.6 Hz, 2 H), 7.32 (d,

J = 7.6 Hz, 2 H), 7.17 (d, J = 7.6 Hz, 2 H), 7.14 (d, J = 7.6 Hz, 2 H),

6.47 (s, 1 H), 2.36 (s, 6 H), 2.09 (d, J = 6.8 Hz, 2 H), 1.96–1.90 (m,

1 H), 0.87 (s, 3 H), 0.85 (s, 3 H).

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Stereoselective Synthesis of (Z)-1,2-Dithio-1-alkenes

387

H), 2.13 (t, J = 7.6 Hz, 2 H), 1.66–1.59 (m, 2 H), 1.44–1.36 (m, 4

H), 1.25 (br m, 10 H), 1.18 (br m, 8 H), 0.88–0.83 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.3, 131.5, 130.5, 130.2, 129.5,

37.0, 34.0, 31.8, 31.7, 30.4, 29.2, 29.1, 28.7, 28.6, 28.4, 22.6, 21.0,

14.0.

¹³C NMR (100 MHz, CDCl₃): d = 133.7, 132.3, 131.9, 130.4, 128.3,

128.0, 127.7, 127.6, 127.1, 126.3, 125.6, 37.4, 34.1, 31.8, 30.5,

29.3, 29.2, 28.8, 28.6, 28.5, 22.7, 22.6, 14.1.

HRMS (TOF): m/z calcd for C₂₈H₄₂S₂: 442.2728; found: 442.2715.

(Z)-2-{[1-(Octylthio)dec-1-en-2-yl]thio}pyridine (3bb)

Light yellow oil; yield: 181 mg (92%).

HRMS (TOF): m/z calcd for C₂₅H₄₂S₂: 406.2728; found: 406.2731.

(Z)-Butyl[2-(p-tolylthio)dec-1-en-1-yl]sulfane (3w)

Light yellow oil; yield: 156 mg (89%).

¹H NMR (400 MHz, CDCl₃): d = 8.37 (d, J = 4.8 Hz, 1 H), 7.44 (td,

J = 8.0, 1.2 Hz, 1 H), 7.10 (d, J = 8.0 Hz, 1 H), 6.94–6.91 (m, 1 H),

6.55 (s, 1 H), 2.67 (t, J = 7.4 Hz, 2 H), 2.32 (t, J = 7.4 Hz, 2 H),

1.62–1.54 (m, 2 H), 1.49–1.46 (m, 2 H), 1.34–1.28 (m, 2 H), 1.21–

1.19 (br m, 18 H), 0.84–0.80 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 158.4, 149.6, 136.4, 136.2, 127.3,

121.5, 119.6, 38.3, 33.7, 31.7, 31.6, 30.3, 29.2, 29.1, 29.0, 28.8,

28.5, 28.4, 22.5, 14.0, 13.9.

¹H NMR (400 MHz, CDCl₃): d = 7.23 (d, J = 8.0 Hz, 2 H), 7.09 (d,

J = 8.4 Hz, 2 H), 6.28 (s, 1 H), 2.74 (t, J = 7.6 Hz, 2 H), 2.32 (s, 3

H), 2.17 (t, J = 7.4 Hz, 2 H), 1.70–1.62 (m, 2 H), 1.50–1.41 (m, 4

H), 1.31–1.22 (m, 10 H), 0.95 (t, J = 7.2 Hz, 3 H), 0.89 (t, J = 6.8

Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.3, 131.5, 130.5, 130.4, 130.1,

129.5, 36.9, 33.7, 32.4, 31.8, 29.2, 29.1, 28.7, 28.4, 22.6, 21.7, 21.0,

14.0, 13.6.

HRMS (TOF): m/z calcd for C₂₃H₃₉NS₂: 393.2524; found:

393.2523.

HRMS (TOF): m/z calcd for C₂₁H₃₄S₂: 350.2102; found: 350.2104.

(Z)-2-{[1-(Octylthio)dec-1-en-2-yl]thio}thiophene (3cc)

Light yellow oil; yield: 185 mg (93%).

(Z)-Octyl[2-(phenylthio)dec-1-en-1-yl]sulfane (3x)

Light yellow oil; yield: 175 mg (89%).

¹H NMR (400 MHz, CDCl₃): d = 7.35 (d, J = 5.6 Hz, 1 H), 7.16 (d,

J = 3.2 Hz, 1 H), 6.97–6.95 (m, 1 H), 6.06 (s, 1 H), 2.72 (t, J = 7.4

Hz, 2 H), 2.11 (t, J = 7.4 Hz, 2 H), 1.69–1.58 (m, 2 H), 1.50–1.40

(m, 4 H), 1.29–1.23 (m, 18 H), 0.90–0.86 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 134.5, 133.9, 131.5, 129.7, 127.2,

126.1, 36.1, 34.3, 31.8, 31.7, 30.3, 29.2, 29.1, 28.7, 28.5, 28.4, 22.6,

14.0.

¹H NMR (400 MHz, CDCl₃): d = 7.31 (d, J = 7.6 Hz, 2 H), 7.26 (t,

J = 7.6 Hz, 2 H), 7.18 (t, J = 7.2 Hz, 1 H), 6.37 (s, 1 H), 2.73 (t,

J = 7.4 Hz, 2 H), 2.20 (t, J = 7.2 Hz, 2 H), 1.70–1.63 (m, 2 H), 1.49–

1.39 (m, 4 H), 1.29 (br m, 10 H), 1.23 (br m, 8 H), 0.91–0.87 (m, 6

H).

¹³C NMR (100 MHz, CDCl₃): d = 134.3, 132.0, 130.5, 129.7, 128.7,

126.1, 37.2, 34.0, 31.8, 31.7, 30.4, 29.2, 29.1, 28.8, 28.5, 28.4, 22.6,

14.0.

HRMS (TOF): m/z calcd for C₂₂H₃₈S₃: 398.2136; found: 398.2133.

(Z)-Octyl[2-(p-tolylthio)oct-1-en-1-yl]sulfane (3dd)

Light yellow oil; yield: 170 mg (90%).

HRMS (TOF): m/z calcd for C₂₄H₄₀S₂: 392.2571; found: 392.2584.

(Z)-Octyl[2-(o-tolylthio)dec-1-en-1-yl]sulfane (3y)

Light yellow oil; yield: 187 mg (92%).

¹H NMR (400 MHz, CDCl₃): d = 7.21 (d, J = 8.0 Hz, 2 H), 7.06 (d,

J = 7.6 Hz, 2 H), 6.26 (s, 1 H), 2.71 (t, J = 7.4 Hz, 2 H), 2.30 (s, 3

H), 2.15 (t, J = 7.6 Hz, 2 H), 1.69–1.61 (m, 2 H), 1.46–1.38 (m, 4

H), 1.28–1.19 (m, 14 H), 0.90–0.83 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.3, 131.5, 130.5, 130.2, 129.5,

37.0, 34.1, 31.7, 31.5, 30.4, 29.1, 28.6, 28.4, 22.6, 22.5, 21.0, 14.0,

13.9.

¹H NMR (400 MHz, CDCl₃): d = 7.28–7.25 (m, 1 H), 7.18–7.15 (m,

1 H), 7.14–7.09 (m, 2 H), 6.33 (s, 1 H), 2.73 (t, J = 7.4 Hz, 2 H),

2.39 (s, 3 H), 2.12 (t, J = 7.6 Hz, 2 H), 1.70–1.62 (m, 2 H), 1.47–

1.40 (m, 4 H), 1.30 (br m, 10 H), 1.22 (br m, 8 H), 0.92–0.87 (m, 6

H).

¹³C NMR (100 MHz, CDCl₃): d = 138.7, 133.0, 130.8, 130.5, 130.4,

130.2, 126.5, 126.1, 37.0, 34.1, 31.8, 31.7, 30.4, 29.2, 29.1, 28.7,

28.5, 28.4, 22.6, 20.3, 14.0.

HRMS (TOF): m/z calcd for C₂₃H₃₈S₂: 378.2415; found: 378.2421.

(Z)-[4-Methyl-1-(octylthio)pent-1-en-2-yl](p-tolyl)sulfane (3ee)

Light yellow oil; yield: 170 mg (97%).

HRMS (TOF): m/z calcd for C₂₅H₄₂S₂: 406.2728; found: 406.2727.

¹H NMR (400 MHz, CDCl₃): d = 7.23 (d, J = 8.0 Hz, 2 H), 7.08 (d,

J = 7.6 Hz, 2 H), 6.25 (s, 1 H), 2.73 (t, J = 7.2 Hz, 2 H), 2.31 (s, 3

H), 2.02 (d, J = 6.8 Hz, 2 H), 1.90–1.83 (m, 1 H), 1.70–1.63 (m, 2

H), 1.43–1.40 (m, 2 H), 1.29 (br m, 8 H), 0.89 (t, J = 6.6 Hz, 3 H),

0.83 (s, 3 H), 0.81 (s, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.3, 131.2, 130.6, 130.5, 130.4,

129.5, 46.2, 34.1, 31.7, 30.4, 29.1, 28.5, 26.8, 22.6, 22.0, 21.0, 14.0.

(Z)-(4-Methoxyphenyl)[1-(octylthio)dec-1-en-2-yl]sulfane (3z)

Light yellow oil; yield: 184 mg (87%).

¹H NMR (400 MHz, CDCl₃): d = 7.30 (d, J = 8.8 Hz, 2 H), 6.81 (d,

J = 8.4 Hz, 2 H), 6.15 (s, 1 H), 3.77 (s, 3 H), 2.71 (t, J = 7.2 Hz, 2

H), 2.09 (t, J = 7.4 Hz, 2 H), 1.69–1.62 (m, 2 H), 1.44–1.39 (m, 4

H), 1.28–1.18 (m, 18 H), 0.90–0.85 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 159.0, 133.4, 132.9, 127.7, 124.3,

114.3, 55.1, 36.5, 34.1, 31.8, 31.7, 30.3, 29.2, 29.1, 28.7, 28.6, 28.4,

22.6, 14.0.

HRMS (TOF): m/z calcd for C₂₁H₃₄S₂: 350.2102; found: 350.2109.

(Z)-[3-Methyl-1-(octylthio)but-1-en-2-yl](p-tolyl)sulfane (3ff)

Light yellow oil; yield: 159 mg (95%).

HRMS (TOF): m/z calcd for C₂₅H₄₂OS₂: 422.2677; found:

422.2678.

¹H NMR (400 MHz, CDCl₃): d = 7.19 (d, J = 8.4 Hz, 2 H), 7.08 (d,

J = 8.0 Hz, 2 H), 6.45 (s, 1 H), 2.74 (t, J = 7.2 Hz, 2 H), 2.49–2.44

(m, 1 H), 2.32 (s, 3 H), 1.70–1.63 (m, 2 H), 1.43–1.38 (m, 2 H), 1.30

(br m, 8 H), 1.13 (s, 3 H), 1.11 (s, 3 H), 0.91 (t, J = 6.8 Hz, 3 H).

(Z)-Naphthalen-2-yl[1-(octylthio)dec-1-en-2-yl]sulfane (3aa)

Light yellow oil; yield: 199 mg (90%).

¹H NMR (400 MHz, CDCl₃): d = 7.81–7.75 (m, 4 H), 7.49–7.41 (m,

3 H), 6.46 (s, 1 H), 2.78 (t, J = 7.2 Hz, 2 H), 2.27 (t, J = 7.4 Hz, 2

H), 1.74–1.67 (m, 2 H), 1.57–1.51 (m, 2 H), 1.46–1.42 (m, 2 H),

1.31–1.23 (m, 18 H), 0.94–0.87 (m, 6 H).

¹³C NMR (100 MHz, CDCl₃): d = 135.9, 135.6, 131.8, 131.5, 129.5,

128.9, 35.7, 34.0, 31.7, 30.4, 29.1, 28.6, 22.6, 22.1, 20.9, 14.0.

HRMS (TOF): m/z calcd for C₂₀H₃₂S₂: 336.1945; found: 336.1941.

Synthesis 2012, 44, 380–388

388

H. Xu et al.

PAPER

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(Z)-[3,3-Dimethyl-1-(octylthio)but-1-en-2-yl](p-tolyl)sulfane

(3gg)

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Light yellow oil; yield: 166 mg (95%).

(11) Cai, M. Z.; Wang, Y. G.; Hao, W. Y. Green Chem. 2007, 9,

¹H NMR (400 MHz, CDCl₃): d = 7.10 (d, J = 8.0 Hz, 2 H), 7.03 (d,

J = 8.0 Hz, 2 H), 6.71 (s, 1 H), 2.67 (t, J = 7.2 Hz, 2 H), 2.27 (s, 3

H), 1.64–1.57 (m, 2 H), 1.37–1.26 (m, 10 H), 1.18 (s, 9 H), 0.88 (t,

J = 6.6 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 136.8, 136.1, 134.4, 132.5, 129.4,

126.5, 39.7, 33.8, 31.7, 30.5, 29.4, 29.1, 29.0, 28.5, 22.6, 20.9, 14.0.

1180.

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Tetrahedron 2010, 66, 2823.

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Commun. 2009, 39, 2464.

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HRMS (TOF): m/z calcd for C₂₁H₃₄S₂: 350.2102; found: 350.2104.

(Z)-[2-Cyclohexyl-2-(p-tolylthio)ethenyl](octyl)sulfane (3hh)

Light yellow oil; yield: 175 mg (93%).

¹H NMR (400 MHz, CDCl₃): d = 7.16 (d, J = 8.0 Hz, 2 H), 7.06 (d,

J = 8.0 Hz, 2 H), 6.46 (s, 1 H), 2.71 (t, J = 7.4 Hz, 2 H), 2.30 (s, 3

H), 2.11–2.05 (m, 1 H), 1.89 (d, J = 11.6 Hz, 2 H), 1.73 (d, J = 9.2

Hz, 2 H), 1.68–1.61 (m, 3 H), 1.41–1.36 (m, 2 H), 1.32–1.15 (m, 13

H), 0.90 (t, J = 6.4 Hz, 3 H).

¹³C NMR (100 MHz, CDCl₃): d = 135.3, 134.7, 132.9, 131.7, 129.5,

128.4, 46.0, 33.9, 32.7, 31.7, 30.4, 29.1, 28.5, 26.4, 26.1, 22.6, 20.9,

14.0.

HRMS (TOF): m/z calcd for C₂₃H₃₆S₂: 376.2258; found: 376.2259.

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2002, 4, 2803.

Supporting Information for this article is available online at

http://www.thieme-connect.com/ejournals/toc/synthesis.

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12, 3930.

Acknowledgment

This project is supported by the Natural Science Foundation of Chi-

na (21072170).

(26) Zhao, Q. W.; Li, L.; Fang, Y. W.; Sun, D. Q.; Li, C. Z.

J. Org. Chem. 2009, 74, 459.

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Synthesis 2012, 44, 380–388

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