S1

Supporting Information

Highly Dispersed Ni2P Nanoparticles on N,P-codoped

Carbon for Efficient Cross-Dehydrogenative Coupling to

Access Alkynyl Thioethers

Tao Song,a Peng Ren,a,b Jianliang Xiao c Youzhu Yuand and Yong Yang* a

*Corresponding author

E-mail: yangyong@qibebt.ac.cn

Table Contents

1. General considerations ...........................................................................................................................................S2

2. Preparation of catalysts ..........................................................................................................................S3

3. Characterization results .........................................................................................................................S3

4. General procedure.....................................................................................................................................................S9

5. Catalytic studies ..........................................................................................................................................................S9

5.1 Recyclability of catalyst ............................................................................................................................................S9

5.2 Effect of removal of the Ni2P@NPC-800 catalyst during the reaction. .............................................S10

5.3 Poisoning experiment ................................................................................................................................................S10

5.4 Comparison of catalytic performance for this work with other previous reports for synthesis of

alkynyl thioethers via CDC strategy ...........................................................................................................................S11

6. Characterization of the products .................................................................................................................S11

7. 1H and 13C NMR spectra of products....................................................................................S21

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2020

S2

1. General considerations

Unless otherwise noted, all reagents were purchased commercially from Sigma-

Aldrich, or Aladdin and used as received without further purification. The fresh bamboo

shoots were obtained from Anhui Taiping Test Centre, International Centre for Bamboo

and Rattan, Anhui Province, China. All operations were carried out in an argon

atmosphere using glovebox and Schlenk techniques unless otherwise specified. The X-

ray diffraction (XRD) patterns of all the catalysts were obtained on a Bruker D8

Advance X-ray diffraction diffractometer equipped with Cu Ka radiation (λ= 1.5147

Å). The morphology of catalysts was examined by an H-7600 transmission electron

microscopy (TEM), a Tecnai G2 F30 high-resolution TEM (HRTEM) and a FEI Tecnai

G2 F20 scanning transmission electron microscopy (STEM). Nitrogen adsorption–

desorption data were obtained on a Micromeritics ASAP 2020 static volumetric

sorption analyzer. The specific surface area of the samples was calculated by the

Brunauer-Emmet-Teller (BET) method. The micropore volume was calculated by t-plot

method. The pore size distributions were determined by non-local density functional

theory (NLDFT). The X-ray photoelectron spectroscopy (XPS) data was collected on

an ESCALAB 250Xi (Thermo Scientific, UK) instrument equipped with a

monochromatized Al Ka line source. All the binding energies obtained were calibrated

based on the C 1s peak at 284.8 eV. The elemental composition analysis of the catalysts

was conducted on Vario El elemental analyzer. Ion Chromatography was conducted on

a Thermo Scientific Dionex ICS-5000 equipped with CS-12 column with

methanesulfonic acid (20 mM) as an eluent. Raman spectra were obtained on a Horiba

Jobin Yvon LabRAM HR800 Raman spectrometer system using a 532 nm wavelength

laser at room temperature. Inductively coupled plasma atomic emission spectroscopy

(ICP-AES) was conducted on a PerkinElmer Optima 5300 DV instrument. Gas

chromatography analysis was performed on an Agilent HP-7890 instrument with a

flame ionization detector (FID) and an HP-5MS capillary column (30 m, 0.25 mm i.d.,

0.25 μm film thicknesses) using helium as the carrier gas. Gas chromatography-mass

spectrometry analysis was carried out on an Agilent HP-7890 instrument with an

S3

Agilent HP-5975 with triple-axis detector and HP-5 capillary column using helium

carrier gas. NMR spectra were from a Bruker DRX-400, or DRX-600, instrument and

calibrated using residual non-deuterated solvent (CDCl3: δH = 7.26 ppm, δC = 77.16

ppm; DMSO-d6, δH = 2.50 ppm, δC = 39.60 ppm) as an internal reference. High-

resolution mass data were recorded on Bruke Maxis UHR TOF mass spectrometers in

ESI mode.

2. Preparation of catalysts

The hydrochars were firstly prepared by hydrothermal method using bamboo shoots as

raw material. The fresh bamboo shoots were cut into slices, dried and ground into a

powder. 2 g of the dried bamboo shoots were added to 20 mL of deionized water in a

100 mL Teflon-inner stainless steel autoclave, which was sealed and heated at 180 oC

for 5.5 h. The resulting solids were obtained by filtration, washed thoroughly using

distilled water to remove any soluble metals, and dried by vacuum freeze-drying. After

that, 1 g of the obtained hydrochars were mixed with 20 mL of Ni(OAc)2 aqueous

solution (0.4 mmol Ni) and 120 μL phytic acid (PA, 1.1 mol/L), the suspension was

stirred at 60 oC for 2 h and then dried at 100 oC for 10 h to remove water. Afterward,

the solids were grinded to fine powders and heated to 700, 800 or 900 oC at a rate of 5

oC/min and maintained at this temperature for 2 h under N2 atmosphere. The obtained

catalyst was named as Ni2P@NPC-T, where T represents the calcination temperature.

For comparison, the catalysts Ni@NC-800 without addition of PA and Ni@NPC-800-

X (X represent the amount of PA) with addition of different amount of PA were

prepared in the same procedure.

3. Characterization results

S4

Figure S1. (a) HAADF STEM image, and (b-f) EDX mapping of C, N, P, and Ni of

Ni2P@NPC-800.

1000 2000 3000

Inte

nsity

/ a.

u.

Raman shift (cm-1)

Ni2P@NPC-700 Ni2P@NPC-800 Ni2P@NPC-900

D G

IG/ID

1.01

1.02

1.05

Figure S2. Raman spectra of the catalysts Ni2P@NPC-700, Ni2P@NPC-800, and

Ni2P@NPC-900.

S5

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00

20

40

60

80

100

120

1 10 100

0.000

0.002

0.004

0.006

0.008

Incr

emen

tal v

olum

e(cm

3 /g)

Pore size (nm)

Ni2P@NCP-700 Ni2P@NCP-800 Ni2P@NCP-900

Relative pressure P/P0

Ads

orbe

d vo

lum

e (c

m3 /g

, STP

)

Figure S3. N2 sorption isotherms and pore size distribution calculated using a nonlocal density function theory (NLDFT) method for the catalysts Ni2P@NPC-700, Ni2P@NPC-800, and Ni2P@NPC-900.

10 30 50 7020 40 60 80

Ni2P@NPC-700 Ni2P@NPC-800 Ni2P@NPC-900

Inte

nsity

/ a

.u.

2 / degree

Ni2P PDF-# 03-0953

Figure S4. XRD patterns of Ni2P@NPC-700, Ni2P@NPC-800, and Ni2P@NPC-900.

S6

10 30 50 7020 40 60 80

Ni/NC-800-0 mL

Ni PDF-# 04-0850

Inte

nsity

/ a.

u.

Ni/NPC-800-6 0 L

Ni12P5 PDF-# 22-1190

2 / degree

Ni/NPC-800-240 L Ni/NPC-800-2 mL

Ni2P PDF-# 03-0953

Figure S5. XRD patterns of the catalysts with different amount of phytic acid under 800oC

S7

Figure S6. Ni 2p, P 2p, N 1s, C 1s XPS spectra of the catalysts Ni2P@NPC-700, Ni2P@NPC-800, Ni2P@NPC-900.

S8

Table S1. Chemical composition and texture properties of the catalyst Ni/NCP-T.Elemental analysis

BET analysisSample Nia content (wt%)

Pa

content (wt%)C(wt%) N(wt%) SBET

b

(m2 g−1)Pore volume

(cm3 g−1)

Catalyst yield(wt%)

Content of Ni2P in catalyst

(wt%)c

Ni/NC-800 4.27 0 84.20 3.72 155.5 0.121 22.2 -

Ni2P/NPC-700-120μL 3.05 3.52 75.48 5.01 106.9 0.089 24.0 -

Ni2P /NPC-800-120μL 4.58 2.50 75.50 5.01 51.3 0.040 22.7 3.15

Ni2P /NPC-900-120 μL 4.96 2.30 76.44 3.36 81.9 0.065 18.5 3.23

Ni/NPC-800-60μL 4.98 1.41 80.56 5.17 - - - -

Ni/NPC-800-240μL 3.24 4.25 68.32 3.96 - - - -

Ni/NPC-800-2 mL 1.99 8.94 59.96 3.24 - - - -

aDetermined by ICP-OES. bSpecific surface areas were determined by the BET multipoint method. cDetermined by XPS.

S9

4. General procedure for synthesis of alkynyl thioethers.

A 25 mL sealing tube was charged with a magnetic stirring bar, alkyne (0.2 mmol) ,

thiol (0.3 mmol), Ni2P@NPC-800 (20 mg, 8 mol% of Ni), 2 mL DMF. The reaction

was stirred for 4 h at 50°C under atmospheric air. After completion of the reaction, the

reaction mixture was cooled to room temperature and the conversion and selectivity

was analyzed by GC-MS. The products were purified by column chromatography and

structurally confirmed by NMR.

5. Catalytic studies

5.1. Recyclability of catalyst

The synthesis of alkynyl thioethers was chosen as the model reaction to investigate the

recyclability of the catalyst Ni2P@NPC-800. A 25 mL sealing tube was charged with a

magnetic stirring bar, phenylacetylene (0.2 mmol), para-chlorobenzenethiol (0.3

mmol), Ni2P@NPC-800 (20 mg, 8 mol% of Ni), 2 mL DMF. The reaction was stirred

for 4 h at 50 °C under atmospheric air. After completion of the reaction, the reaction

mixture was cooled to room temperature and the conversion and selectivity was

analyzed by GC-MS. The residue was dispersed in 5 mL of ethanol and the resulting

mixture was stirred for 10 min, the catalyst were separated by centrifuge. Such

operation was repeated for 3 times. Finally, the obtained black solid was dried under

vacuum at 40oC overnight for successive use.

Ni2P@NPC-800(8 mol%)

DMF, 50oC, 4 h, Air+

SH

Cl

S

Cl

2a1a 3a

S10

1 2 3 4 5 60

20

40

60

80

100

0

20

40

60

80

100

Sele

ctiv

ity / %

Recycle Number

Conversion (%) Selectivity (%)

Con

vers

ion

/ %

Figure S7. Recyclability of the catalyst Ni2P@NPC-800 for the synthesis of alkynyl

thioethers via CDC strategy.

5.2 Effect of removal of the Ni2P@NPC-800 catalyst during the reaction.Ni2P@NPC-800

(8 mol%)

DMF, 50oC, 4 h, Air+

SH

Cl

S

Cl

2a1a 3a

0 1 2 3 40

20

40

60

80

100

Time / h

yie

ld /

%

Hot filtration

Figure S8. Effect of removal of the Ni2P@NPC-800 catalyst during the reaction. (○)

after removal of Ni2P@NPC-800 and (●) without removal of Ni2P@NPC-800. The

arrow indicates the time when the Ni2P@NPC-800 catalyst was removed from the reaction mixture.

5.3 Poisoning experiment.

S11

SH

Cl+ Ni2P@NPC-800

DMF, 50oC, 4h, Air1 eq. H3PO4

S

Cl

0 % yield1a 5a

(1.5 eq.)

2a

0% conversion

A 25 mL sealing tube was charged with a magnetic stirring bar, Ni2P@NPC-800 (20

mg, 8 mol% of Ni), H3PO4 (0.2 mmol), 2 mL DMF, the mixture was stirred 1h. Then

phenylacetylene (0.2 mmol), para-chlorobenzenethiol (0.3 mmol) were added, the

reaction was stirred for 4 h at 50 °C under atmospheric air.

5.4 Comparison of catalytic performance for this work with other previous reports

for synthesis of alkynyl thioethers via CDC strategy.

Table S2. Comparison of catalytic performance for this work with other previous

reports for synthesis of alkynyl thioethers via CDC strategy.Catalyst Reaction condition Substrate scopes Yield Ref.

S ArAr 81%

S AlkylAr 64%

S ArAlkyl 79-86%

RhH(PPh3)4 + dppf

terminal alkyne (0.25 mmol), disulfide (0.75 mmol), RhH(PPh3)4 (2 mol%), dppf (2-4 mol%), acetone (0.5 mL), Ar atmosphere, reflux for 1 h.

S AlkylAlkyl 54-86%

[9a]

S ArAr 76-95%

S AlkylAr -

S ArAlkyl 74-90%

MCM-41-2N-CuCl

Complexes

terminal alkyne (0.5 mmol), thiol (0.55 mmol), MCM-41-2N-CuCl (5 mol%), K2CO3 (10 mol%), DMSO (2 mL), 70 oC, 1 atm O2, 1 h. (The heterogeneous catalyst can be recycled 10 times without any decreases in activity) S AlkylAlkyl -

[9b]

S ArAr 14-97%

S AlkylAr 58-71%

S ArAlkyl 91-93%

CuCl

terminal alkyne (0.5 mmol), thiol (0.55 mmol), CuCl (5 mol%), K2CO3 (10 mol%), DMSO (2 mL), 70 °C,1 atm O2, 1 h.

S AlkylAlkyl 34%

[9c]

S12

S ArAr -

S AlkylAr -

S ArAlkyl 30-92%

CuI

terminal alkyne (0.25 mmol), disulfide (0.125 mmol), CuI (4 mol%), K2CO3 (0.5 mmol), DMSO (2 mL), 70°C, 1 atm O2, 1 h.

S AlkylAlkyl -

[9d]

S ArAr 71-93%

S AlkylAr 61-67%

S ArAlkyl 72%-82%

Ni2P@NPC-800

terminal alkyne (0.2 mmol), thiol (0.3 mmol), Ni2P@NPC-800 (8 mol% of Ni), DMF (2 mL), air atmosphere, 50oC, 4h

S AlkylAlkyl 52-57%

This work

6. Characterization of products

S

Cl

(4-chlorophenyl)(phenylethynyl)sulfane (2a), yellow solid; 1H NMR (600 MHz,

CDCl3): δ 7.53-7.49 (m, 2H), 7.41 (d, J = 8.6 Hz, 3H), 7.37-7.30 (m, 5H). 13C NMR

(151 MHz, CDCl3): δ 132.5, 131.8, 131.6, 129.4, 128.9, 128.5, 127.5, 122.6, 98.4, 74.8.

HRMS: calcd. for C14H9ClS [M], 244.0013; found,244.0115.

S

ClF

(4-chlorophenyl)((4-fluorophenyl)ethynyl)sulfane (2b), yellow oil; 1H NMR (600

MHz, CDCl3) δ 7.52-7.48 (m, 2H), 7.41-7.37 (m, 2H), 7.34-7.30 (m, 2H), 7.07-7.02

(m, 2H). 13C NMR (151 MHz, CDCl3): δ 162.89 (d, J = 250.8 Hz), 134.01 (d, J = 8.6

Hz), 132.6, 131.4, 129.4, 127.6, 118.73 (d, J = 3.6 Hz), 115.83 (d, J = 22.2 Hz), 97.2,

74.6. HRMS: calcd. for C14H18ClFS [M], 262.0019; found,262.0023.

S13

S

Cl

Cl

(4-chlorophenyl)((3-chlorophenyl)ethynyl)sulfane (2c), yellow oil; 1H NMR (600

MHz, CDCl3): δ 7.69 (s, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.43-7.38 (m, 3H), 7.34 (d, J =

8.6 Hz, 2H), 7.21 (t, J = 8.0 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 134.3, 132.8,

131.9, 130.9, 130.2, 129.9, 129.5, 127.7, 124.6, 122.3, 96.6. HRMS: calcd. for

C14H18Cl2S [M], 277.9724; found,277.9717.

S

Cl

Br

((3-bromophenyl)ethynyl)(4-chlorophenyl)sulfane (2d), yellow oil; 1H NMR (600

MHz, CDCl3): δ 7.67 (s, 1H), 7.52 (d, J = 8.1 Hz, 1H), 7.47-7.41 (m, 3H), 7.37 (d, J =

8.6 Hz, 2H), 7.25 (t, J = 7.9 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 134.4, 132.9,

131.9, 131.1, 130.2, 129.9, 129.6, 127.8, 124.7, 122.3. 96.7. HRMS: calcd. for

C14H18BrClS [M], 321.9219; found, 321.9221.

S

Cl

(4-chlorophenyl)(p-tolylethynyl)sulfane (2e), White solid; 1H NMR (600 MHz,

CDCl3): δ 7.44 (dt, J = 4.6, 4.0 Hz, 4H), 7.37-7.33 (m, 2H), 7.19 (d, J = 7.9 Hz, 2H),

2.41 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 139.3, 132.4, 131.9, 131.8, 129.4, 129.3,

127.4, 119.7, 119.5, 98.67, 73.8, 21.6. HRMS: calcd. for C15H11ClS [M], 258.0270;

found, 258.0271.

S14

S

Cl

(4-chlorophenyl)(o-tolylethynyl)sulfane (2f), Colorless oil; 1H NMR (400 MHz,

CDCl3): δ 7.46 (d, J = 7.6 Hz, 1H), 7.44-7.40 (m, 2H), 7.34-7.29 (m, 2H), 7.24 (ddd, J

= 17.1, 10.3, 3.8 Hz, 2H), 7.19-7.14 (m, 1H), 2.47 (s, 3H). 13C NMR (151 MHz, CDCl3):

δ 140.5, 132.5 132.2, 131.9, 129.6, 129.4, 128.9, 127.4, 125.7, 122.5, 97.4, 78.2, 20. 9.

HRMS: calcd. for C15H11ClS [M], 258.0270; found, 258.0273.

S

ClMeO

(4-chlorophenyl)((4-methoxyphenyl)ethynyl)sulfane (2g), colorless oil; 1H NMR

(600 MHz, CDCl3): δ 7.49-7.40 (m, 2H), 7.41-7.33 (m, 2H), 7.33-7.19 (m, 2H), 6.92-

6.78 (m, 2H), 3.79 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 160.3, 133.9, 132.3, 132.1,

129.4, 127.3, 114.7, 114.1, 98.6, 72.9, 55.4. HRMS: calcd. for C15H11ClOS [M],

274.0219; found, 274.0216.

S

Cl

OMe

(4-chlorophenyl)((3-methoxyphenyl)ethynyl)sulfane (2h), colorless oil; 1H NMR

(400 MHz, CDCl3): δ 7.47-7.36 (m, 2H), 7.34-7.26 (m, 2H), 7.29-7.21 (m, 1H), 7.14-

7.07 (m, 1H), 7.02 (dd, J = 2.3, 1.5 Hz, 1H), 6.97-6.85 (m, 1H), 3.80 (s, 3H). 13C NMR

(151 MHz, CDCl3): δ 159.4, 132.6, 131.5, 129.6, 129.4, 127.5, 124.4, 123.6, 116.6,

115.5, 98.4, 55.4. HRMS: calcd. for C15H11ClOS [M], 274.0219; found, 274.0219.

S

ClOMe

S15

(4-chlorophenyl)((2-methoxyphenyl)ethynyl)sulfane (2i), yellow oil; 1H NMR (400

MHz, CDCl3): δ 7.57-7.39 (m, 3H), 7.35-7.26 (m, 3H), 6.91 (ddd, J = 16.9, 11.8, 4.5

Hz, 2H), 3.89 (s, J = 3.0 Hz, 3H).. 13C NMR (151 MHz, CDCl3): δ 160.3, 133.3, 132.2,

132.0, 130.3, 129.3, 127.3, 120.6, 111.9, 110.7, 95.3, 78.4, 55.8. HRMS: calcd. for

C15H11ClOS [M], 274.0219; found, 274.02120.

S

ClN

4-(((4-chlorophenyl)thio)ethynyl)-N,N-dimethylaniline (2j), yellow oil; 1H NMR

(600 MHz, CDCl3): δ 7.45-7.35 (m, 4H), 7.31-7.26 (m, 2H), 6.66-6.62 (m, 2H), 3.00

(s, 3H). 13C NMR (151 MHz, CDCl3): δ 150.7, 133.9, 132.9, 131.9, 129.2, 127.1, 111.7,

108.9, 100.1, 71.3, 40.2. HRMS: calcd. for C16H14ClNS [M], 287.0535; found,

287.0536.

S

Cl

NH2

3-(((4-chlorophenyl)thio)ethynyl)aniline (2k), colorless solid; 1H NMR (600 MHz,

CDCl3): δ 7.52-7.35 (m, 2H), 7.35-7.27 (m, 2H), 7.11 (t, J = 7.8 Hz, 1H), 6.90 (d, J =

7.6 Hz, 1H), 6.70-6.61 (m, 1H), 3.69 (s, 2H). 13C NMR (151 MHz, CDCl3): δ 146.4,

132.4, 131.7, 129.4, 129.3, 127.4, 123.3, 122.2, 117.8, 115.9, 98.8, 74.0. HRMS: calcd.

for C14H10ClNS [M], 259.0222, 259.0224.

S

ClF3C

2-(thiophen-3-yl)quinazoline (2l), colorless oil; 1H NMR (600 MHz, CDCl3): δ 7.58

(q, J = 8.5 Hz, 4H), 7.40 (t, J = 8.9 Hz, 2H), 7.33 (d, J = 8.6 Hz, 2H). 13C NMR (151

MHz, CDCl3): δ 133.0, 131.6, 130.7, 130.27 (d, J = 32.8 Hz), 129. 6, 129.3, 127.8,

S16

125.40 (q, J = 3.8 Hz), 123.84 (d, J = 272.3 Hz), 96.8, 78.4. HRMS: calcd. for

C15H8ClF3S [M], 311.9987; found, 311.9989.

S

ClMeO2C

methyl 4-(((4-chlorophenyl)thio)ethynyl)benzoate (2m), White solid; 1H NMR (600

MHz, CDCl3): δ 8.01 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.6 Hz,

2H), 7.35 (d, J = 8.6 Hz, 2H), 3.93 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 166.4,

132.9, 131.2, 130.8, 129.8, 129.6, 129.6, 127.8, 127.3 98.9, 78.8, 52.3. HRMS: calcd.

for C16H11ClO2S [M], 302.0168; found,302.0169.

N

S

Cl

3-(((4-chlorophenyl)thio)ethynyl)pyridine (2n), yellow solid; 1H NMR (600 MHz,

CDCl3): δ 8.73 (d, J = 1.5 Hz, 1H), 8.56 (dd, J = 4.9, 1.6 Hz, 1H), 7.77 (dt, J = 7.9, 1.9

Hz, 1H), 7.45-7.39 (m, 2H), 7.37-7.32 (m, 2H), 7.31-7.24 (m, 1H). 13C NMR (151 MHz,

CDCl3): δ 152.3, 149.0, 138.6, 133.0, 130.7, 129.6, 127.8, 123.1, 119.9, 94.7, 79.1.

HRMS: calcd. for C13H8ClNS [M], 245.0066; found,245.0067.

S

ClS

2-(((4-chlorophenyl)thio)ethynyl)thiophene (2o), yellow solid; 1H NMR (600 MHz,

CDCl3): δ 7.40-7.27 (m, 6H), 7.00 (dd, J = 5.0, 3.8 Hz, 1H). 13C NMR (151 MHz,

CDCl3): δ 134.2, 132.7, 131.5, 129.4, 129.0, 127.6, 127.2, 122.7, 91.2, 76.9. HRMS:

calcd. for C12H7ClS2 [M], 249.9678; found, 249.9676.

S17

S

F

(4-fluorophenyl)(phenylethynyl)sulfane (2p), White solid; 1H NMR (400 MHz,

CDCl3): δ 7.45-7.34 (m, 4H), 7.29-7.22 (m, 3H), 7.02-6.94 (m, 2H). 13C NMR (101

MHz, CDCl3): δ 161.90 (d, J = 246.5 Hz), 131.8, 128.8, 128.5, 128.5, 128.4, 127.90 (d,

J = 3.3 Hz), 122.8, 116.50 (d, J = 22.4 Hz), 97.6, 75.7. HRMS: calcd. for C14H9FS [M],

228.0409; found, 228.0410.

S

naphthalen-2-yl(phenylethynyl)sulfane (2q), white solid; 1H NMR (400 MHz,

CDCl3):δ 7.95 (d, J = 1.4 Hz, 1H), 7.86-7.77 (m, 3H), 7.58-7.53 (m, 3H), 7.53-7.44 (m,

2H), 7.40-7.34 (m, 3H). 13C (101 MHz, CDCl3): δ 132.1, 131.8, 130.3, 129.0, 128.7,

128.5, 127.8, 127.2, 126.9, 126.0, 124.6, 124.2. HRMS: calcd. for C18H12S [M],

260.0660; found, 260.0667.

S

hex-1-yn-1-yl(phenyl)sulfane (2r), colorless oil; 1H NMR (600 MHz, CDCl3): δ 7.50-

6.92 (m, 4H), 2.45 (t, J = 7.1 Hz, 2H), 1.72-1.51 (m, 2H), 1.50-1.32 (m, 2H), 0.94 (t, J

= 7.3 Hz, 3H). 13C NMR (151 MHz, CDCl3): δ 132.5, 131.9, 129.2, 127.0, 100.7, 64.0,

30.7, 22.0, 20.01, 13.6. HRMS: calcd. for C12H14S [M], 190.0816; found,190.0818.

SOH

8-(phenylthio)oct-7-yn-1-ol (2s), colorless oil; 1H NMR (600 MHz, CDCl3): δ 7.34-

7.25 (m, 4H), 3.63 (t, J = 6.6 Hz, 2H), 2.45 (t, J = 7.1 Hz, 2H), 1.59 (ddd, J = 15.0,

10.8, 7.5 Hz, 4H), 1.49-1.37 (m, 4H). 13C NMR (151 MHz, CDCl3) δ 132.4, 131.9,

S18

129.2, 127.0, 100.6, 64.2, 62.7, 40.8, 32.6, 28.7, 28.5, 25.3, 20.2. HRMS: calcd. for

C14H18OS [M], 234.1078; found, 234.1079.

SOH

1-((phenylthio)ethynyl)cyclohexan-1-ol (2t), colorless oil; 1H NMR (600 MHz,

CDCl3): δ 7.36-7.28 (m, 4H), 2.07-1.91 (m, 2H), 1.73 (dt, J = 11.8, 8.3 Hz, 2H), 1.70-

1.62 (m, 4H), 1.61-1.52 (m, 4H). 13C NMR (151 MHz, CDCl3): δ 132.5, 131.4, 129.4,

127.3, 39.8, 34.7, 25.3, 25.1, 23.3, 21.5. HRMS: calcd. for C14H16OS [M], 232.0922;

found, 232.0924.

S

(cyclohex-1-en-1-ylethynyl)(phenyl)sulfane (2u), colorless oil; 1H NMR (600 MHz,

CDCl3) δ 7.38-7.27 (m, 4H), 6.23 (td, J = 4.0, 2.0 Hz, 1H), 2.19 (tt, J = 6.2, 2.3 Hz,

2H), 2.16-2.12 (m, 2H), 1.70-1.64 (m, 2H), 1.63-1.58 (m, 2H). 13C NMR (151 MHz,

CDCl3): δ 136.7, 132.3, 132.1, 129.3, 127.1, 120.6, 100.6, 71.3, 29.1, 25.8, 22.2, 21.4.

HRMS: calcd. for C14H14S [M], 214.0816; found, 214.0811.

S

Cl

(4-chlorophenyl)(cyclohexylethynyl)sulfane (2v), colorless oil; 1H NMR (600 MHz,

CDCl3): δ 7.30 (dd, J = 25.2, 8.6 Hz, 4H), 2.67-2.58 (m, 1H), 1.87 (d, J = 7.0 Hz, 2H),

1.76-1.71 (m, 2H), 1.54 (dd, J = 11.1, 8.2 Hz, 3H), 1.34 (s, 3H). 13C NMR (151 MHz,

CDCl3) δ 132.6, 131.9, 129.2, 126.9, 104.7, 64.1, 32.6, 30.6, 25.8, 24.8. HRMS: calcd.

for C14H15ClS [M], 250.0583; found, 250.0588.

S19

S

hexyl(phenylethynyl)sulfane (2w), colorless oil; 1H NMR (400 MHz, CDCl3): δ 7.44-

7.35 (m, 2H), 7.31-7.23 (m, 3H), 2.84-2.73 (m, 2H), 1.79 (dt, J = 14.9, 7.4 Hz, 2H),

1.49-1.38 (m, 2H), 1.37-1.23 (m, 4H), 0.89 (dd, J = 8.8, 5.2 Hz, 4H). 13C NMR (101

MHz, CDCl3): δ 131.4, 128.3, 127.9, 123.6, 92.9, 79.7, 35.8, 31.3, 29.4, 28.0, 22.5,

14.1. HRMS: calcd. for C14H18S [M], 218.1129; found, 218.1131.

S

cyclohexyl(phenylethynyl)sulfane (2x), colorless oil; 1H NMR (400 MHz, CDCl3): δ

7.41 (dd, J = 6.5, 3.2 Hz, 2H), 7.35-7.23 (m, 3H), 3.00 (tt, J = 10.9, 3.8 Hz, 1H), 2.19-

2.00 (m, 2H), 1.89-1.76 (m, 2H), 1.63 (ddd, J = 11.9, 7.6, 3.7 Hz, 1H), 1.57 (d, J = 3.5

Hz, 1H), 1.43-1.32 (m, 2H), 1.27 (ddd, J = 11.5, 8.3, 3.1 Hz, 2H). 13C NMR (101 MHz,

CDCl3): δ 131.4, 128.3, 127.9, 123.7, 94.4, 78.6, 47.7, 33.0, 26.1, 25.5. HRMS: calcd.

for C14H16S [M], 216.0973; found, 216.0977.

S

hex-1-yn-1-yl(hexyl)sulfane (2y), colorless oil; 1H NMR (400 MHz, CDCl3) δ 2.75-

2.58 (m, 2H), 2.30 (t, J = 6.9 Hz, 2H), 1.71 (dt, J = 14.8, 7.3 Hz, 2H), 1.54-1.46 (m,

2H), 1.45-1.36 (m, 2H), 1.36-1.28 (m, 4H), 0.96-0.84 (m, 4H). 13C NMR (101 MHz,

CDCl3): δ 94.2, 68.3, 35.5, 31.4, 30.9, 29.2, 27.9, 22.5, 21.9, 19.8, 14.0, 13.6. HRMS:

calcd. for C12H22S [M], 198.1442; found, 198.1447.

S

(cyclohex-1-en-1-ylethynyl)(cyclohexyl)sulfane (2z), colorless oil; 1H NMR (400

S20

MHz, CDCl3): δ 6.07-5.92 (m, 1H), 2.82 (tt, J = 10.8, 3.7 Hz, 1H), 2.05-1.97 (m, 4H),

1.77-1.67 (m, 4H), 1.57-1.51 (m, 4H), 1.46-1.36 (m, 2H), 1.26 -1.21 (m, 4H). 13C NMR

(101 MHz, CDCl3): δ 134.3, 121.1, 96.3, 74.6, 32.91, 32.87, 29.3, 26.1, 25.7, 25.5, 22.3,

21.5. HRMS: calcd. for C14H20S [M], 220.1286; found, 220.1286.

S21

7. 1H and 13C NMR spectra of products

-4-3-2-10123456789101112131415

f1(ppm)

4.79

2.07

2.31

7.25

7.31

7.32

7.32

7.33

7.34

7.34

7.34

7.35

7.35

7.35

7.36

7.40

7.42

7.43

7.45

7.50

7.50

7.50

7.51

7.51

S

Cl

0102030405060708090100110120130140150160170180190200210f1(ppm)

74.6

5

98.3

2

122.6

112

7.49

128.4

712

8.89

129.4

112

9.80

131.60

131.84

132.5

3

S

Cl

S22

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.03

1.06

1.00

1.01

1.25

1.26

1.34

1.57

2.61

7.02

7.03

7.03

7.04

7.05

7.06

7.06

7.26

7.28

7.29

7.31

7.31

7.32

7.32

7.33

7.33

7.38

7.39

7.39

7.40

7.40

7.41

7.49

S

Cl

F

0102030405060708090100110120130140150160170180190200210f1(ppm)

74.6

2

97.1

8

115.75

115.90

118.75

127.5

512

9.43

131.44

132.6

213

3.98

162.0

616

3.72

S

Cl

F

S23

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.23

2.13

3.34

1.08

1.00

7.20

7.21

7.23

7.26

7.33

7.34

7.39

7.41

7.42

7.48

7.49

7.64

S

Cl

Cl

0102030405060708090100110120130140150160170180190200210f1(ppm)

96.6

4

122.2

612

4.61

127.7

312

9.52

129.9

013

0.17

130.9

913

1.92

132.8

513

4.32

S

Cl

Cl

S24

-4-3-2-1012345678910111213141516f1(ppm)

1.23

2.13

3.34

1.08

1.00

7.23

7.25

7.26

7.29

7.36

7.38

7.42

7.44

7.45

7.51

7.52

7.67

S

Cl

Br

-100102030405060708090100110120130140150160170180190200210f1(ppm)

76.8

877

.10

77.3

1

96.7

0

122.3

212

4.67

127.7

912

9.58

129.9

613

0.23

131.05

131.98

132.9

113

4.38

S

Cl

Br

S25

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.63

1.00

0.97

1.98

2.41

7.19

7.20

7.34

7.35

7.35

7.36

7.43

7.43

7.44

7.44

7.45

7.46

S

Cl

CH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

21.6

0

73.8

076

.85

77.0

677

.27

98.6

6

119.56

127.3

9

139.2

9

S

Cl

CH3

S26

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

3.00

0.96

2.00

1.84

1.83

0.95

2.47

7.15

7.15

7.16

7.17

7.17

7.21

7.23

7.24

7.24

7.24

7.25

7.26

7.26

7.30

7.31

7.31

7.32

7.32

7.33

7.41

7.41

7.41

7.42

S

Cl

CH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

20.8

7

76.8

577

.06

77.2

778

.22

97.4

4

122.5

112

5.72

127.4

012

8.88

129.4

0

140.5

2

S

Cl

CH3

S27

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.00

0.64

0.63

0.61

0.62

3.79

6.84

6.84

6.85

6.85

7.27

7.27

7.28

7.28

7.36

7.36

7.36

7.37

7.37

7.44

7.44

7.46

S

Cl

O

CH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

55.3

7

72.9

576

.93

77.1

477

.35

98.6

0

114.14

114.67

127.3

212

9.36

132.1

413

2.32

133.9

2

160.3

1

S

Cl

O

CH3

S28

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

3.00

0.92

0.90

0.92

1.04

1.92

1.84

3.80

6.90

6.90

6.90

6.91

6.92

6.92

7.01

7.02

7.02

7.02

7.09

7.10

7.10

7.23

7.24

7.26

7.30

7.30

7.31

7.31

7.39

S

Cl

OCH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

55.3

5

74.7

176

.86

77.0

877

.29

98.3

5

115.49

116.58

123.5

912

4.38

127.5

312

9.43

129.5

6

159.4

0

S

Cl

OCH3

S29

2.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8f1(ppm)

3.00

1.89

2.74

2.70

3.88

3.89

6.88

6.89

6.90

6.91

6.92

6.92

6.93

6.93

7.29

7.29

7.30

7.30

7.31

7.31

7.32

7.32

7.43

7.45

S

Cl

OCH3

-100102030405060708090100110120130140150160170180190200210f1(ppm)

55.8

2

76.8

977

.10

77.3

178

.41

95.3

4

110.69

111.98

120.5

512

7.25

129.3

013

0.25

133.2

8

160.2

9

S

Cl

OCH3

S30

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

6.04

2.19

2.00

4.03

3.00

6.63

6.63

6.64

6.64

7.25

7.28

7.28

7.29

7.29

7.38

7.38

7.39

7.40

7.41

7.41

7.42

S

Cl

NCH3

CH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

40.1

6

71.34

76.8

477

.05

77.2

6

100.1

3

108.9

711

1.65

127.0

512

9.22

131.97

132.9

313

3.91

150.7

2

S

Cl

NCH3

CH3

S31

2.63.03.43.84.24.65.05.45.86.26.67.07.47.88.28.69.0f1(ppm)

2.23

1.00

1.13

1.21

1.98

2.04

3.69

6.65

6.65

6.66

6.67

6.67

6.67

6.80

6.80

6.80

6.90

6.91

7.10

7.11

7.13

7.24

7.29

7.30

7.30

7.31

7.31

7.32

7.37

7.38

7.39

S

Cl

NH2

-100102030405060708090100110120130140150160170180190200210f1(ppm)

74.0

276

.88

77.0

977

.30

98.8

2

115.92

117.86

122.2

112

3.28

127.4

312

9.39

146.4

0

S

Cl

NH2

S32

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.00

1.22

2.04

7.33

7.34

7.38

7.40

7.41

7.56

7.57

7.58

7.60

S

ClF

FF

0102030405060708090100110120130140150160170180190200210f1(ppm)

77.2

578

.38

96.8

6

122.9

412

4.74

125.3

612

5.39

125.4

112

5.44

127.8

412

9.32

129.3

312

9.56

130.1

613

0.38

130.7

213

1.62

133.0

0

S

ClF

FF

S33

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.00

0.60

0.60

0.63

0.64

3.93

7.26

7.34

7.36

7.41

7.43

7.53

7.54

8.01

8.02 S

Cl

O

OCH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

52.3

2

78.8

1

127.2

512

7.82

129.5

512

9.62

129.7

813

0.85

131.22

132.9

5

166.4

3

S

Cl

O

OCH3

S34

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.20

2.04

2.01

1.02

1.03

1.00

7.27

7.27

7.28

7.28

7.29

7.29

7.29

7.33

7.33

7.34

7.34

7.35

7.35

7.40

7.40

7.41

7.41

7.42

7.42

7.76

7.78

8.56

8.56

8.57

8.57

8.73

8.73

N

S

Cl

0102030405060708090100110120130140150160170180190200210f1(ppm)

76.8

577

.06

77.2

779

.16

94.7

3

119.93

123.1

112

7.87

129.5

613

0.69

133.0

013

8.56

149.0

015

2.30

N

S

Cl

S35

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.00

6.42

7.00

7.00

7.01

7.01

7.29

7.30

7.31

7.33

7.33

7.34

7.36

7.37

7.38

S

ClS

0102030405060708090100110120130140150160170180190200210f1(ppm)

76.8

877

.09

77.3

079

.36

91.2

4

122.7

012

7.21

127.5

912

9.02

129.4

613

1.52

132.7

113

4.15

S

ClS

S36

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

1.00

1.57

2.02

6.95

6.96

6.97

6.98

6.98

6.98

6.99

6.99

7.00

7.01

7.01

7.17

7.24

7.24

7.25

7.25

7.26

7.26

7.27

7.27

7.28

7.35

7.36

7.36

7.37

7.38

7.38

7.39

7.39

7.40

7.41

7.41

7.41

7.42

7.43

7.44

7.44

S

F

0102030405060708090100110120130140150160170180190200210f1(ppm)

75.6

876

.73

77.0

577

.37

97.5

7

116.39

116.61

122.7

712

7.88

128.3

912

8.47

132.5

3

160.6

716

3.12

S

F

S37

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

2.83

2.46

2.80

3.26

1.00

7.26

7.36

7.37

7.38

7.44

7.44

7.46

7.46

7.48

7.48

7.48

7.50

7.50

7.52

7.52

7.54

7.54

7.55

7.55

7.56

7.56

7.57

7.78

7.80

7.81

7.82

7.83

7.84

7.95

7.95

S

0102030405060708090100110120130140150160170180190200210f1(ppm)

75.5

0

98.0

4

122.9

212

4.18

124.6

112

6.01

126.8

912

7.17

127.8

612

8.46

128.7

312

9.02

130.2

613

1.83

132.0

613

3.78

S

S38

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

2.79

1.93

1.90

1.86

4.00

0.93

0.94

0.95

1.25

1.46

1.56

1.58

2.44

2.45

2.46

7.26

7.28

7.29

7.29

7.32

7.33

7.34

SCH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

13.5

8

20.0

1

30.6

7

64.0

4

100.7

2

127.0

212

9.18

131.97

132.4

7

SCH3

S39

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

3.90

3.57

1.95

2.11

3.78

1.35

1.37

1.38

1.40

1.41

1.45

1.46

1.47

1.61

2.44

2.45

2.46

3.62

3.63

3.64

7.26

7.27

7.28

7.28

7.29

7.29

7.31

7.31

7.32

7.32

7.33

SOH

-100102030405060708090100110120130140150160170180190200210f1(ppm)

20.2

425

.28

28.5

328

.68

32.5

9

40.8

2

62.7

564

.23

76.9

177

.12

77.3

3

100.5

8

127.0

212

9.17

131.98

132.3

8

SOH

S40

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

3.74

3.67

2.54

2.26

4.00

1.54

1.54

1.55

1.56

1.56

1.57

1.58

1.58

1.59

1.59

1.60

1.60

1.64

1.65

1.66

1.68

1.69

1.71

1.72

1.73

1.98

7.26

7.30

7.30

7.31

7.31

7.31

7.32

7.33

7.33

7.34

7.34

SOH

0102030405060708090100110120130140150160170180190200210f1(ppm)

21.4

523

.25

25.1

125

.32

34.6

539

.82

127.2

912

9.37

131.42

132.4

6

SOH

S41

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

2.37

2.31

2.36

2.28

1.07

4.00

1.56

1.59

1.60

1.61

1.62

1.63

1.65

1.67

2.12

2.12

2.13

2.13

2.14

2.14

2.15

2.15

2.15

2.19

6.22

6.23

6.23

6.23

6.24

6.24

7.26

7.28

7.28

7.28

7.29

7.30

7.30

7.32

7.33

7.33

7.34

7.34

7.34

S

0102030405060708090100110120130140150160170180190200210f1(ppm)

21.3

922

.23

25.8

029

.10

71.25

76.8

377

.05

77.2

6

100.6

4

120.5

6

127.1

112

9.25

132.1

313

2.28

136.7

2

S

S42

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

3.26

3.00

2.01

2.43

0.98

4.00

1.34

1.52

1.54

1.54

1.56

1.56

1.72

1.73

1.74

1.87

2.61

2.62

2.63

2.63

2.64

7.27

7.29

7.31

7.33

S

Cl

0102030405060708090100110120130140150160170180190200210f1(ppm)

24.8

525

.81

30.6

232

.55

64.0

5

76.8

577

.06

77.2

7

104.7

0

126.9

012

9.17

131.89

132.6

1

S

Cl

S43

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

6.09

4.06

3.93

1.99

2.05

1.91

2.00

0.88

0.89

0.90

0.91

0.93

1.26

1.31

1.42

1.50

2.28

2.30

2.64

2.66

2.68

S

CH3CH3

0102030405060708090100110120130140150160170180190200210f1(ppm)

13.5

814.

0219

.81

27.9

629

.20

30.8

931

.35

35.4

8

68.3

0

76.7

177

.02

94.2

0

S

CH3CH3

S44

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

2.31

1.94

0.76

1.28

1.72

1.87

1.00

3.10

1.61

1.25

1.25

1.30

1.33

1.39

1.43

1.57

1.62

1.84

2.09

2.48

2.97

2.97

2.98

2.99

3.00

3.01

3.02

3.03

3.04

7.26

7.27

7.27

7.28

7.28

7.29

7.29

7.30

7.31

7.40

7.41

7.42

7.43

S

0102030405060708090100110120130140150160170180190200210f1(ppm)

25.4

526

.07

33.0

4

47.7

0

76.7

077

.02

77.3

478

.57

94.3

6

123.7

412

7.87

128.2

613

1.41

S

S45

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)

4.34

2.26

4.03

3.66

4.25

0.96

1.00

1.18

1.21

1.27

1.31

1.42

1.49

1.53

1.57

1.74

1.99

2.04

2.79

2.79

2.80

2.81

2.82

2.83

2.84

2.85

2.86

5.99

6.00

6.00

6.01

6.01

7.19

S

0102030405060708090100110120130140150160170180190200210f1(ppm)

21.5

122

.33

25.4

725

.66

25.7

126

.06

26.1

029

.33

32.8

732

.91

74.6

4

96.2

8

121.12

134.3

2

S