Supporting Information

Switchable Reactivity between Vinyl Azides and Terminal

Alkyne by Nano Copper Catalysis

Jinghe Cen, Yaodan Wu, Jianxiao Li, Liangbin Huang, Wanqing Wu,

Zhongzhi Zhu, Shaorong Yang* and Huanfeng Jiang *

Key Laboratory of Functional Molecular Engineering of Guangdong Province,

School of Chemistry and Chemical Engineering, South China University of

Technology, Guangzhou 510640, P. R. China

[email protected]

Contents

1. General Information ..............................................................................................S2

2. General Procedures for the Synthesis of Substrates .............................................S2
3. Preparation and Characterization of Cu NPs Catalysts.........................................S3
4. General Procedures for CuNPs-Catalyzed Synthesize of Pyrroles .......................S3
5. Optimization of the Reaction Conditions .............................................................S5
6. Recycling of Cu nanoparticles ..............................................................................S5
7. Analysis Data of Pyrrole Products ........................................................................S6
8. Mechanistic Studies ............................................................................................S17
9. References ...........................................................................................................S18
10. NMR Spectra of Quinoline Products...............................................................S19
11. X-ray Crystallographic Data .......................................................................S7070
12. GC-MS Analysis of NH Imine Generated from Copper Intermediate VI ......S71
S1
 1. General Information

1H and 13C NMR spectra were recorded using a 400 MHz NMR spectrometer. Chemical shifts
were reported in ppm from the solvent resonance as the internal reference (DMSOd6 δH = 2.50
ppm, downfield from TMS, δC = 39.50 ppm. Multiplicity was indicated as follows: s (singlet), d
(doublet), t (triplet), q (quartet), m (multiplet). IR spectra were obtained as potassium bromide
pellets between two potassium bromide pellets with a spectrometer. GC-MS was obtained using
electron ionization. HRMS was obtained with a LCMS-IT-TOF mass spectrometer or recorded on
an EI-ion trap High Resolution mass spectrometer. Powder X-ray diffraction (PXRD) patterns
were collected on a Bruker D8 powder diffractometer at 40kV, 40mA with Cu Kα radiation
(λ=1.5406 Å), with a step size of 0.01995o (2θ). TLC was performed by using commercially
prepared 100-400 mesh silica gel plates and visualization was effected at 254 nm. X-ray structural
analyses were conducted on an x-ray analysis instrument.

Materials Acetonitrile was distilled from phosphorus pentoxide. Other commercially available
reagents were purchased and used without further purification unless otherwise specified.
Analytical thin-layer chromatography was performed on 0.20 mm silica gel plates (GF254) using
UV light as a visualizing agent. Flash column chromatography was conducted using silica gel
(200–300 mesh) with the indicated solvent system. All the reaction temperatures reported are oil
bath temperatures.

2. General Procedures for the Synthesis of Substrates

Vinyl azides 2a was prepared according to the previously reported procedure with slight
modification on the conditions.1

To a solution of (1,2-dibromoethyl)benzene (2.62g, 10 mmol, 1 equiv ) in dry DMF (30 mL) was
added NaN3 (1.95g, 30 mmol, 3 equiv). The mixture was stirred for 24 h at room temperature,
then diluted with water and extracted with petroleum ether. The combined organic layers were
washed three times with brine, dried with Na2SO4. After evaporation of solvents, the crude residue
was purified by flash column chromatography (silica gel; pure petroleum ether) to give vinyl
azides 2a (1.31g, 9 mmol) in 90% yield.

Vinyl azides 2b-2p was prepared according to the previously reported procedure with slight
modification on the conditions.2

R N3 R N3 R
ICl, NaN3 t-BuOK

Ar CH3CN, CH2Cl2 Ar I Et2O, 0 oC Ar

-20 oC 2b

To a suspension of NaN3 (812.5 mg, 12.5 mmol, 2.5 equiv) in acetonitrile (3 mL) was added
dropwise a solution of iodine monochloride (1214.0 mg, 7.5 mmol, 1.5 equiv) in CH2Cl2 (5 mL) at
S2
-20 °C, and the mixture was stirred at the same temperature. After 30 min, a solution of
1-fluoro-2-vinylbenzene (610.3 mg, 5 mmol, 1 equiv) in CH2Cl2 (5 mL) was added slowly, and
the mixture was stirred for 1 h. The reaction was quenched with saturated aqueous Na2S2O3, and
the organic materials were extracted two times with Et2O. The combined extracts were washed
with brine and dried over MgSO4. After evaporation of solvents, the resulting crude materials were
used immediately for the next step without any further purification. To a solution of the obtained
compounds above in Et2O (10 mL) was added t-BuOK (672.0mg, 6 mmol, 1.2 equiv) at 0 °C, and
the mixture was stirred for 1.5 h at the same temperature. The reaction was quenched by adding
NH4HCO3 saturated solution, and the organic materials were extracted with ethyl acetate. The
organic layer was washed with brine and dried over Na2SO4. The solvent was removed in vacuo,
and the resulting crude materials were purified by flash column chromatography (silica gel; pure
petroleum ether) to give 1-(1-azidovinyl)-2-fluorobenzene (2b) (619.4 mg, 76% yield) as a yellow
liquid.

3. Preparation and Characterization of Cu NPs Catalysts

Preparation of Catalysts. The Cu NPs catalyst was prepared by the reductive method according
to the reported literature with slight modification on the conditions3. A 100 mL round-bottom flask
was charged with CuSO4 (399 mg, 2.5 mmol) and distilled water (5 mL). The resulting solution
was stirred at room temperature, and then excess ammonium hydroxide was added until the
precipitate dissolve and the mixture turn out to be a deep blue transparent solution. During
continuous stirring, PEG600 (35 mL) was added. To this suspension a freshly prepared aqueous
NaBH4 (1 M, 20 mL) was added dropwise while it was vigorously stirred at 65 oC. Then the
mixture was stirred at 65 oC for 30 min. This process was accompanied by a change in color from
blue to dark which indicated the formation of the Cu NPs. The crude products were then
centrifuged and the obtained precipitates were washed several times with absolute ethanol and
distilled water. Finally, the Cu NPs was dried under vacuum for 24 hours at 60 oC. Pure Cu NPs
(149.8 mg, 2.34 mmol) was obtained as an atropurpureus solid.

Characterization.

(111)
3000
2500
2000
I (a.u.)

1500
(200)
1000 (220)
500
0
20 30 40 50 60 70 80
o
2θ / ( )
Figure 1. SEM image of the Cu NPs Figure 2. XRD spectrum of the Cu NPs

4. General Procedures for CuNPs-Catalyzed Synthesize of Pyrroles

General Procedure A:

S3
(1) In a 25 mL sealed test tube, CuNPs (30 mol %), 5 mL of DCE, alkyne 1 (0.2 mmol) and vinyl
azides 2 (0.36 mmol, 1.8 equiv) was added in sequence. The reaction mixture was sealed under a
nitrogen atmosphere and vigorously stirred together at 135 oC for 3 h. After completion of the
reaction, the resulting mixture was cooled to room temperature and then was filtered. The filtrate
was then concentrated in vacuum. Further purification by flash column chromatography on silica
gel (eluting with petroleum ether/ethyl acetate) afforded the pure product 3.
(2) Large-scale synthesis of 3a. In a 100 mL sealed test tube, CuNPs (30 mol %, 19 mg), 20 mL of
DCE, 1-ethynyl-4-methoxybenzene 1a (1 mmol, 132mg) and (1-azidovinyl)benzene 2a (1.8 mmol,
261 mg, 1.8 equiv) was added in sequence. The reaction mixture was sealed under a nitrogen
atmosphere and vigorously stirred together at 135 oC for 6 h. After completion of the reaction, the
resulting mixture was cooled to room temperature and then was filtered. The filtrate was then
concentrated in vacuum. Further purification by flash column chromatography on silica gel (eluent:
PET: EA = 20: 1) to afford the corresponding 2-(4-methoxyphenyl)-5-phenyl-1H-pyrrole 3a
(174.4 mg, 0.7 mmol) in 70% yield.

General Procedure B:

(1) In a 25 mL sealed test tube, Cu NPs (30 mol %), 5 mL of DCE, alkyne 1 (0.2 mmol) and
vinyl azides 2 (0.5 mmol, 2.5 equiv) was added in sequence. The reaction mixture was sealed
under a nitrogen atmosphere and vigorously stirred together at 135 oC for 3 h. After
completion of the reaction, the resulting mixture was cooled to room temperature and then
was filtered. The filtrate was then concentrated in vacuum. Further purification by flash
column chromatography on silica gel (eluting with petroleum ether/ethyl acetate) afforded the
pure product 5.
(2) In a 100 mL sealed test tube, Cu NPs (30 mol %, 19 mg), 20 mL of DCE,
ethynyltriisopropylsilane 1w (1 mmol, 182 mg) and (1-azidovinyl)benzene 2a (2.5 mmol,
362.5 mg, 2.5 equiv) was added in sequence. The reaction mixture was sealed under a
nitrogen atmosphere and vigorously stirred together at 135 oC for 6 h. After completion of the
reaction, the resulting mixture was cooled to room temperature and then was filtered. The
filtrate was then concentrated in vacuum. Further purification by flash column
chromatography on silica gel (eluent: PET: EA = 10: 1) to afford the corresponding
2,4-diphenyl-3-((triisopropylsilyl) ethynyl)-1H-pyrrole 5c (251.4 mg, 0.63 mmol) in 63 %
yield.

S4
5. Optimization of the Reaction Conditions

o
entry [Cu] (mol %) Solvent (mL) temp. ( C) yield of 3a (%) yield of 3a’ (%)

1 CuI (30) CH3CN (4) 135 5 40

2 CuI (30) DCE (4) 135 18 n.d.

3 CuTC (30) DCE (4) 135 n.d 76

4 CuCl (30) DCE (4) 135 45 n.d.

5 CuSCN (30) DCE (4) 135 60 n.d.

6 CuBr (30) DCE (4) 135 37 n.d.

7 CuCN (30) DCE (4) 135 48 n.d.

b
6 CuNPs (30) DCE (4) 135 81(77) n.d.

7 Cu dust(30) DCE (4) 135 23 n.d.

8 - DCE (4) 135 n.d. n.d.

9 FeCl2 (30) DCE (4) 135 n.d. n.d.

10 Pd(OAc)2 (30) DCE (4) 135 n.d. n.d.

11 CuNPs (30) DCM (4) 135 63 n.d.

12 CuNPs (30) CH3CN (4) 135 n.d n.d.

13 CuNPs (15) DCE (4) 135 74 n.d.

14 CuNPs (50) DCE (4) 135 60 n.d.

15 CuNPs (30) DCE (4) 145 81 n.d.

16 CuNPs (30) DCE (4) 125 78 n.d.

c
17 CuNPs (30) DCE (4) 135 67 n.d.

18d CuNPs (30) DCE (4) 135 80 n.d.

e
19 CuNPs (30) DCE (4) 135 80 n.d.
aAlkyne (0.1 mmol), vinyl azides (0.18 mmol) were stirred for 3 h under a nitrogen atmosphere.
Yields were determined by 1HNMR using CH2ClBr as internal standard. bIsolated yields. cUnder air
atmosphere. d 1 equiv H2O was added. eAlkyne (0.2 mmol), vinyl azides (0.36 mmol), DCE (5 mL).

6. Recycling of Cu nanoparticles

S5
 run catalyst recovery [%] yield of 3a [%]
a
1 95 81
2b 91 79
3b 86 75
a Reaction conditions: CuNPs (30 mol %), alkyne 1a (0.2 mmol),
vinyl azides 2a (0.36 mmol), DCE (5 mL) were stirred for 3 h at 135
oC under a nitrogen atmosphere. b The recovered catalyst was used
under identical reaction conditions to those for the first run.

7. Analysis Data of Pyrrole Products

2-(4-Methoxyphenyl)-5-phenyl-1H-pyrrole (3a)

Yield: 77% (38.4 mg) as a yellow solid (m.p. = 162-163 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.43; 1H NMR (400 MHz, DMSO) δ 11.15 (s, 1H), 7.76 (d, J = 7.6 Hz, 2H), 7.71
(d, J = 8.8 Hz, 2H), 7.36 (t, J = 7.8 Hz, 2H), 7.16 (t, J = 7.4 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H),
6.57 (d, J = 2.0 Hz, 1H), 6.46 (s, 1H), 3.77 (s, 3H). 13C NMR (100 MHz, DMSO) δ 157.7, 133.2,
132.8, 132.2, 128.6, 125.6, 125.5, 125.4, 123.7, 114.1, 107.5, 106.5, 55.1 ppm; IR (KBr)/cm-1
3860, 3448, 2922, 1629, 1464, 1393, 1253, 1028, 832, 759, 682, 503; HRMS (ESI) m/z: calcd for
C17H15NO [M+] 249.1148; found: 249.1147.

2-Phenyl-5-(p-tolyl)-1H-pyrrole (3b)

Yield: 70% (32.6 mg) as a yellow solid (m.p. = 142-143 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.75; 1H NMR (400 MHz, DMSO) δ 11.17 (s, 1H), 7.76 (d, J = 7.6 Hz, 2H), 7.66
(d, J = 8.0 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.17 (t, J = 8.8 Hz, 3H), 6.57 (t, J = 3.0 Hz, 1H), 6.53
(t, J = 2.8 Hz, 1H), 2.30 (s, 3H). 13C NMR (100 MHz, DMSO) δ 134.9 133.2, 132.6, 132.6, 129.9,
129.1, 128.6, 125.6, 123.9, 123.8, 107.5, 107.1, 20.7 ppm; IR (KBr)/cm-1 3781, 3455, 2920, 1621,
1456, 1396, 1056, 761, 684, 505; HRMS (ESI) m/z: calcd for C17H16N [M+H]+ 234.1277; found:
234.1274.

4-(5-Phenyl-1H-pyrrol-2-yl) aniline (3c)

Yield: 73% (34.2 mg) as a yellow solid (m.p. = 160-161 oC); TLC (petroleum ether/ethyl acetate =

S6
10/1, v/v): Rf = 0.05; 1H NMR (400 MHz, DMSO) δ 10.93 (s, 1H), 7.72 (d, J = 8.0 Hz, 2H), 7.46
(d, J = 8.0 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.12 (t, J = 7.4 Hz, 1H), 6.62 (d, J = 8.4 Hz, 2H),
6.52 (s, 1H), 6.31 (s, 1H), 5.17 (s, 2H). 13C NMR (100 MHz, DMSO) δ 146.9, 134.5, 132.9, 131.2,
128.5, 125.2, 125.1, 123.5, 121.1, 114.1, 107.3, 104.9 ppm; IR (KBr)/cm-1 3788, 2922, 1607, 1482,
1399, 1275, 1054, 758, 675, 481; HRMS (ESI) m/z: calcd for C16H15N2 [M+H]+ 235.1230; found:
235.1233.

N, N-dimethyl-4-(5-phenyl-1H-pyrrol-2-yl) aniline (3d)

Yield: 82% (43.0 mg) as a brown solid (m.p. = 148-149 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.33; 1H NMR (400 MHz, DMSO) δ 11.06 (s, 1H), 7.77 (d, J = 7.6 Hz, 2H), 7.64
(d, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 7.4 Hz, 1H), 6.77 (d, J = 8.4 Hz, 2H),
6.57 (d, J = 2.4 Hz, 1H), 6.40 (s, 1H), 2.91 (s, 6H). 13C NMR (100 MHz, DMSO) δ 148.8, 134.0,
132.9, 131.5, 128.5, 125.1, 125.1, 123.6, 121.3, 112.5, 107.4, 105.4, 40.1 ppm; IR (KBr)/cm-1
3787, 3422, 1603, 1479, 1049, 820, 755, 685, 535; HRMS (ESI) m/z: calcd for C18H19N2 [M+H] +
263.1543; found: 263.1545.

2-(4-Fluorophenyl)-5-phenyl-1H-pyrrole (3e)

Yield: 60% (28.5 mg) as a yellow crystal (m.p. = 148-149 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.58; 1H NMR (400 MHz, DMSO) δ 11.26 (s, 1H), 7.82-7.75 (m, 4H), 7.37 (t, J
= 7.6 Hz, 2H), 7.24-7.16 (m, 3H), 6.59 (t, J = 2.8 Hz, 1H), 6.56 (t, J = 2.6 Hz, 1H). 13C NMR (100
MHz, DMSO) δ 160.6 (d, J = 242.7 Hz), 133.0, 132.5, 132.1, 129.3 (d, J = 3.0 Hz), 128.6, 125.9,
125.8 (d, J = 2.1 Hz), 123.9, 115.5, 115.3, 107.6 (d, J = 3.0 Hz) ppm; IR (KBr)/cm-1 3864, 3793,
3455, 2925, 1606, 1460, 1394, 834, 760, 510; HRMS (ESI) m/z: calcd for C16H13FN [M+H]+
238.1027; found: 238.1023.

2-(4-Chlorophenyl)-5-phenyl-1H-pyrrole (3f)

Yield: 57% (28.9 mg) as a yellow solid (m.p. = 153-154 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.58; 1H NMR (400 MHz, DMSO) δ 11.32 (s, 1H), 7.79 (dd, J = 8.8, 8.0 Hz, 4H),
7.46-7.34 (m, 4H), 7.19 (t, J = 7.4 Hz, 1H), 6.63 (t, J = 3.0 Hz, 1H), 6.61 (t, J = 3.0 Hz, 1H). 13C
NMR (100 MHz, DMSO) δ 133.5, 132.4, 131.8, 131.4, 130.0, 128.6, 128.5, 125.9, 125.5, 124.0,
108.3, 107.8 ppm; IR (KBr)/cm-1 3789, 3455, 2920, 1633, 1462, 1400, 1102, 829, 760, 683, 503;
HRMS (ESI) m/z: calcd for C16H13ClN [M+H]+ 254.0731; found: 254.0726.

2-Phenyl-5-(4-(trifluoromethyl)phenyl)-1H-pyrrole (3g)

S7
Yield: 56% (32.2 mg) as a yellow solid (m.p. = 168-169 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.58; 1H NMR (400 MHz, DMSO) δ 11.48 (s, 1H), 7.98 (d, J = 8.0 Hz, 2H), 7.80
(d, J = 7.6 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.4 Hz, 1H),
6.78 (d, J = 2.4 Hz, 1H), 6.65 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, DMSO) δ 136.3, 134.5,
132.2, 131.4, 128.6, 126.3, 125.7, 125.5 (dd, J = 7.6, 3.7 Hz), 125.4, 124.3, 124.0, 109.8, 108.1
ppm; IR (KBr)/cm-1 3455, 2920, 1625, 1330, 1116, 840, 762, 686, 503; HRMS (ESI) m/z: calcd
for C17H13F3N [M+H]+ 288.0995; found: 288.0993.

2-Phenyl-5-(o-tolyl)-1H-pyrrole (3h)

Yield: 69% (32.2 mg) as a yellow crystal (m.p. = 63-64 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.80; 1H NMR (400 MHz, DMSO) δ 11.21 (s, 1H), 7.75 (d, J = 6.8 Hz, 2H), 7.50
(d, J = 7.2 Hz, 1H), 7.36 (t, J = 7.6 Hz, 2H), 7.29-7.15 (m, 4H), 6.62 (s, 1H), 6.29 (d, J = 1.6 Hz,
1H), 2.44 (s, 3H). 13C NMR (100 MHz, DMSO) δ 134.8, 132.8, 132.8, 132.3, 132.0, 130.6, 128.6,
128.6, 126.5, 125.7, 125.5, 123.7, 110.3, 106.8, 21.0 ppm; IR (KBr)/cm-1 3794, 3424, 1596, 1467,
1255, 1046, 750, 683, 470; HRMS (ESI) m/z: calcd for C17H16N [M+H] + 234.1277; found:
234.1275.

2-Phenyl-5-(m-tolyl)-1H-pyrrole (3i)

Yield: 68% (31.7 mg) as a yellow solid (m.p. = 132-133 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.67; 1H NMR (400 MHz, DMSO) δ 11.22 (s, 1H), 7.78 (d, J = 7.6 Hz, 2H), 7.62
(s, 1H), 7.57 (d, J = 7.6 Hz, 1H), 7.37 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 7.6 Hz, 1H), 7.18 (t, J = 7.2
Hz, 1H), 7.00 (d, J = 7.6 Hz, 1H), 6.59 (s, 2H), 2.35 (s, 3H). 13C NMR (101 MHz, DMSO) δ 137.6,
133.1, 132.9, 132.6, 132.5, 128.5, 128.4, 126.5, 125.7, 124.5, 123.9, 121.2, 107.6, 107.5, 21.1 ppm;
IR (KBr)/cm-1 3841, 3652, 3443, 2921, 1599, 1397, 1276, 1050, 758, 686, 499; HRMS (ESI) m/z:
calcd for C17H16N [M+H]+ 234.1277; found: 234.1272.

2-(3-Fluorophenyl)-5-phenyl-1H-pyrrole (3j)

Yield: 63% (29.9 mg) as a yellow solid (m.p. = 116-117 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.73; 1H NMR (400 MHz, DMSO) δ 11.31 (s, 1H), 7.78 (d, J = 7.6 Hz, 2H), 7.67
(d, J = 11.2 Hz, 1H), 7.61 (d, J = 7.6 Hz, 1H), 7.38 (t, J = 7.2 Hz, 3H), 7.20 (t, J = 7.2 Hz, 1H),
6.98 (t, J = 8.4 Hz, 1H), 6.70 (s, 1H), 6.61 (s, 1H). 13C NMR (100 MHz, DMSO) δ 162.8 (d, J =
241.8 Hz), 134.9 (d, J = 8.6 Hz), 133.7, 132.3, 131.7 (d, J = 2.6 Hz), 130.4 (d, J = 8.8 Hz), 128.6,

S8
126.0, 124.1, 119.9 (d, J = 2.4 Hz), 112.0 (d, J = 21.2 Hz), 110.2 (d, J = 23.0 Hz), 108.8, 107.8
ppm; IR (KBr)/cm-1 3781, 3434, 2920, 1596, 1471, 1275, 1180, 1052, 846, 761, 682, 532; HRMS
(ESI) m/z: calcd for C16H13FN [M+H]+ 238.1027; found: 238.1024.

2-(Naphthalen-2-yl)-5-phenyl-1H-pyrrole (3k)

Yield: 78% (42.0 mg) as a brown solid (m.p. = 162-163 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.68; 1H NMR (400 MHz, DMSO) δ 11.46 (s, 1H), 8.34 (s, 1H), 7.95 (d, J = 8.4
Hz, 1H), 7.91-7.83 (m, 5H), 7.51 (t, J = 7.4 Hz, 1H), 7.45-7.38 (m, 3H), 7.21 (t, J = 7.2 Hz, 1H),
6.77 (t, J = 2.8 Hz, 1H), 6.67 (t, J = 2.8 Hz, 1H). 13C NMR (100 MHz, DMSO) δ 133.6, 133.5,
133.0, 132.5, 131.5, 130.1, 128.6, 128.0, 127.6, 127.5, 126.5, 125.9, 125.2, 124.1, 123.5, 120.9,
108.6, 107.9 ppm; IR (KBr)/cm-1 3868, 3783, 3658, 3553, 3455, 2921, 2856, 2789, 1624, 1391,
758, 685, 479; HRMS (ESI) m/z: calcd for C20H16N [M+H]+ 270.1277; found: 270.1272.

2-Phenyl-5-(thiophen-2-yl)-1H-pyrrole (3l)

Yield: 76% (34.2 mg) as a red solid (m.p. = 108-109 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.65; 1H NMR (400 MHz, DMSO) δ 11.41 (s, 1H), 7.75 (d, J = 8.0 Hz, 2H), 7.44
(d, J = 3.6 Hz, 1H), 7.39- 7.33 (m, 3H), 7.19 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 4.4 Hz, 1H), 6.56 (t, J
= 3.0 Hz, 1H), 6.38 (t, J = 2.8 Hz, 1H). 13C NMR (100 MHz, DMSO) δ 136.0, 132.6, 132.3, 128.6,
127.8, 127.7, 125.8, 123.9, 122.8, 121.5, 108.0, 107.4 ppm; IR (KBr)/cm-1 3780, 3443, 2926, 2849,
1607, 1403, 1058, 762, 681, 489; HRMS (ESI) m/z: calcd for C14H12NS [M+H]+ 226.0685; found:
226.0680.

2-Cyclopropyl-5-phenyl-1H-pyrrole (3m)

Yield: 60% (22.0 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.50;
1H NMR (400 MHz, DMSO) δ 10.93 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.08 (t, J = 7.2 Hz, 1H), 6.34 (d, J = 2.4 Hz, 1H), 5.71 (s, 1H), 1.95-1.78 (m, 1H), 0.91-0.74 (m,
2H), 0.63 (q, J = 5.2 Hz, 2H). 13C NMR (100 MHz, DMSO) δ 136.1, 133.1, 129.6, 128.5, 124.8,
122.9, 105.5, 104.1, 8.5, 7.3 ppm; IR (KBr)/cm-1 3788, 3454, 2921, 2850, 1602, 1397, 748, 670,
472; HRMS (ESI) m/z: calcd for C13H14N [M+H]+ 184.1121; found: 184.1116.

2-Cyclopentyl-5-phenyl-1H-pyrrole (3n)

Yield: 61% (25.8 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.63;
1H NMR (400 MHz, DMSO) δ 10.81 (s, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.09 (t, J = 7.2 Hz, 1H), 6.35 (t, J = 2.8 Hz, 1H), 5.84 (t, J = 2.8 Hz, 1H), 3.10-2.95 (m, 1H), 1.99
(d, J = 3.6 Hz, 2H), 1.71 (m, 2H), 1.67-1.52 (m, 4H). 13C NMR (100 MHz, DMSO) δ 138.2, 133.3,

S9
129.8, 128.5, 124.7, 123.0, 105.2, 104.6, 38.3, 33.0, 24.6 ppm; IR (KBr)/cm-1 3780, 3412, 1607,
1396, 1059, 751, 680, 474; HRMS (ESI) m/z: calcd for C15H18N [M+H]+ 212.1434; found:
212.1431.

2-Cyclohexyl-5-phenyl-1H-pyrrole (3o)

Yield: 63% (28.4 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.73;
1H NMR (400 MHz, DMSO) δ 10.78 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.08 (t, J = 7.6 Hz, 1H), 6.34 (t, J = 2.8 Hz, 1H), 5.79 (t, J = 2.4 Hz, 1H), 2.59-2.54 (m, 1H), 1.96
(d, J = 9.6 Hz, 2H), 1.77 (dd, J = 6.8, 2.8 Hz, 2H), 1.68 (d, J = 12.4 Hz, 1H), 1.43-1.33 (m, 4H),
1.22 (dd, J = 15.7, 6.7 Hz, 1H). 13C NMR (100 MHz, DMSO) δ 139.8, 133.3, 129.5, 128.5, 124.7,
123.0, 105.2, 104.0, 36.5, 32.9, 26.0, 25.7 ppm; IR (KBr)/cm-1 3793, 2920, 2850, 1601, 1395,
1051, 751, 678, 475; HRMS (ESI) m/z: calcd for C16H20N [M+H]+ 226.1590; found: 226.1588.

2-(Tert-butyl)-5-phenyl-1H-pyrrole (3p)

Yield: 58% (23.1 mg) as a colorless oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.44;
1H NMR (400 MHz, DMSO) δ 10.55 (s, 1H), 7.64 (d, J = 7.6 Hz, 2H), 7.32 (t, J = 7.6 Hz, 2H),

7.11 (t, J = 7.2 Hz, 1H), 6.31 (t, J = 2.8 Hz, 1H), 5.81 (t, J = 2.8 Hz, 1H), 1.31 (s, 9H). 13C NMR
(100 MHz, DMSO) δ 143.4, 133.3, 130.3, 128.4, 124.9, 123.4, 104.9, 103.69, 31.39, 30.29 ppm;
IR (KBr)/cm-1 3782, 3676, 2924, 1622, 1401, 659, 571, 476; HRMS (ESI) m/z: calcd for C14H17N
[M+] 199.1356; found: 199.1354.

2-Isopentyl-5-phenyl-1H-pyrrole (3q)

Yield: 65% (27.7 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.53;
1H NMR (400 MHz, DMSO) δ 10.86 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.08 (t, J = 7.6 Hz, 1H), 6.36 (s, 1H), 5.81 (s, 1H), 2.59 (t, J = 8.0 Hz, 2H), 1.61-1.57 (m, 1H),
1.56-1.49 (m, 2H), 0.92 (d, J = 6.4 Hz, 6H). 13C NMR (100 MHz, DMSO) δ 134.3, 133.2, 129.5,
128.5, 124.7, 122.8, 106.0, 105.5, 38.6, 27.1, 25.1, 22.3 ppm; IR (KBr)/cm-1 3789, 3411, 2936,
1605, 1512, 1455, 1046, 754, 681, 468; HRMS (ESI) m/z: calcd for C15H20N [M+H]+ 214.1590;
found: 214.1587.

2-Hexyl-5-phenyl-1H-pyrrole (3r)

Yield: 50% (22.7 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 20/1, v/v): Rf = 0.44;
1H NMR (400 MHz, DMSO) δ 10.86 (s, 1H), 7.58 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.08 (t, J = 7.6 Hz, 1H), 6.36 (t, J = 2.8 Hz, 1H), 5.81 (t, J = 2.4 Hz, 1H), 2.57 (t, J = 7.6 Hz, 2H),
1.64-1.57 (m, 2H), 1.35-1.27 (m, 6H), 0.87 (t, J = 6.4 Hz, 3H). 13C NMR (100 MHz, DMSO) δ

S10
134.3, 133.3, 129.6, 128.5, 124.7, 122.9, 106.2, 105.5, 31.1, 29.4, 28.4, 27.3, 22.1, 13.9 ppm; IR
(KBr)/cm-1 3788, 3415, 2924, 2856, 1604, 1395, 1060, 753, 677, 472; HRMS (ESI) m/z: calcd for
C16H22N [M+H]+ 228.1747; found: 228.1743.

2-Phenyl-5-(3-phenylpropyl)-1H-pyrrole (3s)

Yield: 48% (25.1 mg) as a colorless oil; TLC (petroleum ether/ethyl acetate = 10/1, v/v): Rf = 0.65;
1H NMR (400 MHz, DMSO) δ 10.92 (s, 1H), 7.60 (d, J = 7.9 Hz, 2H), 7.30 (q, J = 7.30 Hz, 4H),

7.25-7.15 (m, 3H), 7.09 (t, J = 7.2 Hz, 1H), 6.40 (s, 1H), 5.87 (s, 1H), 2.67-2.60 (m, 4H),
1.99-1.90 (m, 2H). 13C NMR (100 MHz, DMSO) δ 142.0, 133.8, 133.2, 129.7, 128.5, 128.3, 128.2,
125.6, 124.8, 122.9, 106.4, 105.5, 34.9, 31.0, 26.9 ppm; IR (KBr)/cm-1 3782, 3413, 2921, 1601,
1397, 749, 679, 471; HRMS (ESI) m/z: calcd for C19H20N [M+H]+ 262.1590; found: 262.1585.

4-(5-Phenyl-1H-pyrrol-2-yl)butanenitrile (3t)

Yield: 61% (25.6 mg) as a brown oil; TLC (petroleum ether/ethyl acetate = 10/1, v/v): Rf = 0.13;
1H NMR (400 MHz, DMSO) δ 10.99 (s, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H),

7.11 (t, J = 7.2 Hz, 1H), 6.40 (t, J = 2.8 Hz, 1H), 5.89 (t, J = 2.6 Hz, 1H), 2.70 (t, J = 7.6 Hz, 2H),
2.51 (t, J = 6.8 Hz, 2H), 1.97-1.88 (m, 2H). 13C NMR (100 MHz, DMSO) δ 133.1, 132.1, 130.2,
128.6, 125.0, 123.0, 120.4, 106.8, 105.6, 26.2, 25.1, 15.8 ppm; IR (KBr)/cm-1 3787, 3699, 3354,
1603, 1399, 1055, 758, 678, 470; HRMS (ESI) m/z: calcd for C14H15N2 [M+H]+ 211.1230; found:
211.1226.

2-(4-Chlorobutyl)-5-phenyl-1H-pyrrole (3u)

Yield: 72% (33.6 mg) as an orange oil; TLC (petroleum ether/ethyl acetate = 10/1, v/v): Rf = 0.44;
1H NMR (400 MHz, DMSO) δ 10.91 (s, 1H), 7.57 (d, J = 7.2 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H),

7.09 (t, J = 7.2 Hz, 1H), 6.37 (t, J = 2.8 Hz, 1H), 5.83 (t, J = 2.6 Hz, 1H), 3.64 (t, J = 6.0 Hz, 2H),
2.60 (t, J = 7.2 Hz, 2H), 1.80-1.71 (m, 4H). 13C NMR (100 MHz, DMSO) δ 133.7, 133.2, 129.8,
128.6, 124.9, 123.0, 106.5, 105.6, 45.3, 31.7, 26.7, 26.5 ppm; IR (KBr)/cm-1 3794, 3429, 2930,
1598, 1509, 1449, 1044, 756, 685, 509; HRMS (ESI) m/z: calcd for C14H17ClN [M+H]+ 234.1044;
found: 234.1040.

2-(4-Methoxyphenyl)-5-(p-tolyl)-1H-pyrrole (4a)

Yield: 75% (39.5 mg) as a yellow solid (m.p. = 192-193 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.55; 1H NMR (400 MHz, DMSO) δ 11.06 (s, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.63
(d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.6 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H), 6.49 (s, 1H), 6.43 (s, 1H),
3.77 (s, 3H), 2.29 (s, 3H); 13C NMR (100 MHz, DMSO) δ 157.6, 134.6, 132.7, 132.4, 130.1, 129.1,

S11
125.6, 125.3, 123.7, 114.0, 106.9, 106.3, 55.1, 20.7 ppm; IR (KBr)/cm-1 3893, 3457, 2930, 1641,
1254, 1034, 830, 770, 516; HRMS (ESI) m/z: calcd for C18H17NO [M+] 263.1305; found:
263.1303.

2-(4-(Tert-butyl)phenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4b)

Yield: 77% (47.0 mg) as a white solid (m.p. = 177-178 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.62; 1H NMR (400 MHz, DMSO) δ 11.09 (s, 1H), 7.68 (t, J = 9.2 Hz, 4H), 7.38
(d, J = 8.4 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.49 (t, J = 3.0 Hz, 1H), 6.44 (t, J = 2.8 Hz, 1H),
3.77 (s, 3H), 1.30 (s, 9H); 13C NMR (100 MHz, DMSO) δ 157.6, 147.9, 132.7, 132.3, 130.1, 125.7,
125.3, 125.2, 123.6, 114.0, 106.9, 106.3, 55.1, 34.1, 31.1 ppm; IR (KBr)/cm-1 3626, 3455, 2960,
1641, 1529, 1462, 1260, 1034, 834, 775, 513; HRMS (ESI) m/z: calcd for C21H24NO [M+H]+
306.1852; found: 306.1847.

2-(4-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4c)

Yield: 73% (39.0 mg) as a yellow solid (m.p. = 160-161 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.55; 1H NMR (400 MHz, DMSO) δ 11.14 (s, 1H), 7.78 (t, J = 6.8 Hz, 2H), 7.69
(d, J = 8.0 Hz, 2H), 7.20 (t, J = 8.6 Hz, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.52 (s, 1H), 6.45 (s, 1H),
3.77 (s, 3H); 13C NMR (100 MHz, DMSO) δ 160.5 (d, J = 242.3 Hz), 157.7, 133.1, 131.3, 129.5
(d, J = 3.0 Hz), 125.6, 125.5 (d, J = 2.1 Hz), 125.3, 115.4 (d, J = 21.4 Hz), 114.1, 107.4, 106.4,
55.1 ppm; IR (KBr)/cm-1 3456, 2925, 1645, 1518, 1252, 1032, 835, 770, 522; HRMS (ESI) m/z:
calcd for C17H14FNO [M+] 267.1054; found: 267.1052.

2-(4-Chlorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4d)

Yield: 70% (39.6 mg) as a yellow solid (m.p. = 204-205 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.38; 1H NMR (400 MHz, DMSO) δ 11.19 (s, 1H), 7.77 (d, J = 8.0 Hz, 2H), 7.69
(d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.59 (s, 1H), 6.46 (s, 1H),
3.78 (s, 3H); 13C NMR (100 MHz, DMSO) δ 157.8, 133.6, 131.6, 130.9, 129.6, 128.5, 125.4,
125.3, 125.2, 114.1, 108.1, 106.6, 55.1 ppm; IR (KBr)/cm-1 3531, 3453, 2928, 1641, 1111, 1034,
833, 772, 517; HRMS (ESI) m/z: calcd for C17H14ClNO [M+]+ 283.0758; found: 283.0755.

2-(4-Bromophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4e)

S12
Yield: 52% (34.0 mg) as a yellow solid (m.p. = 225-226 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.38; 1H NMR (400 MHz, DMSO) δ 11.18 (s, 1H), 7.69 (t, J = 7.6 Hz, 4H), 7.53
(d, J = 8.4 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.60 (t, J = 2.8 Hz, 1H), 6.46 (t, J = 2.8 Hz, 1H),
3.78 (s, 3H); 13C NMR (100 MHz, DMSO) δ 157.8, 133.7, 131.9, 131.4, 130.9, 125.6, 125.4,
125.3, 118.0, 114.1, 108.2, 106.6, 55.1 ppm; IR (KBr)/cm-1 3900, 3777, 3544, 3448, 2922, 1624,
1397, 1043, 831, 774, 495; HRMS (ESI) m/z: calcd for C17H14BrNO [M+] 327.0253; found:
327.0252.

2-(4-Methoxyphenyl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrrole (4f)

Yield: 81% (51.4 mg) as a white solid (m.p. = 196-197 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.45; 1H NMR (400 MHz, DMSO) δ 11.37 (s, 1H), 7.96 (d, J = 8.0 Hz, 2H), 7.73
(d, J = 8.4 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 6.75 (t, J = 2.8 Hz, 1H),
6.51 (t, J = 2.8 Hz, 1H), 3.78 (s, 3H); 13C NMR (100 MHz, DMSO) δ 158.1, 136.5, 134.7, 130.6,
126.0, 125.7, 125.5 (dd, J = 7.7, 3.9 Hz, 3H), 125.1, 123.7, 123.3, 114.1, 109.7, 107.0, 55.1 ppm;
IR (KBr)/cm-1 3457, 2930, 1609, 1437, 1324, 1120, 1041, 837, 773, 518; HRMS (ESI) m/z: calcd
for C18H15F3NO [M+H]+ 318.1100; found: 318.1098.

4-(5-(4-methoxyphenyl)-1H-pyrrol-2-yl)benzonitrile (4g)

Yield: 80% (43.8 mg) as a yellow solid (m.p. = 147-148 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.11; 1H NMR (400 MHz, DMSO) δ 11.37 (s, 1H), 7.92 (d, J = 8.4 Hz, 2H), 7.77
(d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H), 6.81 (s, 1H), 6.53 (s, 1H),
3.78 (s, 3H). 13C NMR (100 MHz, DMSO) δ 158.2, 136.8, 135.3, 132.5, 130.4, 125.8, 124.9,
123.7, 119.4, 114.1, 110.7, 107.3, 106.7, 55.1 ppm; IR (KBr)/cm-1 3769, 3567, 3354, 2924, 2217,
1599, 1488, 1258, 1173, 1031, 829, 773; HRMS (ESI) m/z: calcd for C18H14N2O [M+] 274.1101;
found: 274.1099.

4-(5-(4-Methoxyphenyl)-1H-pyrrol-2-yl)phenyl acetate (4h)

Yield: 54% (33.2 mg) as a white solid (m.p. = 153-154 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.13; 1H NMR (400 MHz, DMSO) δ 11.18 (s, 1H), 7.79 (d, J = 8.4 Hz, 2H), 7.71
(d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 6.56 (s, 1H), 6.47 (s, 1H),
3.78 (s, 3H), 2.28 (s, 3H); 13C NMR (100 MHz, DMSO) δ 169.4, 157.7, 148.4, 133.3, 131.6, 130.6,
125.5, 125.4, 124.7, 122.0, 114.1, 107.7, 106.5, 55.1, 20.8 ppm; IR (KBr)/cm-1 3415, 2927, 1741,
1501, 1217, 1033, 914, 837, 779, 557; HRMS (ESI) m/z: calcd for C19H18NO3 [M+H]+ 308.1281;
found: 308.1285.

S13
2-(4-Methoxyphenyl)-5-(m-tolyl)-1H-pyrrole (4i)

Yield: 77% (40.5 mg) as a yellow solid (m.p. = 170-171 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.43; 1H NMR (400 MHz, DMSO) δ 11.11 (s, 1H), 7.71 (d, J = 8.4 Hz, 2H), 7.60
(s, 1H), 7.55 (d, J = 7.6 Hz, 1H), 7.24 (t, J = 7.6 Hz, 1H), 6.97 (t, J = 7.6 Hz, 3H), 6.55 (s, 1H),
6.45 (s, 1H), 3.78 (s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz, DMSO) δ 157.7, 137.8, 133.0, 132.7,
132.3, 128.4, 126.2, 125.6, 125.4, 124.3, 121.0, 114.0, 107.4, 106.4, 55.1, 21.2 ppm; IR
(KBr)/cm-1 3787, 3436, 2915, 1590, 1473, 1241, 1021, 828, 759, 523; HRMS (ESI) m/z: calcd for
C18H17NO [M+] 263.1305; found: 263.1306.

2-(3-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4j)

Yield: 74% (39.5 mg) as a yellow solid (m.p. = 130-131 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.53; 1H NMR (400 MHz, DMSO) δ 11.21 (s, 1H), 7.71 (d, J = 8.4 Hz, 2H), 7.65
(d, J = 11.2 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.37 (dd, J = 7.6, 7.6 Hz, 1H), 6.96 (t, J = 11.2 Hz,
3H), 6.67 (s, 1H), 6.48 (s, 1H), 3.78 (s, 3H); 13C NMR (100 MHz, DMSO) δ 162.8 (d, J = 241.6
Hz), 157.9, 135.1 (d, J = 8.7 Hz), 133.8, 130.9 (d, J = 2.6 Hz), 130.4 (d, J = 8.8 Hz), 125.5, 125.3,
119.7 (d, J = 2.2 Hz), 114.1, 111.7 (d, J = 21.2 Hz), 110.0 (d, J = 23.0 Hz), 108.7, 106.6, 55.1 ppm;
IR (KBr)/cm-1 3460, 2941, 1589, 1468, 1257, 1182, 1031, 840, 768, 494; HRMS (ESI) m/z: calcd
for C17H14FNO [M+] 267.1054; found:267.1051.

2-(2-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4k)

Yield: 83% (44.3 mg) as a yellow solid (m.p. = 113-114 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.48; 1H NMR (400 MHz, DMSO) δ 11.20 (s, 1H), 7.93 (t, J = 7.8 Hz, 1H), 7.72
(d, J = 8.4 Hz, 2H), 7.26-7.22 (m, 3H), 6.97 (d, J = 8.4 Hz, 2H), 6.62 (d, J = 1.2 Hz, 1H), 6.52 (s,
1H), 3.77 (s, 3H); 13C NMR (100 MHz, DMSO) δ 158.3 (d, J = 245.4 Hz), 158.0, 133.5, 127.0 (d,
J = 8.4 Hz), 126.9 (d, J = 3.7 Hz), 125.9 (d, J = 2.2 Hz), 125.7, 125.4, 124.5 (d, J = 3.1 Hz), 120.8
(d, J = 12.1 Hz), 116.1 (d, J = 22.1 Hz), 114.2, 111.5 (d, J = 10.0 Hz), 106.6, 55.1 ppm; IR
(KBr)/cm-1 3804, 3456, 1643, 1467, 1233, 1024, 753, 541; HRMS (ESI) m/z: calcd for
C17H14FNO [M+] 267.1054; found: 267.1054.

2-(4-Methoxyphenyl)-5-(naphthalen-2-yl)-1H-pyrrole (4m)

Yield: 71% (42.5 mg) as a brown solid (m.p. = 193-194 oC); TLC (petroleum ether/ethyl acetate =
10/1, v/v): Rf = 0.35; 1H NMR (400 MHz, DMSO) δ 11.32 (s, 1H), 8.28 (s, 1H), 7.93-7.83 (m,

S14
4H), 7.75 (d, J = 8.4 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.41 (t, J = 7.4 Hz, 1H), 6.98 (d, J = 8.4 Hz,
2H), 6.73 (s, 1H), 6.52 (s, 1H), 3.78 (s, 3H); 13C NMR (100 MHz, DMSO) δ 157.8, 133.7, 133.6,
132.2, 131.4, 130.3, 128.1, 127.6, 127.5, 126.5, 125.5, 125.5, 125.1, 123.5, 120.6, 114.2, 108.5,
106.8, 55.2 ppm; IR (KBr)/cm-1 3904, 3785, 3557, 3457, 2921, 1608, 1486, 1250, 1033, 830, 774,
478; HRMS (ESI) m/z: calcd for C21H18NO [M+H] + 300.1383; found: 300.1378.

2,4-diphenyl-3-((trimethylsilyl)ethynyl)-1H-pyrrole (5a)

Yield: 68% (42.8 mg) as a yellow crystal (m.p. = 111-112 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.63; 1H NMR (400 MHz, DMSO) δ 11.74 (s, 1H), 7.97 (d, J = 7.6 Hz, 2H),
7.82 (d, J = 7.6 Hz, 2H), 7.43 (t, J = 7.4 Hz, 2H), 7.37-7.29 (m, 3H), 7.26-7.20 (m, 2H), 0.22 (s,
9H). 13C NMR (100 MHz, DMSO) δ 135.7, 134.8, 131.7, 128.4, 128.2, 127.0, 126.3, 126.2, 125.9,
125.4, 117.2, 103.2, 98.7, 97.3, -0.07 ppm; HRMS (ESI) m/z: calcd for C21H22NSi [M+H]+
316.1516; found: 316.1521.

2,4-diphenyl-3-((triethylsilyl)ethynyl)-1H-pyrrole (5b)

Yield: 71% (50.7 mg) as a yellow crystal (m.p. = 114-115 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.65; 1H NMR (400 MHz, DMSO) δ 11.75 (s, 1H), 8.02 (d, J = 7.6 Hz, 2H),
7.87 (d, J = 7.6 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.31 (q, J = 7.31 Hz, 3H), 7.25-7.19 (m, 2H),
1.01 (t, J = 7.6 Hz, 9H), 0.64 (q, J = 8.0 Hz, 6H). 13C NMR (100 MHz, DMSO) δ 135.8, 134.8,
131.7, 128.3, 128.1, 127.0, 126.3, 126.2, 125.8, 125.4, 117.2, 104.1, 98.9, 94.8, 7.4, 4.1 ppm;
HRMS (ESI) m/z: calcd for C24H28NSi [M+H]+ 358.1986; found: 358.1990.

2,4-diphenyl-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5c)

Yield: 75% (59.9 mg) as a Green crystal (m.p. =150-151 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.70; 1H NMR (400 MHz, DMSO) δ 11.74 (s, 1H), 8.03 (d, J = 8.0 Hz, 2H),
7.88 (d, J = 8.0 Hz, 2H), 7.38 (t, J = 7.6 Hz, 2H), 7.30 (dd, J = 7.6, 1.6 Hz, 3H), 7.24 (d, J = 2.8
Hz, 1H), 7.20 (t, J = 7.2 Hz, 1H), 1.08 (s, 21H). 13C NMR (100 MHz, DMSO) δ 136.3, 135.3,
132.2, 128.8, 128.6, 127.4, 126.9, 126.8, 126.3, 125.9, 117.7, 104.9, 99.5, 93.9, 19.0, 11.5 ppm;
HRMS (ESI) m/z: calcd for C27H34NSi [M+H]+ 400.2455; found: 400.2456.

2,4-bis(4-methoxyphenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5d)

S15
Yield: 70% (64.3 mg) as a yellow crystal (m.p. = 133-134 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.33; 1H NMR (400 MHz, DMSO) δ 11.50 (s, 1H), 7.94 (d, J = 8.4 Hz, 2H),
7.76 (d, J = 8.8 Hz, 2H), 7.06 (d, J = 2.0 Hz, 1H), 6.94 (d, J = 8.4 Hz, 2H), 6.86 (d, J = 8.4 Hz,
2H), 3.78 (s, 3H), 3.75 (s, 3H), 1.08 (s, 21H). 13C NMR (100 MHz, DMSO) δ 158.3, 157.5, 135.8,
127.5, 127.4, 126.8, 126.0, 124.6, 115.6, 113.7, 113.5, 104.9, 97.8, 92.7, 55.2, 55.0, 18.5, 11.0
ppm; HRMS (ESI) m/z: calcd for C29H38NO2Si [M+H]+ 460.2666; found: 460.2662.

2,4-bis(4-fluorophenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5e)

Yield: 78% (67.9 mg) as a yellow crystal (m.p. =122-123 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.50; 1H NMR (400 MHz, DMSO) δ 11.76 (s, 1H), 8.07-8.03 (m, 2H), 7.89-7.86
(m, 2H), 7.22-7.18 (m, 3H), 7.10 (t, J = 8.6 Hz, 2H), 1.05 (s, 21H). 13C NMR (100 MHz, DMSO)
δ 162.1 (d, J = 42.0 Hz), 159.7(d, J = 39.9 Hz), 134.9, 131.2 (d, J = 2.9 Hz), 128.3 (d, J = 3.0 Hz),
128.1 (d, J = 7.6 Hz), 127.5 (d, J = 10.8 Hz), 125.4, 117.0, 115.1 (d, J = 21.2 Hz), 114.7 (d, J =
20.9 Hz), 104.0, 98.9, 93.4, 18.4, 10.9 ppm; HRMS (ESI) m/z: calcd for C27H32F2NSi [M+H]+
436.2267; found: 436.2269.

2,4-bis(4-(tert-butyl)phenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5f)

Yield: 50% (51.1 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 10/1, v/v): Rf = 0.28;
1H NMR (400 MHz, DMSO) δ 11.60 (s, 1H), 7.93 (d, J = 8.2 Hz, 2H), 7.74 (d, J = 8.1 Hz, 2H),

7.38 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 7.13 (s, 1H), 1.28 (d, J = 5.3 Hz, 19H), 1.07 (s,
20H). 13C NMR (101 MHz, DMSO) δ 149.3, 148.0, 135.8, 132.0, 129.0, 126.4, 126.2, 125.3,
125.0, 124.7, 116.4, 104.7, 98.9, 92.9, 34.2, 34.0, 31.1, 31.0, 18.5, 11.0 ppm; IR (KBr)/cm-1 3829,
3672, 3616, 3533, 3359, 2930, 2856, 2136, 1655, 1465, 1257, 1035, 532; HRMS (ESI) m/z: calcd
for C35H50NSi [M+H]+ 512.3707; found: 512.3708.

2,4-bis(4-(trifluoromethyl)phenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5g)

S16
Yield: 82% (87.8 mg) as a colorless crystal (m.p. = 185-186 oC); TLC (petroleum ether/ethyl
acetate = 10/1, v/v): Rf = 0.14; 1H NMR (400 MHz, DMSO) δ 12.16 (s, 1H), 8.21 (d, J = 8.0 Hz,
2H), 8.07 (d, J = 8.0 Hz, 2H), 7.71 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 2.0
Hz, 1H), 1.05 (d, J = 4.4 Hz, 21H). 13C NMR (100 MHz, DMSO) δ 138.7, 135.3, 134.4, 127.3,
127.0, 126.7, 126.5, 126.2, 125.8, 125.6, 125.3 (q, 4.4Hz), 125.0 (q, J = 3.6 Hz), 123.1, 122.9,
119.8,103.2, 100.7, 95.2, 18.4, 10.9 ppm; IR (KBr)/cm-1 3406, 2943, 2867, 2139, 1614, 1326,
1125, 844, 771, 668, 581; HRMS (ESI) m/z: calcd for C29H32F6NSi [M+H]+ 536.2203; found:
536.2208.

2,4-di(naphthalen-2-yl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5h)

Yield: 70% (69.9 mg) as a yellow crystal (m.p. = 153-154 oC); TLC (petroleum ether/ethyl acetate
= 10/1, v/v): Rf = 0.50; 1H NMR (400 MHz, DMSO) δ 11.99 (s, 1H), 8.50 (s, 1H), 8.44 (s, 1H),
8.25 (d, J = 8.8 Hz, 1H), 8.04 (d, J = 8.4 Hz, 1H), 7.93 (t, J = 9.0 Hz, 2H), 7.88-7.80 (m, 4H),
7.56-7.41 (m, 5H), 1.15-1.08 (m, 21H). 13C NMR (100 MHz, DMSO) δ 136.1, 133.2, 133.0, 132.4,
131.9, 131.6, 129.3, 127.8, 127.7, 127.6, 127.6, 127.5, 127.3, 126.5, 126.5, 126.0, 125.9, 125.7,
125.2, 124.1, 123.7, 123.7, 118.4, 104.4, 99.5, 93.6, 18.6, 11.0 ppm; HRMS (ESI) m/z: calcd for
C35H38NSi [M+H]+ 500.2768; found: 500.2773.

2-methyl-3,5-diphenyl-4-((triisopropylsilyl)ethynyl)-1H-pyrrole (5i)

Yield: 53% (43.8 mg) as a yellow oil; TLC (petroleum ether/ethyl acetate = 10/1, v/v): Rf = 0.31;
1H NMR (400 MHz, DMSO) δ 11.40 (s, 1H), 8.04 (d, J = 7.6 Hz, 2H), 7.51 (d, J = 7.6 Hz, 2H),

7.37-7.31 (m, 4H), 7.22 (q, J = 7.22 Hz, 2H), 2.30 (s, 3H), 1.02 (s, 21H). 13C NMR (100 MHz,
DMSO) δ 134.7, 132.9, 131.8, 128.8, 128.2, 127.7, 126.4, 125.8, 125.5, 125.0, 123.7, 104.5, 100.3,
92.3, 18.4, 11.8, 10.9 ppm; IR (KBr)/cm-1 3849, 2931, 2858, 2138, 1664, 1607, 1395, 1267, 1108,
999, 764, 673; HRMS (ESI) m/z: calcd for C28H36NSi [M+H]+ 414.2612; found: 414.2615.

8. Mechanistic Studies
Radical control experiments

S17
For (eq1), in a 25 mL sealed test tube, Cu NPs (30 mol %), TEMPO (0.25 mmol, 2.5 equiv), 4 mL
of DCE, 1-ethynyl-4-methoxybenzene 1a (0.1 mmol) and (1-azidovinyl)benzene 2a (0.18 mmol,
1.8 equiv) was added in sequence. The reaction mixture was sealed under a nitrogen atmosphere
and vigorously stirred together at 135 oC for 3 h. The reaction mixture was diluted with CH2Cl2
and monitored by GCMS after filtration.
For (eq2), in a 25 mL sealed test tube, Cu NPs (30 mol %), TEMPO (0.25 mmol, 2.5 equiv), 4 mL
of DCE, 1-ethynyl-4-methoxybenzene 1w (0.1 mmol) and (1-azidovinyl)benzene 2a (0.25 mmol,
2.5 equiv) was added in sequence. The reaction mixture was sealed under a nitrogen atmosphere
and vigorously stirred together at 135 oC for 3 h. The reaction mixture was diluted with CH2Cl2
and monitored by GCMS after filtration.

9. References
(1) Xiang, L.; Niu, Y.; Pang, X.; Yang, X.; Yan, R. Chem. Commun. 2015, 51, 6598-6600;
(2) Zhang, F.-L.; Wang, Y.-F.; Lonca, G. H.; Zhu, X.; Chiba, S. Angew. Chem., Int. Ed. 2014, 53,
4390-4394;
(3) Li, J.; He, W.; Wang, S.; Zhou, G.; Tan, Z. Electron Compounds and Materials 2015, 34,
27-30.

S18
 10. NMR Spectra of Quinoline Products
2-(4-Methoxyphenyl)-5-phenyl-1H-pyrrole (3a)

S19
2-Phenyl-5-(p-tolyl)-1H-pyrrole (3b)

S20
4-(5-Phenyl-1H-pyrrol-2-yl)aniline (3c)

N Ph
H2N H

N Ph
H2N H

S21
N, N-dimethyl-4-(5-phenyl-1H-pyrrol-2-yl)aniline (3d)

S22
2-(4-Fluorophenyl)-5-phenyl-1H-pyrrole (3e)

S23
S24
2-(4-Chlorophenyl)-5-phenyl-1H-pyrrole (3f)

S25
2-Phenyl-5-(4-(trifluoromethyl)phenyl)-1H-pyrrole (3g)

S26
S27
2-Phenyl-5-(o-tolyl)-1H-pyrrole (3h)

S28
2-Phenyl-5-(m-tolyl)-1H-pyrrole (3i)

S29
2-(3-Fluorophenyl)-5-phenyl-1H-pyrrole (3j)

S30
S31
2-(Naphthalen-2-yl)-5-phenyl-1H-pyrrole (3k)

S32
2-Phenyl-5-(thiophen-2-yl)-1H-pyrrole (3l)

S33
2-Cyclopropyl-5-phenyl-1H-pyrrole (3m)

S34
2-Cyclopentyl-5-phenyl-1H-pyrrole (3n)

S35
2-Cyclohexyl-5-phenyl-1H-pyrrole (3o)

S36
2-(Tert-butyl)-5-phenyl-1H-pyrrole (3p)

S37
2-Isopentyl-5-phenyl-1H-pyrrole (3q)

S38
2-Hexyl-5-phenyl-1H-pyrrole (3r)

S39
2-Phenyl-5-(3-phenylpropyl)-1H-pyrrole (3s)

S40
4-(5-Phenyl-1H-pyrrol-2-yl)butanenitrile (3t)

S41
2-(4-Chlorobutyl)-5-phenyl-1H-pyrrole (3u)

S42
2-(4-Methoxyphenyl)-5-(p-tolyl)-1H-pyrrole (4a)

N
MeO H Me

N
MeO H Me

S43
2-(4-(Tert-butyl)phenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4b)

S44
 161.665
159.256
157.685
131.309

125.604
125.527
125.506
125.335
115.456

114.060
107.401
106.394

S45
2-(4-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4c)

55.066
40.126
39.918
39.709
39.500
39.292
39.083
38.875
S46
2-(4-Chlorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4d)

S47
2-(4-Bromophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4e)

S48
2-(4-Methoxyphenyl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrrole (4f)

S49
S50
4-(5-(4-methoxyphenyl)-1H-pyrrol-2-yl)benzonitrile (4g)

S51
4-(5-(4-Methoxyphenyl)-1H-pyrrol-2-yl)phenyl acetate (4h)

S52
2-(4-Methoxyphenyl)-5-(m-tolyl)-1H-pyrrole (4i)

S53
 164.034
161.632
157.887
133.833

130.932
130.457
130.369
125.290
119.666
114.087
111.850
111.640
110.083

S54
109.854
108.673
106.627
2-(3-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4j)

55.070
40.127
39.918
39.709
39.500
39.291
39.082
38.874
S55
 159.547
157.964
157.093

133.489
126.939
126.865
125.836
125.349
124.511

S56
120.697
115.938
111.564
106.609
2-(2-Fluorophenyl)-5-(4-methoxyphenyl)-1H-pyrrole (4k)

55.127
40.127
39.918
39.709
39.500
39.291
39.082
38.872
S57
2-(4-Methoxyphenyl)-5-(naphthalen-2-yl)-1H-pyrrole (4m)

S58
2,4-diphenyl-3-((trimethylsilyl)ethynyl)-1H-pyrrole (5a)

S59
2,4-diphenyl-3-((triethylsilyl)ethynyl)-1H-pyrrole (5b)

S60
2,4-diphenyl-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5c)

S61
2,4-bis(4-methoxyphenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5d)

S62
2,4-bis(4-fluorophenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5e)

S63
S64
2,4-bis(4-(tert-butyl)phenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5f)

t-Bu
TIPS

H N
H t-Bu

t-Bu
TIPS

H N
H t-Bu

S65
2,4-bis(4-(trifluoromethyl)phenyl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5g)

S66
S67
2,4-di(naphthalen-2-yl)-3-((triisopropylsilyl)ethynyl)-1H-pyrrole (5h)

S68
2-methyl-3,5-diphenyl-4-((triisopropylsilyl)ethynyl)-1H-pyrrole (5i)

S69
 11. X-ray Crystallographic Data
Single-crystal X-ray diffraction data for 3ac were collected on a Rigaku Mercury CCD
diffractometer operated at 90 kV and 50 mA using MoKα radiation ( = 0.71073 Å) at the
temperature 100.00(10)K. All empirical absorption corrections were performed using the
CrystalClear program. The structure was solved by a direct method and refined on F2 by the
full-matrix least squares technique using the SHELXTL-97 program package. All non-hydrogen
atoms were refined with anisotropic displacement parameters. Hydrogen atoms attached to carbon
were placed in geometrically idealized positions and refined using a riding model.
Crystallographic data for compound 3ac is given in Table S1. Metrical parameters for the
structures of 3ac are available free of charge from the Cambridge Crystallographic Data Centre
under accession numbers CCDC-1865535, respectively.

Figure S1. X-ray crystal structure of compound 5c

Table S1. Crystal data and structure refinements for 5c

Compound 5c
Empirical formula C27H33NSi
Formula weight 399.63
Temperature (K) 100.01(10)
Wavelength (Å) 0.71073
Crystal system Orthorhombic
Space group Pna21

a = 15.8494(5)Å α = 90

b = 16.5920(5)Å β = 90

c = 17.8554(8)Å γ = 90
S70
Volume (Å3) 4695.5(3)
Z 8
Density (calcd g cm-3) 1.131
Absorption coeff. (mm-1) 0.113
F(000) 1728.0
Crystal size (mm) 0.14 × 0.13 × 0.12
Crystal color and shape Colorless block
2θ range for data collection 4.224 to 63.286 deg.
Limiting indices -16 ≤ h ≤ 22, -22 ≤ k ≤ 23, -22 ≤ l ≤ 21
Reflections collected 25969
Unique 10291 [R(int) = 0.0436, R(sigma) = 0.0589]
Refinement method Full-matrix least-squares on F2
Data/restraints/parameters 10291/3/551
Goodness-of-fit on F2 1.041
Final R indexes [I>=2σ (I)] R1 = 0.0536, wR2 = 0.1209
R indexes (all data) R1 = 0.0689, wR2 = 0.1314

12. GC-MS Analysis of NH Imine Generated from Copper Intermediate VI

F:\CJH\experement 2\2-871 9/22/2018 2:42:48 PM

RT: 0.00 - 21.06

5.35 NL:
100 1.30E9
TIC MS
90 2-871

80
19.69
70
Relative Abundance

60 11.76

50

40 4.46

30 11.39

20
4.76
10 20.69
11.84 12.79 12.86 16.79
5.56 6.13 6.73 7.44 7.79 8.49 9.35 10.55 10.73 13.70 14.01 15.75 16.36 17.60 17.85 18.88 20.16
3.20 3.47 4.19
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Time (min)

2-871 #554 RT: 11.76 AV: 1 NL: 1.29E8

T: {0,0} + c EI Full ms [50.00-600.00]
256.20
100

90

80

70
Relative Abundance

60

50

40
214.15
30 186.11 299.25
257.22
74.12
20
100.35 169.10
60.10 197.14 228.14 300.24
10 99.84 258.20
104.12 143.08 155.08 229.18 301.25
284.22 341.04 355.15 370.29 401.06 415.06 429.23 443.21 475.17 489.21 514.21 527.29 555.30 581.24 595.20
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580
m/z

S71