• Supporting Information

One-Pot Three-Component Synthesis of Enamine-Functionalized

1,2,3-Triazoles via Cu-Catalytic Azide-Alkyne Click (CuAAC) and

Cu-Catalyzed Vinyl Nitrene Transfer Sequence

Wei Zhou,ab Min Zhang,a Hanhui Li,a and Wanzhi Chen*a

a
Department of Chemistry, Zhejiang University, Hangzhou 310028, China.
b
College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou
310014, China.
Email: chenwzz@zju.edu.cn

I. General Information................................................................................2
II. Experimental Section……………………………………..…………….2
1. Synthesis of starting materials 3………………………………………..2
2. Optimization of Reaction Conditions………………………………….5
3. General procedure for the synthesis of 4……………………………....6
4. Scale-up synthesis of product 4q……………………………...............16
5. Transformation experiments of 4q and 4a…………..……………......16
III. References……………………………………………………………......18
1
IV. H, 13C and 19F NMR Spectra of 2H-Azirines (3a~3h)……………….…19
1
V. H, 13C and 19F NMR Spectra of products (4a~4y)…….………………28
1
VI. H and 13C Spectra of 5a and 5b……………………….…………….....57

1
I. General Information.

1
H NMR spectra were recorded in deuterated solvents on a Bruker 400 (400 MHz)
spectrometer and calibrated to the residual solvent peak or tetramethylsilane (δ = 0
ppm). Multiplicities are abbreviated as follows: s = singlet, d = doublet, t = triplet, q =
quartet, m = multiplet, dd = doublet of doublet, dt = doublet of triplet, br = broad. J-
values are in Hz. HRMS was measured by a Finnigan MA+ mass spectrometer or a
GCT Premier (7000FWHM). Organic solvents used were dried by standard methods
when necessary. Commercially obtained reagents were used without further
purification. All reactions were monitored by TLC with Huanghai GF254 silica gel
coated plates. Flash column chromatography was carried out using 300-400 mesh
silica gel at increased pressure. All reactions were performed under nitrogen using
standard Schlenk techniques.

II. Experimental Section

1. Synthesis of starting materials 3
The preparation and the chemistry of 2H-Azirines have been fully documented.
Herein, 2H-Azirines 3a~3h were readily prepared from phenylethylenes in 0.5-3.5 g
scale according to the known procedures.1-3
Note: 2H-Azirines are reactive in nature and they should be stored at low
temperature and in dark place. 2H-Azirines 3a~3h prepared here are of high purity
and they were found to be stable for two months in refrigerator (0~5 oC). However,
2H-Azirines, especially those in the form of liquid, were found to decompose and
polymerize slowly when stored at room temperature.

3-phenyl-2H-azirine (3a)
Light yellow oil; 1H NMR (400 MHz, CDCl3): δ = 7.91 (d, J = 7.2 Hz, 2H), 7.59 (t, J

2
 13
= 6.8, Hz, 3H), 1.80 (s, 2H). C NMR (100 MHz, CDCl3): δ = 165.8, 132.9, 129.6,
129.1, 125.5, 19.7.

3-(p-tolyl)-2H-azirine (3b)
Light yellow oil; 1H NMR (400 MHz, CDCl3): δ = 7.79 (d, J = 8.0 Hz, 2H), 7.36 (d, J
13
= 8.0 Hz, 2H), 2.45 (s, 3H), 1.75 (s, 2H). C NMR (100 MHz, CDCl3): δ = 165.3,
143.7, 129.8, 129.6, 122.8, 21.8, 19.5.

3-(4-(tert-butyl)phenyl)-2H-azirine (3c)
Light yellow oil; 1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 8.0 Hz, 2H), 7.58 (d, J
13
= 8.0 Hz, 2H), 1.76 (s, 2H), 1.37 (s, 9H). C NMR (100 MHz, CDCl3): δ = 165.2,
156.7, 129.5, 126.1, 122.7, 35.2, 31.1, 19.4.

3-(4-fluorophenyl)-2H-azirine (3d)
Light yellow oil; 1H NMR (400 MHz, CDCl3): δ = 7.92 (m, 2H), 7.26 (m, 2H), 1.80 (s,
13
2H). C NMR (100 MHz, CDCl3): δ = 165.5 (J = 253.7 Hz), 164.7, 131.9 (J = 9.9
19
Hz), 121.9 (J =2.6Hz), 116.5 (J =22.2Hz), 19.8. F NMR (376 MHz, CDCl3): δ = -
104.7

3
3-(4-chlorophenyl)-2H-azirine (3e)
White solid; 1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 7.2 Hz, 2H), 7.54 (d, J =
13
7.2 Hz, 2H), 1.80 (s, 2H). C NMR (100 MHz, CDCl3): δ = 165.1, 139.2, 130.7,
129.5, 124.0, 19.9.

3-(4-bromophenyl)-2H-azirine (3f)
White solid; 1H NMR (400 MHz, CDCl3): δ = 7.77 (m, 2H), 7.70 (m, 2H), 1.80 (m,
2H). 13C NMR (100 MHz, CDCl3): δ = 165.3, 132.5, 130.8, 127.8, 124.4, 19.9.

3-(2-chlorophenyl)-2H-azirine (3g)
Light yellow oil; 1H NMR (400 MHz, CDCl3): δ = 7.85 (m, 1H), 7.56-7.43 (m, 3H),
13
1.84 (m, 2H). C NMR (100 MHz, CDCl3): δ = 164.8, 136.1, 133.5, 132.3, 130.6,
127.2, 123.9, 20.1.

2,3-diphenyl-2H-azirine (3h)
White solid; 1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J = 6.8 Hz, 2H), 7.60-7.51 (m,

4
 13
3H), 7.29-7.16 (m, 3H), 7.14 (d, J = 6.8 Hz, 2H), 3.32 (s, 1H). C NMR (100 MHz,
CDCl3): δ = 163.5, 140.9, 133.2, 129.9, 129.3, 128.3, 127.1, 126.1, 124.1, 34.5.

2. Optimization of Reaction Conditions

Table S1. Reaction Conditions Screening

Entry Cat.(10 mol %) base solvent T (ºC) Yield a (%)

1 CuI DIEA, 1.2 eq CH2Cl2 rt. 47
2 CuI DIEA, 1.2 eq CH2Cl2 -20~-10 82
3 CuI DIEA, 1.2 eq CH2Cl2 0~rt 85
4 CuBr DIEA, 1.2 eq CH2Cl2 0~rt 76
5 CuCl DIEA, 1.2 eq CH2Cl2 0~rt 79
6 Cu(OAc)2 DIEA, 1.2 eq CH2Cl2 0~rt 42
7 CuCl2 DIEA, 1.2 eq CH2Cl2 0~rt 75
8 CuI Et3N, 1.2 eq CH2Cl2 0~rt 79
9 CuI DIEA, 1.2 eq CHCl3 0~rt 70
10 CuI DIEA, 1.2 eq THF 0~rt 82
11 CuI DIEA, 1.2 eq toluene 0~rt 65
12 CuI DIEA, 0.2 eq CH2Cl2 0~rt 73
13 CuI - CH2Cl2 0~rt 40
14b CuI DIEA, 1.2 eq CH2Cl2 0~rt 75
15c CuI DIEA, 1.2 eq CH2Cl2 0~rt 71
Reaction conditions: 1a (0.65 mmol), 2a (0.6 mmol), 3a (0.5 mmol), Catalyst (10 %
mol), base, solvent (1 mL), under N2; all reagents except 3a were added and mixed
for 30 min on ice-water bath, then 3a was added into the reaction mixture and mixed
for 11.5 h. a isolated yield. b
the molar ratio of substrates =1/1/1. c all reagents were
added at once and mixed for 12 h.

5
3. General procedure for the synthesis of 4
To a flame-dried Schlenk tube were added 4-methyphenylenthyne 1a (0.65 mmol,
1.3 equiv) and CuI (0.005 mmol, 0.01 equiv). The tube was evacuated and filled with
N2 for 3 times. DCM (1.0 mL), TsN3 2a (0.6 mmol, 1.2 equiv) and DIEA (0.6 mmol,
1.2 equiv) was added to this tube via a syringe under N2. Then the reaction mixture
was stirred for 30 mins in an ice-water bath, followed by the addition of 3-phenyl-2H-
azirine 3a (0.5 mmol) via a syringe. The mixture was stirred at 0 oC~ rt for another
11.5 h (during the reaction time, the temperature of ice-water bath rose up slowly to
rt). The reaction mixture was directly transformed to the silica gel column, eluted with
the mixture of petroleum and ethyl acetate (v/v = 4/1) to afford the desired product 4a
as white solid.
Products 4b-4y were prepared with the same procedure.

N-(1-phenylvinyl)-4-(p-tolyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4a)

White solid, 0.1830 g, yield 85%; mp: 136-137 oC; 1H NMR (400 MHz, CDCl3): δ
7.91 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.62-7.60 (m, 2H), 7.45 (m, 3H),
7.28 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 5.80 (s, 1H), 3.55 (s, 2H), 2.40 (s,
3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 147.3, 146.5, 142.3, 138.5, 138.2,
134.1, 131.1, 130.1, 129.7, 129.3, 128.9, 128.5, 127.2, 126.6, 126.1, 81.9, 21.8, 21.4;
HRMS (GC-TOF) for C24H22N4O2S: calcd. 430.1463, Found 430.1478.

4-(4-methoxyphenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4b)

Light yellow solid, 0.1780 g, yield 80%; mp: 213-216 oC; 1H NMR (400 MHz,
CDCl3): δ 7.91 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.8 Hz, 2H), 7.62 (m, 2H), 7.47-7.46

6
(m, 3H), 7.28 (d, J = 8.0 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 5.81 (s, 1H), 3.81 (s, 3H),
3.56 (s, 2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.8, 147.2, 146.5, 142.1,
138.2, 134.1, 130.6, 130.1, 129.7, 128.9, 128.4, 128.1, 126.1, 122.5, 114.0, 81.9, 55.3,
21.8; HRMS (GC-TOF) for C24H22N4O3S: calcd. 446.1413, Found 446.1408.

4-(4-butylphenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4c)
Yellow solid, 0.1962 g, yield 83%; mp: 86-88 oC; 1H NMR (400 MHz, CDCl3): δ 7.91
(d, J = 7.6 Hz, 2H), 7.78 (d, J = 7.6 Hz, 2H), 7.62-7.61 (m, 2H), 7.47-7.46 (m, 3H),
7.28 (d, J = 8.0Hz, 2H), 7.19 (d, J = 7.6 Hz, 2H), 5.81 (s, 1H), 3.55 (s, 2H), 2.60 (t, J
= 7.2 Hz, 2H), 2.41 (s, 3H), 1.59 (quint, J = 7.2 Hz, 2H), 1.33 (sext, J = 7.2 Hz, 2H),
0.91 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 147.3, 146.5, 143.6, 142.3,
138.2, 134.1, 131.1, 130.1, 129.7, 128.9, 128.7, 128.5, 127.3, 126.6, 126.2, 81.9, 35.5,
33.4, 22.4, 21.8, 13.9; HRMS (GC-TOF) for C27H28N4O2S: calcd. 472.1933, Found
472.1924.

4-(4-fluorophenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4d)

White solid, 0.1140 g, yield 52%; mp: 146-148 oC; 1H NMR (400 MHz, CDCl3): δ
7.92 (d, J = 8.0 Hz, 2H), 7.88-7.85 (m, 2H), 7.62-7.61 (m, 2H), 7.48-7.47 (m, 3H),
7.29 (d, J = 8.4 Hz, 2H), 7.07 (t, J = 8.4 Hz, 2H), 5.79 (s, 1H), 3.56 (s, 2H), 2.41 (s,
13
3H); C NMR (100 MHz, CDCl3): δ 162.8 (d, J = 246.8 Hz), 147.4, 146.6, 141.5,
137.9, 134.0, 131.2, 130.1, 129.8, 129.0, 128.5 (d, J = 8.6 Hz), 128.5, 126.2 (d, J =
3.2 Hz), 126.1, 115.6 (d, J = 21.2 Hz), 81.5, 21.8; 19F NMR (376 MHz, CDCl3): δ = -
112.3; HRMS (GC-TOF) for C23H19FN4O2S: calcd. 434.1213, Found 434.1219.

7
4-(4-chlorophenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4e)
Yellow solid, 0.1521 g, yield 67%; mp: 135-138 oC; 1H NMR (400 MHz, CDCl3): δ
7.92 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.0 Hz, 2H), 7.62 (m, 2H), 7.48 (m, 3H), 7.35 (d,
J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 5.79 (s, 1H), 3.58 (s, 2H), 2.41(s, 3H); 13C
NMR (100 MHz, CDCl3): δ 147.6, 146.7, 141.2, 137.9, 134.4, 133.9, 131.5, 130.2,
129.9, 129.0, 128.8, 128.5, 128.5, 127.9, 126.1, 81.4, 21.8; HRMS (GC-TOF) for
C23H19ClN4O2S: calcd. 450.0917, Found 450.0922.

4-(4-bromophenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4f)

Yellow solid, 0.1470 g, yield 59%; mp: 132-134 oC. 1H NMR (400 MHz, CDCl3): δ
7.92 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.62-7.61 (m, 2H), 7.51-7.47 (m,
13
5H), 7.29 (d, J = 8.0 Hz, 2H), 5.78 (s, 1H), 3.59 (s, 2H), 2.41(s, 3H); C NMR (100
MHz, CDCl3): δ 147.6, 146.7, 141.2, 137.9, 133.9, 131.8, 131.6, 130.2, 129.9, 129.0,
128.9, 128.5, 128.2, 126.1, 122.7, 81.3, 21.8; HRMS (GC-TOF) for C23H19BrN4O2S:
calcd. 494.0412, Found 494.0415.

4-phenyl-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4g)

Off-white solid, 0.1020 g, yield 49%; mp: 126-129 oC; 1H NMR (400 MHz, CDCl3):
δ 7.91 (d, J = 8.0 Hz, 2H), 7.87 (d, J = 8.0 Hz, 2H), 7.62-7.61 (m, 2H), 7.47 (m, 3H),
13
7.38-7.26 (m, 5H), 5.81 (s, 1H), 3.55 (s, 2H), 2.41(s, 3H); C NMR (100 MHz,
CDCl3): δ 147.4, 146.5, 142.2, 138.1, 134.0, 131.5, 130.1, 130.0, 129.7, 128.9, 128.6,
8
128.6, 128.4, 126.6, 126.1, 81.6, 21.8; HRMS (GC-TOF) for C23H20N4O2S: calcd.
416.1307, Found 416.1308.

4-(4-acetylphenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4h)

Light yellow solid, 0.0981 g, yield 43%; mp: 127-129 oC; 1H NMR (400 MHz,
CDCl3): δ 8.02-7.96 (m, 4H), 7.94 (d, J = 8.0 Hz, 2H), 7.65-7.62 (m, 2H), 7.50-7.48
(m, 3H), 7.31 (d, J = 8.0 Hz, 2H), 5.83 (s, 1H), 3.59 (s, 2H), 2.60 (s, 3H), 2.42 (s, 3H);
13
C NMR (100 MHz, CDCl3): δ 197.6, 147.9, 146.8, 141.1, 137.8, 136.6, 134.6, 133.9,
132.4, 130.2, 129.9, 129.1, 128.6, 128.5, 126.6, 126.1, 81.2, 26.6, 21.8; HRMS (ESI):
m/z (M+H)+ for C25H22N4O3S: calcd. 459.1485, Found 459.1447.

N-(1-phenylvinyl)-4-(o-tolyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4i)

Yellow viscous solid, 0.1291 g, yield 60%; 1H NMR (400 MHz, CDCl3): δ 7.95 (d, J
= 8.0 Hz, 2H), 7.52-7.51 (m, 2H), 7.46-7.41 (m, 5H), 7.32 (d, J = 8.0 Hz, 2H), 7.27-
7.26 (m, 1H), 7.21 (t, J = 6.0 Hz, 1H), 5.88 (s, 1H), 3.46 (s, 2H), 2.43 (s, 3H), 2.29 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 147.7, 146.6, 142.0, 138.6, 137.7, 134.1, 133.8,
130.7, 130.2, 130.0, 129.7, 129.6, 129.1, 128.8, 128.5, 126.2, 126.1, 81.9, 21.8, 20.3;
HRMS (ESI): m/z (M+H)+ for C24H22N4O2S: calcd. 431.1536, Found431.1537.

N-(1-phenylvinyl)-4-(m-tolyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4j)

Off-white solid; 0.1580 g, yield 73%, mp: 134-136 oC; 1H NMR (400 MHz, CDCl3):

9
δ 7.92 (d, J = 8.0 Hz, 2H), 7.73 (s, 1H), 7.64-7.61 (m, 3H), 7.46 (m, 3H), 7.28 (d, J =
7.6 Hz, 2H), 7.26 (t, J = 7.6 Hz, 1H), 7.14 (d, J = 7.6 Hz, 2H), 5.80 (s, 1H), 3.54 (s,
2H), 2.40 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 147.4, 146.5, 142.4,
138.3, 138.2, 134.1, 131.5, 130.1, 129.9, 129.7, 129.4, 128.9, 128.5, 128.4, 127.4,
126.1, 123.7, 81.8, 21.8, 21.5; HRMS (GC-TOF) for C24H22N4O2S: calcd. 430.1463,
Found 430.1462.

4-(3-aminophenyl)-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4k)

Light yellow solid, 0.1021 g, yield 47%; mp: ˃250 oC; 1H NMR (400 MHz, DMSO-
d6): δ 7.87 (d, J = 8.4 Hz, 2H), 7.61 (m, 2H), 7.47 (m, 5H), 7.11 (s, 1H), 7.01 (t, J =
7.6 Hz, 1H), 6.93 (d, J = 7.6 Hz, 1H), 6.55 (d, J = 7.2 Hz, 1H), 5.30 (s, 1H), 5.14 (s,
13
2H), 5.08 (s, 2H), 2.40 (s, 3H); C NMR (100 MHz, DMSO-d6): δ 149.5, 149.1,
147.2, 142.6, 138.7, 133.8, 132.4, 131.1, 130.9, 129.7, 129.4, 129.0, 128.4, 126.9,
114.5, 112.4, 77.6, 21.7; HRMS (ESI): m/z (M+H)+ for C23H21N5O2S: calcd. 432.1489,
Found 432.1485.

4-(naphthalen-2-yl)-N-(1-phenylvinyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4l)
Off-white solid, 0.1430 g, yield 61%; mp: 151-153 oC; 1H NMR (400 MHz, CDCl3):
δ 8.31 (s, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.94 (d, J = 7.2 Hz, 2H), 7.84-7.79 (m, 3H),
7.63 (m, 2H), 7.47 (m, 5H), 7.29 (d, J = 7.2 Hz, 2H), 5.88 (s, 1H), 3.56 (s, 2H), 2.40
13
(s, 3H); C NMR (100 MHz, CDCl3): δ 147.6, 146.6, 142.2, 138.2, 134.1, 133.3,
133.2, 131.8, 130.2, 129.8, 129.0, 128.5, 128.4, 128.2, 127.7, 127.5, 126.6, 126.4,
126.2, 126.1, 124.3, 81.7, 21.8; HRMS (ESI): m/z (M+H)+ for C27H22N4O2S: calcd.
467.1536, Found 467.1512.
10
4-cyclopropyl-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4m)
Light yellow solid; 0.0785 g, yield 41%, mp: 131-133 oC; 1H NMR (400 MHz,
CDCl3): δ 7.88 (d, J = 8.0 Hz, 2H), 7.67-7.64 (m, 2H), 7.46-7.45 (m, 3H), 7.28 (d, J =
8.0 Hz, 2H), 5.60 (s, 1H), 3.93 (s, 2H), 2.41 (s, 3H), 1.79-1.76 (m, 1H), 1.12-1.10 (m,
13
2H), 1.02-0.97 (m, 2H); C NMR (100 MHz, CDCl3): δ 147.5, 146.3, 145.4, 138.2,
134.2, 132.0, 130.0, 129.6, 128.9, 128.3, 126.2, 82.2, 21.8, 7.6, 7.2; HRMS (GC-TOF)
for C20H20N4O2S: calcd. 380.1307, Found 380.1311.

4-hexyl-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4n)

Yellow viscous solid, 0.1410 g, yield 66%; 1H NMR (400 MHz, CDCl3): δ 7.89 (d, J
= 8.0 Hz, 2H), 7.63-7.62 (m, 2H), 7.47-7.45 (m, 3H), 7.28 (d, J = 8.4 Hz, 2H), 5.47 (s,
1H), 3.61 (s, 2H), 2.61 (t, J = 7.6 Hz, 2H), 2.41 (s, 3H), 1.70-1.66 (m, 2H), 1.26 (m,
13
6H), 0.83 (t, J = 6.8 Hz, 3H); C NMR (100 MHz, CDCl3): δ 147.5, 146.4, 145.6,
137.9, 134.2, 131.7, 130.1, 129.6, 128.9, 128.3, 126.1, 82.3, 31.5, 28.9, 28.4, 25.8,
22.5, 21.8, 14.0; HRMS (GC-TOF) for C23H28N4O2S: calcd. 424.1933, Found
424.1936.

4-butyl-N-(1-phenylvinyl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4o)

Yellow solid, 0.1253 g, yield 63%; mp:62-65 oC; 1H NMR (400 MHz, CDCl3): δ 7.89
(d, J = 7.6 Hz, 2H), 7.64-7.62 (m, 2H), 7.47-7.45 (m, 3H), 7.28 (d, J = 8.0 Hz, 2H),

11
5.48 (s, 1H), 3.61 (s, 2H), 2.62 (t, J = 8.0 Hz, 2H), 2.41 (s, 3H), 1.67 (quint, J = 8.0
13
Hz, 2H), 1.31 (m, J = 7.6 Hz, 2H), 0.88 (t, J = 7.2 Hz, 3H); C NMR (100 MHz,
CDCl3): δ 147.6, 146.4, 145.5, 137.9, 134.1, 131.7, 130.1, 129.6, 128.9, 128.3, 126.1,
82.3, 30.6, 25.5, 22.4, 21.8, 13.8; HRMS (GC-TOF) for C21H24N4O2S: calcd.
396.1620, Found 396.1621.

N-(1-phenylvinyl)-4-(thiophen-2-yl)-1-tosyl-1H-1, 2, 3-triazol-5-amine (4p)

Yellow solid, 0.1603 g, yield 76%; mp:198-200 oC; 1H NMR (400 MHz, CDCl3): δ
7.91 (d, J = 8.4 Hz, 2H), 7.66-7.64 (m, 2H), 7.49-7.48 (m, 3H), 7.34 (d, J = 3.6 Hz,
1H), 7.32-7.28 (m, 3H), 7.05 (dd, J = 3.6 Hz, J = 4.8 Hz, 1H), 5.68 (s, 1H), 3.68 (s,
2H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 148.4, 146.7, 138.8, 138.0, 133.9,
131.3, 130.2, 130.0, 129.9, 129.0, 128.5, 127.5, 126.3, 126.2, 126.0, 81.3, 21.8;
HRMS (GC-TOF) for C21H18N4O2S2: calcd. 422.0871, Found 422.0872.

4-(p-tolyl)-N-(1-(p-tolyl)vinyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4q)
Yellow solid, 0.1701 g, yield 77%; mp: 178-180 oC; 1H NMR (400 MHz, CDCl3): δ
7.89 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H), 7.26 (d, J
= 7.6 Hz, 4H), 7.16 (d, J = 8.0 Hz, 2H), 5.77 (s, 1H), 3.53 (s, 2H), 2.41 (s, 3H), 2.38
13
(s, 3H), 2.33 (s, 3H); C NMR (100 MHz, CDCl3): δ 147.3, 146.5, 142.2, 139.8,
138.5, 135.3, 134.1, 131.3, 130.1, 129.6, 129.3, 128.4, 127.2, 126.6, 126.0, 81.1, 21.8,
21.4, 21.3; HRMS (ESI): m/z (M+H)+ for C25H24N4O2S: calcd. 445.1693, Found
445.1677.

12
N-(1-(4-(tert-butyl)phenyl)vinyl)-4-(p-tolyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4r)
Light yellow solid, 0.1681 g, yield 69%; mp: 137-139 oC; 1H NMR (400 MHz,
CDCl3): δ 7.92 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.4 Hz, 2H),
7.49 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 5.83 (s,
13
1H), 3.53 (s, 2H), 2.41 (s, 3H), 2.34 (s, 3H), 1.38 (s, 9H); C NMR (100 MHz,
CDCl3): δ 153.0, 147.1, 146.4, 142.2, 138.5, 135.3, 134.2, 131.3, 130.1, 129.3, 128.5,
127.2, 126.6, 125.9, 125.9, 81.4, 34.8, 31.3, 21.8, 21.4; HRMS (GC-TOF) for
C28H30N4O2S: calcd. 486.2089, Found 486.2084.

N-(1-(4-fluorophenyl)vinyl)-4-(p-tolyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4s)
Off-white solid, 0.1371 g, yield 61%; mp: 134-136 oC; 1H NMR (400 MHz, CDCl3):
δ 7.89 (d, J = 7.2 Hz, 2H), 7.73 (d, J = 6.8 Hz, 2H), 7.62-7.59 (m, 2H), 7.28 (d, J =
7.2Hz, 2H), 7.18 (d, J = 7.2 Hz, 2H), 7.16-7.12 (m, 2H), 5.73 (s, 1H), 3.52 (s, 2H),
13
2.40(s, 3H), 2.34 (s, 3H); C NMR (100 MHz, CDCl3): δ 163.6 (d, J = 247.6 Hz),
146.6, 146.3, 142.3, 138.6, 134.2 (d, J = 2.4 Hz), 134.1, 130.9, 130.1, 129.4, 128.4,
128.0 (d, J = 9.0 Hz), 127.1, 126.6, 115.9 (d, J = 21.6 Hz), 82.0, 21.8, 21.4; 19F NMR
(376 MHz, CDCl3): δ = -111.2; HRMS (GC-TOF) for C24H21FN4O2S: calcd. 448.1369,
Found 448.1364.

N-(1-(4-chlorophenyl)vinyl)-4-(p-tolyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4t)
13
Light yellow solid, 0.1760 g, yield 76%; mp: 142-144 oC; 1H NMR (400 MHz,
CDCl3): δ 7.90 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 7.2 Hz, 2H), 7.55 (d, J = 7.6 Hz, 2H),
7.43 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 7.6 Hz, 2H), 7.19 (d, J = 7.6 Hz, 2H), 5.78 (s,
13
1H), 3.51 (s, 2H), 2.41 (s, 3H), 2.35 (s, 3H); C NMR (100 MHz, CDCl3): δ 146.6,
146.1, 142.4, 138.7, 136.6, 135.6, 134.0, 130.8, 130.1, 129.4, 129.1, 128.4, 127.5,
127.0, 126.6, 82.4, 21.8, 21.4; HRMS (GC-TOF) for C24H21ClN4O2S: calcd. 464.1074,
Found 464.1070.

N-(1-(4-bromophenyl)vinyl)-4-(p-tolyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4u)
Light yellow solid, 0.2320 g, yield 91%; mp: 144-146 oC; 1H NMR (400 MHz,
CDCl3): δ 7.90 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H),
7.49 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 7.6 Hz, 2H), 5.79 (s,
13
1H), 3.50 (s, 2H), 2.41 (s, 3H), 2.35 (s, 3H); C NMR (100 MHz, CDCl3): δ 146.6,
146.1, 142.4, 138.7, 137.1, 134.0, 132.1, 130.7, 130.1, 129.4, 128.4, 127.7, 127.0,
126.6, 123.8, 82.5, 21.8, 21.4; HRMS (GC-TOF) for C24H21BrN4O2S: calcd. 508.0569,
Found 508.0568.

N-(1-(2-chlorophenyl)vinyl)-4-(p-tolyl)-1-tosyl-1H-1,2,3-triazol-5-amine (4v)
White solid, 0.1320 g, yield 57%; mp: 129-131 oC; 1H NMR (400 MHz, CDCl3): δ
7.98 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.52-7.50 (m, 1H), 7.45-7.43 (m,
1H), 7.37-7.34 (m, 2H), 7.33 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 5.58 (s,
13
1H), 3.64 (s, 2H), 2.42 (s, 3H), 2.36 (s, 3H); C NMR (100 MHz, CDCl3): δ 146.6,
146.1, 142.4, 138.7, 136.6, 135.6, 134.0, 130.8, 130.1, 129.4, 129.1, 128.4, 127.5,
127.0, 126.6, 82.4, 21.8, 21.4; HRMS (GC-TOF) for C24H21ClN4O2S: calcd. 464.1074,
14
Found 464.1078.

1-phenyl-N-(1-phenylvinyl)-4-(p-tolyl)-1H-1,2,3-triazol-5-amine (4w)
Off-white solid, 0.1310 g, 74%; mp: 155-156 oC; 1H NMR (400 MHz, CDCl3): δ 7.88
(d, J = 8.0 Hz, 2H), 7.64 (d, J = 7.6 Hz, 2H), 7.53-7.45 (m, 5H), 7.39-7.38 (m, 3H),
7.23 (d, J = 8.0 Hz, 2H), 5.31 (s, 1H), 3.73 (s, 2H), 2.38(s, 3H); 13C NMR (100 MHz,
CDCl3): δ 147.0, 142.9, 138.3, 137.7, 137.1, 129.9, 129.3, 129.3, 129.2, 128.9, 128.8,
128.6, 126.6, 126.1, 124.8, 83.8, 21.4; HRMS (GC-TOF) for C23H20N4: calcd.
352.1688, Found 352.1692.

1-benzyl-N-(1-phenylvinyl)-4-(p-tolyl)-1H-1,2,3-triazol-5-amine (4x)
Off-white solid, 0.1610 g, yield 88%; mp: 122-125 oC; 1H NMR (400 MHz, CDCl3):
δ 7.84 (d, J = 7.6 Hz, 2H), 7.52-7.50 (m, 2H), 7.42 (m, 3H), 7.32-7.24 (m, 5H), 7.19
13
(d, J = 7.6 Hz, 2H), 5.52 (s, 2H), 5.18 (s, 1H), 3.63 (s, 2H), 2.35 (s, 3H); C NMR
(100 MHz, CDCl3): δ 147.8, 143.2, 138.2, 137.5, 135.6, 129.6, 129.4, 129.3, 128.8,
128.8, 128.7, 128.1, 127.6, 126.1, 126.0, 82.7, 51.9, 21.3; HRMS (GC-TOF) for
C24H22N4: calcd. 366.1844, Found 366.1845.

1-phenethyl-N-(1-phenylvinyl)-4-(p-tolyl)-1H-1,2,3-triazol-5-amine (4y)

15
Off-white solid, 0.1851 g, yield 97%; mp: 147-148 oC; 1H NMR (400 MHz, CDCl3):
δ 7.81 (d, J = 8.0 Hz, 2H), 7.53-7.51 (m, 2H), 7.43-7.42 (m, 3H), 7.27-7.21 (m, 3H),
7.18 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 6.4 Hz, 2H), 4.94 (s, 1H), 4.52 (t, J = 7.6 Hz,
2H), 3.56 (s, 2H), 3.24 (t, J = 7.6 Hz, 2H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 147.8, 142.7, 138.2, 137.7, 137.4, 129.7, 129.4, 129.3, 128.9, 128.8, 128.8, 128.7,
126.9, 126.1, 126.0, 82.5, 49.3, 36.7, 21.3; HRMS (GC-TOF) for C25H24N4: calcd.
380.2001, Found 380.1999.

4. Scale-up synthesis of product 4q

To a flame-dried Schlenk tube was added CuI (0.0665 g, 0.035 mmol, 0.01 equiv)
and the tube was evacuated and filled with N2 for 3 times. Then DCM (7 mL), 4-
methyphenylenthyne 1a (0.56 mL, 4.55 mmol, 1.3 equiv), TsN3 2a (0.95 mL, 4.20
mmol, 1.2 equiv) and DIEA (0.74 mL, 4.20 mmol, 1.2 equiv) were added to this tube
via a syringe, respectively. The reaction mixture was stirred for 30 mins in an ice-
water bath, followed by the addition of 3-(p-tolyl)-2H-azirine 3b (3.50 mmol) via a
syringe. The mixture was stirred at 0 oC~ rt for another 11.5h (during the reaction
time, the temperature of ice-water bath rose up slowly to rt). The reaction mixture was
directly transformed to the silica gel column, eluted with the mixture of petroleum and
ethyl acetate (v/v = 4/1). The collected eluent of the product was condensed using
rotatory evaporator, and the resulting residue was triturated with petroleum (10 mL) to
afford the desired product 4q as a yellow solid (1.2340 g, 79% yield).

5. Transformation experiments of 4q and 4a

Representative Procedure:
To a flame-dried Schlenk tube were added 4q (0.0667 g, 0.15 mmol) and Rh2(S-
PTV)4 (0.0018 g, 1 mol %), and the tube was evacuated and filled with N 2 for 3 times.
16
Then 1,2-dichloroethane (DCE, directly used without further purification, 1.5 mL)
and H2O (27 μL, 10 equiv) were added to the tube via a syringe, respectively, and the
mixture was heated to reflux in an oil-bath (90 oC) for 12 h. A white precipitate 5a
was isolated only by filtration from the reaction mixture after cooling to room
temperature.
Compound 5b was prepared from 4a with the same procedure.
5a, white solid, 0.0475 g, yield 71%; mp 267-271 oC; 1H NMR (400 MHz, DMSO-
d6): δ 7.90 (d, J = 8.0 Hz, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H),
7.21-7.19 (m, 4H), 6.87 (d, J = 8.0 Hz, 2H), 2.40 (s, 3H), 2.34 (s, 3H), 2.01 (s, 3H);
13
C NMR (100 MHz, DMSO-d6): δ 167.6, 143.2, 142.3, 138.0, 136.2, 134.8, 133.8,
130.2, 128.9, 128.8, 128.5, 126.8, 126.7, 125.4, 123.3, 114.4, 21.2, 20.9, 20.7; HRMS
(GC-TOF) for C25H23N3O3S: calcd. 445.1460, Found 445.1456.
5b, white solid, 0.0512 g yield 72%; mp 238-240 oC; 1H NMR (400 MHz, DMSO-
d6): δ 7.82 (d, J = 7.6 Hz, 2H), 7.65-7.59 (m, 3H), 7.49 (t, J = 7.6 Hz, 2H), 7.24-7.19
13
(m, 4H), 6.88 (d, J = 8.4 Hz, 2H), 2.34 (s, 3H), 2.02 (s, 3H); C NMR (100 MHz,
DMSO-d6): δ 187.1, 142.4, 138.1, 136.4, 136.2, 132.8, 130.1, 129.0, 128.9, 127.9,
126.8, 126.7, 125.1, 114.6, 20.9, 20.7; HRMS (GC-TOF) for C24H21N3O3S: calcd.
431.1304, Found 431.1306.
The structure of 5a was further determined by X-ray diffraction.

The X-ray structure of 5a

17
Table S2. Reaction conditions screening

cat. isolated
entry H2O note
(mol %) yield (%)
Rh2(OAc)4 no precipitate; isolated by
1a - 16
(2.5) chromatography
Rh2(Oct)4 no precipitate; isolated by
2a - 23
(2.5) chromatography
Rh2(S-PTV)4 precipitate; isolated only
3a - 42
(2.5) by filtration
Rh2(S-PTV)4 precipitate; isolated only
4b 10 equiv 71
(1) by filtration
Rh2(Oct)4 precipitate; isolated only
5b 10 equiv 40
(2.5) by filtration
precipitate; isolated only
6b - 10 equiv 21
by filtration
a
Reaction conditions: 4q (0.3 mmol), Rh catalyst (as indicated), H2O (as indicated),
DCE (3 mL), 90 oC, 12h, under N2; The solvent DCE was directly used without
b
further purification. 0.15 mmol of 4q and 1.5 mL of DCE were used. “-“ no
addition.

III. Reference:
(1) Fowler, F. W.; Hassner, A.; Levy, L. A. J. Am. Chem. Soc. 1967, 89, 2077.
(2) Hortmann, A. G.; Rorbertson, D. A.; Gillard, B. K. J. Org. Chem. 1972, 37, 322.
(3) Komatsu, M.; Ichijima, S.; Ohshiro, Y.; Agawa, T. J. Org. Chem. 1973, 38, 4341.

18
Ⅳ. 1H, 13C, and 19F NMR Spectra of 2H-Azirines (3a~3h)

19
20
21
22
23
24
25
26
27
V. 1H, 13C and 19F NMR Spectra of products (4a~4y)

28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Ⅵ 1H and 13C Spectra of 5a and 5b

57
58