Rh2(II)-catalyzed synthesis of carbazoles from biaryl azides

Article abstract of DOI:10.1021/jo9002536

An array of carbazoles (23 examples) can be synthesized from substituted biaryl azides at 60 °C using substoichio-metric quantities of Rh ₂(O₂CC₃F₇)₄ or Rh ₂(O₂CC₇H₁₅)₄.

Full text of DOI:10.1021/jo9002536

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 1 of 32
Rh2(II)-Catalyzed Synthesis of Carbazoles from Biaryl Azides
Benjamin J. Stokes, Brankica Jovanović, Huijun Dong,
Kathleen J. Richert, Ryan D. Riell, and Tom G. Driver*
Department of Chemistry, University of Illinois at Chicago,
845 West Taylor Street, Chicago, Illinois, 60607-7061
Supporting Information 1
Contents
I.
Preparation of 2-Aminobiaryls………………………………………………………….s-2
Preparation of 2-Azidobiaryls…………………………………………………………..s-11
Metal-Catalyzed Synthesis of Carbazoles from Aryl Azides….……………………….s-19
References………………………………………………………………………………s-32
II.
III.
IV.
General. 1H NMR and 13C NMR spectra were recorded at ambient temperature using 500 MHz or 300 MHz
spectrometers. The data are reported as follows: chemical shift in ppm from internal tetramethylsilane on the
d scale, multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling
constants (Hz) and integration. High resolution mass spectra were obtained by peak matching. Melting
points are reported uncorrected. Analytical thin layer chromatography was performed on 0.25 mm extra hard
silica gel plates with UV254 fluorescent indicator. Liquid chromatography was performed using forced flow
(flash chromatography) of the indicated solvent system on 60Å (40 – 60 µm) mesh silica gel (SiO2). Medium
pressure liquid chromatography (MPLC) was used to force flow the indicated solvent system down columns
that had been packed with 60Å (40 – 60 µm) mesh silica gel (SiO2). All reactions were carried out under an
atmosphere of nitrogen in glassware, which had been oven-dried. Unless otherwise noted, all reagents were
commercially obtained and, where appropriate, purified prior to use. Acetonitrile, Methanol, Toluene, THF,
Et2O, and CH2Cl2 were dried by filtration through alumina according to the procedure of Grubbs.1 Metal salts
were stored in a nitrogen atmosphere dry box.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
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I.
Preparation of 2-Aminobiaryls
A. General Procedure for the Preparation of 2-Aminobiaryls
Unless otherwise noted, the 2-aminobiaryls were synthesized from substituted 2-bromoanilines using a Suzuki
reaction (s1).2,3 Yields were not optimized.
R2
R2
R1
R1
Br
(HO)2B
Pd(PPh3)4
(s1)
NH2
NH2
In a dry 100 mL round bottom flask, phenylboronic acid (1.00 g, 8.20 mmol, 1.3 equiv), K2CO3 (3.48 g, 25.2
mmol, 4.0 equiv), and Pd(PPh3)4 (0.730 g, 0.631 mmol, 0.1 equiv) were then dissolved in 30 mL of toluene, 20
mL of H2O, and 10 mL of EtOH. 2-Bromoaniline (1.08 g, 0.715 mL, 6.31 mmol, 1.0 equiv) was added, and
the resulting mixture was heated to 95 ˚C for 16 hours. After cooling, the biphasic solution was diluted with
100 mL of saturated aqueous NH4Cl and 100 mL of CH2Cl2 and separated. The aqueous phase was extracted
with an additional 2 × 100 mL of CH2Cl2, and the combined organic phases were washed 1 × 100 mL of water
and 1 × 100 mL of saturated aqueous NaHCO3. The organic phase was dried over Na2SO4 and filtered. The
filtrate was concentrated in vacuo to afford a brown oil. Purification by MPLC (EtOAc:hexanes) afforded the
product.
B. Syntheses of 2-Aminobiaryls
MeO
Br
NH2
s1
2-Bromo-4-methoxyaniline s1.4 Following the procedure by Buchwald and co-workers,4 9.69 g of n-Bu4NBr
(20.1 mmol, 1.0 equiv) and 2.48 g of p-anisole (20.1 mmol, 1.0 equiv) were dissolved in 40 mL of CH3OH and
80 mL of CH2Cl2. After stirring for 30 minutes at 25 ˚C, the mixture was diluted with 200 mL of saturated
aqueous Na2SO3 and 200 mL of CH2Cl2. The phases were separated and the aqueous layer was washed with
an additional 2 × 200 mL of CH2Cl2. The organic phases were combined and washed 1 × 200 mL of water and
1 × 200 mL of brine. The resulting organic phase was dried over Na2SO4, filtered through a plug of silica, and
finally concentrated in vacuo to afford an oil. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded
2-bromo-4-methoxyaniline s1 as a brown liquid (1.310 g, 32 %). The spectral data matched that of Buchwald
and co-workers:4 1H NMR (CDCl3, 500 MHz): δ 7.00 (s, 1H), 6.72 (m, 2H), 3.73 (m, 5H); 13C NMR (CDCl3,
125 MHz): δ 125.7 (C), 137.9 (C), 117.5 (CH), 116.6 (CH), 115.1 (CH), 109.6 (C), 55.9 (CH3); IR (thin film):
3443, 3359, 1600, 1499, 1440, 1274, 1230, 1037 cm–1. HRMS (EI) m / z calcd for C7H8ONBr (M+): 200.9789,
found: 200.9791.
MeO
NH2
s2
Aniline s2.5 The general procedure was followed with 0.604 g of 2-bromo-4-methoxyaniline (2.99 mmol),
0.400 g of phenylboronic acid (3.29 mmol), 0.345 g of Pd(PPh3)4 (0.299 mmol), and 1.650 g of K2CO3 (12.0
mmol) in 20 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s2 as a brown oil (0.490 g, 82 %), Rf = 0.27 (20:80 EtOAc:hexanes). The

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Page 3 of 32
characterization of s2 matched that reported by Smith and co-workers:5 1H NMR (CDCl3, 500 MHz): δ
7.49-7.43 (m, 4H), 7.38-7.34 (m, 1H), 6.80-6.72 (m, 3H), 3.78 (s, 3H), 3.51 (br s, 2H); 13C NMR (CDCl3, 125
MHz): δ 152.8 (C), 139.5 (C), 137.2 (C), 129.1 (CH), 128.8 (2CH), 127.3 (CH), 116.9 (CH), 115.7 (CH), 114.5
(CH), 55.8 (CH3); IR (thin film): 3356, 2830, 1602, 1505, 1416, 1273, 1215, 1175, 1041 cm–1; HRMS (EI) m / z
calcd for C15H13ON (M+): 199.0997, found: 199.0998.
Me
NH2
s3
Aniline s3.6 The general procedure was followed with 0.112 g of 2-bromo-4-methylaniline (0.602 mmol), 0.095
g of phenylboronic acid (0.779 mmol), 0.069 g of Pd(PPh3)4 (0.060 mmol), and 0.332 g of K2CO3 (2.40 mmol)
in 7 mL of toluene, 1.9 mL of ethanol and 2.8 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s3 as tan oil (0.050 g, 46 %). The characterization for s3 was previously
reported by Shudo and co-workers:6 1H NMR (CDCl3, 300 MHz): δ 7.52-7.45 (m, 4H), 7.40-7.37 (m, 1H),
7.04-7.01 (m, 2H), 6.74 (d, J = 8.4 Hz, 1H), 3.78 (s, 2H), 2.33 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 141.0
(C), 139.7 (C), 131.0 (CH), 129.1 (CH), 129.0 (CH), 128.8 (CH), 127.9 (C), 127.7 (C), 127.1 (CH), 115.8 (CH),
20.4 (CH3); IR (thin film): 3126, 1620, 1505, 1490, 1295, 814 cm–1; HRMS (EI) m / z calcd for C13H13N (M+):
183.1048, found: 183.1047.
F
NH2
s4
Aniline s4.7 The general procedure was followed with 0.243 mL of 2-bromo-4-fluoroaniline (2.07 mmol), 0.344
g of phenylboronic acid (2.69 mmol), 0.240 g of Pd(PPh3)4 (0.207 mmol), and 1.150 g of K2CO3 (8.28 mmol) in
25 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
1
afforded aniline s4 as beige needles (0.376 g, 97 %), Rf = 0.37 (20:80 EtOAc:hexanes). H NMR (CDCl3, 500
MHz): δ 7.52-7.45 (m, 4H), 7.43-7.38 (m, 1H), 6.93-6.88 (m, 2H), 6.73-6.69 (m, 1H), 3.65 (br s, 2H); 13C NMR
(CDCl3, 125 MHz): δ 156.4 (d, JCF = 234 Hz, C), 139.7 (C), 138.7 (C), 129.1 (CH), 129.0 (CH), 128.7 (d, JCF =
7.5 Hz, C), 127.7 (CH), 116.7 (d, JCF = 21.25 Hz, CH), 116.5 (d, JCF = 7.5 Hz, CH), 115.0 (d, JCF = 22.5 Hz,
19
CH); F NMR (CDCl3, 282 MHz): δ –127.1; IR (thin film): 3356, 1620, 1601, 1504, 1496, 1420, 1270, 1178
cm–1; HRMS (EI) m / z calcd for C12H10NF (M+): 187.0797, found: 187.0795.
F3C
NH2
s5
Aniline s5.8 The general procedure was followed with 1.163 g of 2-bromo-4-trifluoromethylaniline (4.84 mmol),
0.768 g of phenylboronic acid (6.30 mmol), 0.559 g of Pd(PPh3)4 (0.484 mmol), and 2.680 g of K2CO3 (19.4
mmol) in 30 mL of toluene, 20 mL of H2O and 10 mL of EtOH. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s5 as a white powder (0.934 g, 81%): Rf = 0.27 (20:80 EtOAc:hexanes). The
spectral data matched that reported by Tolmachova and co-workers:8 1H NMR (CDCl3, 500 MHz): δ
7.55-7.40 (m, 7H), 6.80 (d, J = 9.0 Hz, 1H), 4.08 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 146.7 (C), 138.2
(C), 129.2 (CH), 129.0 (CH), 127.9 (CH), 127.7 (d, JCF = 3.8 Hz, CH), 127.0 (C), 125.7 (CH), 125.0 (q, JCF
=

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Page 4 of 32
19
269 Hz, C), 120.2 (q, JCF = 32.5 Hz, C), 114.9 (CH); F NMR (CDCl3, 282 MHz): δ –61.44; IR (thin film):
1338, 1256, 1150, 1103, 1078 cm–1; HRMS (EI) m / z calcd for C13H10NF3 (M+): 237.07653, found: 237.07646.
Me
Br
NH2
s6
2-Bromo-4-methyl-6-phenylaniline s6.
The general procedure was followed with 10.43 g of
2,6-dibromo-4-methylaniline (39.8 mmol), 5.00 g of phenylboronic acid (43.0 mmol), 21.50 g of K2CO3 (156
mmol), and 2.00 g of Pd(PPh3)4 (1.73 mmol) in 150 mL of toluene, 100 mL of H2O, and 50 mL of EtOH.
Purification by MPLC (15:85 benzene:hexanes) afforded 2-bromo-4-methyl-6-phenylaniline as a white powder
(4.90 g, 47%), mp 58 oC, Rf = 0.31 (15:85 benzene:hexanes, visualized by 254 nm UV light). 1H NMR (CDCl3,
13
500 MHz): δ 7.50-7.45 (m, 4H), 7.42-7.38 (m, 1H), 7.31 (s, 1H), 6.93 (s, 1H), 4.04 (s, 2H), 2.30 (s, 3H); C
NMR (CDCl3, 125 MHz): 139.3 (C), 139.0 (C), 132.1 (CH), 130.4 (CH), 129.1 (CH), 128.9 (CH), 128.7 (C),
128.5 (C), 127.7 (CH), 109.9 (C), 20.2 (CH3); IR (thin film): 3477, 3385, 3045, 3028, 2924, 1619, 1593, 1473,
1441, 1302, 1234, 1073, 1058, 861, 638, 575 cm-1. HRMS (EI) m / z calculated for C13H12NBr (M+): 261.0153,
found: 261.0154.
OMe
NH2
s7
Aniline s7.9 The general procedure was followed with 0.691 mL of 2-bromoaniline (6.10 mmol), 1.20 g of
3-methoxyphenylboronic acid (7.89 mmol), 0.700 g of Pd(PPh3)4 (0.610 mmol), and 3.359 g of K2CO3 (24.0
mmol) in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s7 as beige powder (1.037 g, 85%), Rf = 0.35 (20:80 EtOAc:hexanes). The
spectral data matched that reported by Crich and coworkers:9 1H NMR (CDCl3, 500 MHz): δ 7.48 (t, J = 7.5
Hz, 1H), 7.31-7.26 (m, 2H), 7.19 (d, J = 7.5 Hz, 1H), 7.16 (s, 1H), 7.03 (dd, J1 = 7.5 Hz, J2 = 2.0 Hz, 1H), 6.96
(t, J = 7.5 Hz, 1H), 6.84 (d, J = 8.5 Hz, 1H), 3.92 (s, 3H), 3.01 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 160.2
(C), 144.0 (C), 141.3 (C), 130.6 (CH), 130.2 (CH), 128.9 (CH), 127.6 (C), 121.7 (CH), 118.7 (CH), 115.9 (CH),
114.8 (CH), 113.1 (CH), 55.4 (CH3); IR (thin film): 3367, 3072, 1616, 1479, 1304, 1282, 1248, 785 cm–1.
Me
NH2
s8
Aniline s8. The general procedure was followed with 0.258 g of 2-bromoaniline (1.50 mmol), 0.265 g of
m-tolylboronic acid (1.95 mmol), 0.173 g of Pd(PPh3)4 (0.150 mmol), and 0.830 g of K2CO3 (6.01 mmol) in 14
mL of toluene, 4.0 mL of ethanol and 6.0 mL of H2O. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
afforded aniline s8 as tan oil (0.264 g, 96 %). 1H NMR (CDCl3, 500 MHz): δ 7.36 (t, J = 7.5 Hz, 1H),
7.29-7.27 (m, 2H), 7.19-7.14 (m, 3H), 6.84 (td, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.78 (dd, J1 = 8.0 Hz, J2 = 1.0 Hz,
13
1H), 3.78 (s, 2H), 2.42 (s, 3H); C NMR (CDCl3, 125 MHz): δ 143.5 (C), 139.5 (C), 138.5 (C), 130.4 (CH),
129.9 (CH), 128.7 (CH), 128.4 (CH), 127.9 (CH), 127.8 (C), 126.1 (CH), 118.6 (CH), 115.6 (CH), 21.5 (CH3);

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IR (thin film): 3029, 1294, 1234, 908, 789, 667 cm–1; HRMS (EI) m / z calcd for C13H13N (M+): 183.1048, found:
183.1047.
CF3
NH2
s9
Aniline s9. The general procedure was followed with 0.747 g of 2-bromoaniline (4.34 mmol), 0.907 g of
3-(trifluoromethyl)phenylboronic acid (4.78 mmol), 0.500 g of Pd(PPh3)4 (0.434 mmol), and 2.40 g of K2CO3
(17.4 mmol) in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s9 as colorless oil (0.935 g, 91%): Rf = 0.51 (20:80 EtOAc:hexanes). 1H
NMR (CDCl3, 500 MHz): δ 7.94 (s, 1H), 7.78 (t, J = 9.1 Hz, 2H), 7.67 (t, J = 7.7 Hz, 1H), 7.33 (t, J = 7.2 Hz,
13
1H), 7.26 (d, J = 7.4 Hz, 1H), 7.00 (t, J = 7.4 Hz, 1H), 6.87 (d, J = 8.0 Hz, 1H), 3.77 (br s, 2H); C NMR
(CDCl3, 125 MHz): δ 143.7 (C), 140.7 (C), 132.7 (CH), 131.3 (q, JCF = 32.3 Hz, C), 130.6 (CH), 129.5 (CH),
129.4 (CH), 126.1 (C), 126.0 (CH), 124.5 (q, JCF = 270 Hz, C), 124.1 (CH), 119.0 (CH), 116.1 (CH); 19F NMR
(CDCl3, 282 MHz): δ –62.82; IR (thin film): 3473, 3390, 3052, 1619, 1500, 1485, 1459, 1336, 1248, 1168,
1132, 1095, 1074 cm–1; HRMS (EI) m / z calcd for C13H10NF3 (M+): 237.0765, found: 237.0767.
F
NH2
s10
Aniline s10.7 The general procedure was followed with 0.623 mL of 2-bromoaniline (5.50 mmol), 1.00 g of
3-fluorophenylboronic acid (7.17 mmol), 0.636 g of Pd(PPh3)4 (0.550 mmol), and 3.000 g of K2CO3 (22.0 mmol)
in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s10 as a clear oil (0.831 g, 81%), Rf = 0.45 (20:80 EtOAc:hexanes). The
spectral data matched that reported by Dewar and coworkers:7 1H NMR (CDCl3, 500 MHz): δ 7.46-7.40 (m,
1H), 7.27 (d, J = 7.5 Hz, 1H), 7.24-7.17 (m, 2H), 7.14 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.07 (ddt, J1 = 8.5 Hz,
J2 = 2.5 Hz, J3 = 0.5 Hz, 1H), 6.86 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.79 (dd, J1 = 8.0 Hz, J2 = 0.5 Hz, 1H),
13
3.78 (br s, 2H); C NMR (CDCl3, 125 MHz): δ 163.1 (d, JCF = 245 Hz, C), 134.46 (C), 141.7 (d, JCF = 7.5 Hz,
C), 130.6 (CH), 130.5 (CH), 129.0 (CH), 126.3 (C), 124.8 (CH), 118.7 (CH), 116.1 (d, JCF = 20.0 Hz, CH),
115.8 (CH), 114.1 (d, JCF = 21.25, CH);19F NMR (CDCl3, 282 MHz): δ –112.8; IR (thin film): 3390, 3054, 2986,
1618, 1585, 1478, 1425, 1294, 1266, 1183, 886 cm–1. HRMS (EI) m / z calcd for C12H10NF (M+): 187.0797,
found: 187.0791.
Cl
NH2
s11
Aniline s11. The general procedure was followed with 0.566 mL of 2-bromoaniline (5.00 mmol), 1.02 g of
3-chlorophenylboronic acid (6.50 mmol), 0.578 g of Pd(PPh3)4 (0.500 mmol), and 2.780 g of K2CO3 (20.0 mmol)
in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70

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EtOAc:hexanes) afforded aniline s11 as a pale beige powder (0.974 g, 95%), Rf = 0.38 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.49-7.47 (m, 1H), 7.41-7.32 (m, 3H), 7.19 (dt, J1 = 7.5 Hz,
J2 = 1.5 Hz, 1H), 7.11 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 6.84 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.77 (dd, J1 =
8.0 Hz, J2 = 1.0 Hz, 1H), 3.75 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 143.4 (C), 141.4 (C), 134.7 (C), 130.4
(CH), 130.1 (CH), 129.3 (CH), 129.0 (CH), 127.4 (CH), 127.3 (CH), 126.1 (C), 118.8 (CH), 115.8 (CH); IR
(thin film): 3367, 3093, 3074, 1616, 1470, 1242, 885 cm–1. HRMS (EI) m / z calcd for C12H10NCl (M+):
203.0502, found: 203.0500.
OMe
OMe
NH2
s12
Aniline s12. The general procedure was followed with 0.148 mL of 2-bromoaniline (1.31 mmol), 0.310 g of
3,5-dimethoxyphenylboronic acid (1.70 mmol), 0.151 g of Pd(PPh3)4 (0.131 mmol), and 0.725 g of K2CO3 (5.24
mmol) in 25 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70
1
EtOAc:hexanes) afforded aniline s12 as a clear oil (0.186 g, 62%), Rf = 0.21 (20:80 EtOAc:hexanes). H
NMR (CDCl3, 500 MHz): δ 7.15-7.10 (m, 2H), 6.79 (dt, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 6.72 (dd, J1 = 8.5 Hz, J2
= 1.0 Hz, 1H), 6.59 (d, J = 2.5 Hz, 2H), 6.44 (t, J = 2.5 Hz, 1H), 3.81 (br s, 2H), 3.78 (s, 6H); 13C NMR (CDCl3,
125 MHz): δ 161.1 (C), 143.6 (C), 141.6 (C), 130.2 (CH), 128.7 (CH), 127.5 (C), 118.5 (CH), 115.6 (CH),
107.1 (CH), 99.5 (CH), 55.4 (CH3); IR (thin film): 3470, 3388, 3051, 3007, 2963, 2941, 2840, 1593, 1460, 1420,
1266, 1205, 1156, 1064, 732, 706 cm–1. HRMS (EI) m / z calcd for C14H15O2N (M+): 229.1103, found:
229.1105.
Me
F
NH2
s13
Aniline s13. The general procedure was followed with 0.668 mL of 2-bromoaniline (5.90 mmol), 1.18 g of
4-fluoro-3-methylphenylboronic acid (7.60 mmol), 0.682 g of Pd(PPh3)4 (0.590 mmol), and 3.25 g of K2CO3
(24.0 mmol) in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s13 as a pale yellow oil (1.004 g, 85%), Rf = 0.41 (20:80 EtOAc:hexanes).
1H NMR (CDCl3, 500 MHz): δ 7.43 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.40-7.36 (m, 1H), 7.31 (dt, J1 = 8.0 Hz,
J2 = 1.5 Hz, 1H), 7.26 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.24-7.18 (m, 1H), 6.98 (dt, J1 = 7.5 Hz, J2 = 1.5 Hz,
1H), 6.86 (dd, J1 = 8.0 Hz, J2 = 1.0 H, 1H), 3.85 (br s, 2H), 2.48 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 160.8
(d, JCF = 244 Hz, C), 143.9 (C), 135.5 (d, JCF = 2.5 Hz, C), 132.4 (d, JCF = 5.0 Hz, CH), 130.7 (CH), 128.8 (CH),
128.2 (d, JCF = 7.5 Hz, CH), 127.0 (C), 125.4 (d, JCF = 16.25 Hz, C), 118.8 (CH), 115.8 (CH), 115.5 (d, JCF =
21.3 Hz, CH), 14.8 (CH3); 19F NMR (CDCl3, 282 MHz): δ –119.9; IR (thin film): 3464, 3377, 3028, 1615, 1503,
1487, 1452, 1299, 1227, 1119, 821, 752 cm–1. HRMS (EI) m / z calcd for C13H12NF (M+): 201.0954, found:
201.0953.

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Page 7 of 32
OMe
NH2
s14
Aniline s14.9 The general procedure was followed with 0.635 mL of 2-bromoaniline (5.60 mmol), 1.107 g of
4-methoxyphenylboronic acid (7.29 mmol), 0.650 g of Pd(PPh3)4 (0.560 mmol), and 3.098 g of K2CO3 (22.0
mmol) in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s14 as a pale yellow oil (0.979 g, 87%). The spectral data matched that
1
reported by Crich and coworkers: H NMR (CDCl3, 500 MHz): δ 7.39 (d, J = 9.0 Hz, 2H), 7.17-7.11 (m, 2H),
6.99 (d, J = 9.0 Hz, 2H), 6.82 (t, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.77 (d, J = 8.0 Hz, 1H), 3.86 (s, 3H), 3.75 (br s,
13
2H); C NMR (CDCl3, 125 MHz): δ 158.7 (C), 143.6 (C), 131.7 (C), 130.4 (CH), 130.1 (CH), 128.1 (CH),
127.2 (C), 118.5 (CH), 115.4 (CH), 114.1 (CH), 55.2 (CH3); IR (thin film): 3367, 1612, 1514, 1489, 1452, 1296,
1243, 1178, 1032 cm–1.
t-Bu
NH2
s15
Aniline s15. The general procedure was followed with 0.891 g of 2-bromoaniline (5.18 mmol), 1.20 g of
4-tert-butylphenylboronic acid (6.73 mmol), 0.599 g of Pd(PPh3)4 (0.518 mmol), and 2.86 g of K2CO3 (20.7
mmol) in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s15 as white solid (0.853 g, 74 %). 1H NMR (CDCl3, 300 MHz): δ 7.47-7.37
(m, 4H), 7.15-7.12 (m, 2H), 6.81-6.74 (m, 2H), 3.76 (s, 2H), 1.36 (s, 9H); 13C NMR (CDCl3, 75 MHz): δ 149.8,
143.5, 136.4, 130.3, 128.6, 128.1, 127.4, 125.6, 118.4, 115.4, 34.5, 31.4; IR (thin film): 3371, 2951, 1612, 1489,
1201, 732 cm–1; HRMS (EI) m / z calcd for C16H19N (M+): 225.1517, found: 225.1518.
Et
NH2
s16
Aniline s16.10 The general procedure was followed with 0.623 g of 2-bromoaniline (3.62 mmol), 0.701 g of
4-ethylphenylboronic acid (4.67 mmol), 0.421 g of Pd(PPh3)4 (0.364 mmol), and 1.99 g of K2CO3 (14.4 mmol)
in 20 mL of toluene, 6.5 mL of ethanol and 5 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s16 as yellow oil (0.612 g, 86 %). 1H NMR (CDCl3, 500 MHz): δ 7.36 (d, J
= 8 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 7.14-7.11 (m, 2H), 6.89 (t, J = 7.0 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H), 3.72
(s, 2H), 2.68 (q, J = 7.5 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 125 MHz): δ 143.6 (C), 143.1 (C),
136.7 (C), 130.4 (CH), 129.0 (CH), 128.2 (2CH), 127.6 (C), 118.6 (CH), 115.5 (CH), 28.5 (CH2), 15.5 (CH3);
IR (thin film): 3371, 3021, 1614, 1489, 1449, 1294 cm–1; HRMS (EI) m / z calcd for C14H15N (M+): 197.1204,
found: 197.1204.
Me
NH2
s17
Aniline s17.6 The general procedure was followed with 0.258 g of 2-bromoaniline (1.50 mmol), 0.306 g of

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p-tolylboronic acid (2.25 mmol), 0.173 g of Pd(PPh3)4 (0.15 mmol), and 0.595 g of K2CO3 (6.00 mmol) in 15
mL of toluene, 6.0 mL of ethanol and 3 mL of H2O. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
afforded aniline s17 as colorless oil (0.265 g, 96 %). The characterization for s17 matched that reported by
Shudo and co-workers:6 1H NMR (CDCl3, 500 MHz): δ 7.41 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 7.5 Hz, 2H),
7.21-7.17 (m, 2H), 6.87 (td, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.80 (d, J = 7.0 Hz, 1H), 3.79 (s, 2H), 2.45 (s, 3H);
13C NMR (CDCl3, 125 MHz): δ 143.5, 136.8, 136.5, 130.4, 129.4, 128.9, 128.2, 127.5, 118.5, 115.5, 21.1; IR
(thin film): 3368, 1614, 1489, 1294, 820, 748 cm–1.
NH2
s18
Aniline s18. The general procedure was followed with 0.668 mL of 2-bromoaniline (5.90 mmol), 1.14 g of
4-vinylphenylboronic acid (7.70 mmol), 0.682 g of Pd(PPh3)4 (0.590 mmol), and 3.30 g of K2CO3 (24.0 mmol)
in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
1
EtOAc:hexanes) afforded aniline s18 as an orange oil (0.711 g, 62%), Rf = 0.46 (20:80 EtOAc:hexanes). H
NMR (CDCl3, 500 MHz): δ 7.68-7.59 (m, 4H), 7.36-7.30 (m, 2H), 7.02 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.94
(dd, J1 = 16.5 Hz, J2 = 11.0 Hz, 1H), 6.87 (dd, J1 = 8.5 Hz, J2 = 1.0 Hz, 1H), 5.99 (dd, J1 = 17.5 Hz, J2 = 1.0 Hz,
1H), 5.47 (dd, J1 = 11.0 Hz, J2 =1.0 Hz, 1H), 3.86 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 143.9 (C), 139.3
(C), 136.7 (CH), 136.6 (C), 130.6 (CH), 129.5 (CH), 128.8 (CH), 127.4 (C), 126.9 (CH), 118.9 (CH), 115.9
(CH), 114.3 (CH2); IR (thin film): 3455, 3370, 3024, 1614, 1489, 1452, 1292 cm–1. HRMS (EI) m / z calcd for
C14H13N (M+): 195.1048, found: 195.1048.
F
NH2
s19
Aniline s19.11 The general procedure was followed with 0.804 mL of 2-bromoaniline (7.10 mmol), 1.29 g of
4-fluorophenylboronic acid (9.20 mmol), 0.800 g of Pd(PPh3)4 (0.710 mmol), and 3.92 g of K2CO3 (28.0 mmol)
in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s19 as a waxy pale yellow oil (1.226 g, 92 %), Rf = 0.40 (20:80
EtOAc:hexanes). The spectral data matched that reported by Ohwada and coworkers:11 1H NMR (CDCl3,
500 MHz): δ 7.42-7.37 (m, 2H), 7.17-7.12 (dt, 1H), 7.12-7.07 (m, 3H), 6.84-6.79 (dt, 1H), 6.74-6.70 (dd, 1H),
3.67 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 162.1 (d, JCF = 244 Hz, C), 143.7 (C), 135.6 (d, JCF = 1.3 Hz, C),
130.9 (d, JCF = 7.5 Hz, CH), 130.6 (CH), 128.8 (CH), 126.7 (C), 118.8 (CH), 115.9 (CH), 115.8 (d, JCF = 5.0 Hz,
19
CH); F NMR (CDCl3, 282 MHz): δ –115.4; IR (thin film): 3478, 3390, 3054, 2986, 1265, 736, 706 cm–1;
HRMS (EI) m / z calcd for C13H10NF (M+): 187.0797, found: 187.0790.
CO2Et
NH2
s20
Aniline s20.12 The general procedure was followed with 0.240 mL of 2-bromoaniline (2.07 mmol), 0.522 g of
4-ethoxycarbonylphenylboronic acid (2.69 mmol), 0.240 g of Pd(PPh3)4 (0.207 mmol), and 1.150 g of K2CO3
(8.28 mmol) in 25 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70

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Page 9 of 32
1
EtOAc:hexanes) afforded aniline s20 as a beige oil (0.465 g, 93%), Rf = 0.33 (20:80 EtOAc:hexanes). H
NMR (CDCl3, 500 MHz): δ 8.13 (d, J = 8.0 Hz, 2H), 7.56 (d, J = 8.0 Hz, 2H), 7.19 (dt, J1 = 8.0 Hz, J2 = 1.0 Hz,
1H), 7.14 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 6.85 (t, J = 7.5 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 4.41 (q, J = 7.0
Hz, 2H), 3.78 (br s, 2H), 1.43 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 125 MHz): δ 166.5 (C), 144.4 (C), 143.5
(C), 130.3 (CH), 130.1 (CH), 129.2 (CH), 129.1 (CH), 126.4 (C), 118.8 (CH), 115.9 (CH), 61.0 (CH2), 14.4
(CH3); IR (thin film): 3458, 3394, 3054, 2894, 1711, 1618, 1279, 1112, 1103, 728, 708 cm–1. HRMS (EI) m / z
calcd for C15H15O2N (M+): 241.1103, found: 241.1103.
CF3
NH2
s21
Aniline s21. The general procedure was followed with 0.227 g of 2-bromoaniline (1.32 mmol), 0.327 g of
4-(trifluoromethyl)phenylboronic acid (1.72 mmol), 0.153 g of Pd(PPh3)4 (0.132 mmol), and 0.730 g of K2CO3
(5.28 mmol) in 15 mL of toluene, 6.0 mL of ethanol and 3 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s21 as tan oil (0.302 g, 96 %). 1H NMR (CDCl3, 500 MHz): δ 7.48-7.42 (m,
3H), 7.36-7.32 (m, 1H), 7.17-7.12 (m, 2H), 6.82 (td, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.76 (dd, J1 = 7.5 Hz, J2 = 1.0
Hz, 1H), 3.75 (s, 2H); 13C NMR (CDCl3, 125 MHz): δ 143.4 (C), 143.3 (C), 130.4 (CH), 129.5 (CH), 129.4 (q,
JCF = 32.06 Hz, C), 129.3 (CH), 126.1 (C), 125.7 (CH), 124.3 (q, JCF = 270 Hz, C), 118.9 (CH), 115.9 (CH); IR
(thin film): 3367, 1618, 1403, 1106, 848, 757 cm–1; HRMS (EI) m / z calcd for C13H10F3N (M+): 237.0765, found:
237.0764.
NO2
NH2
s22
Aniline s22. The general procedure was followed with 0.325 g of 2-bromoaniline (1.89 mmol), 0.410 g of
4-nitrophenylboronic acid (2.46 mmol), 0.219 g of Pd(PPh3)4 (0.189 mmol), and 1.04 g of K2CO3 (7.56 mmol)
in 14 mL of toluene, 4.0 mL of ethanol and 8.0 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s22 as tan oil (0.400 g, 99 %). 1H NMR (CDCl3, 300 MHz): δ 8.32-8.29 (m,
13
2H), 7.69-7.66 (m, 2H), 7.26-7.12 (m, 2H), 6.90-6.79 (m, 2H), 3.77 (s, 2H); C NMR (CDCl3, 125 MHz): δ
146.9 (C), 146.6 (C), 143.4 (C), 130.3 (CH), 129.9 (CH), 129.8 (CH), 125.1 (C), 124.1 (CH), 119.1 (CH), 116.2
(CH); IR (thin film): 3386, 1622, 1509, 1344, 757 cm–1; HRMS (EI) m / z calcd for C12H10N2O2 (M+): 214.0742,
found: 214.0740.
CN
NH2
s23
Aniline s23. The general procedure was followed with 0.230 mL of 2-bromoaniline (2.07 mmol), 0.395 g of
4-cyanophenylboronic acid (2.69 mmol), 0.240 g of Pd(PPh3)4 (0.207 mmol), and 1.15 g of K2CO3 (8.28 mmol)
in 25 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s23 as a pale yellow solid (0.342 g, 85%), Rf = 0.27 (20:80 EtOAc:hexanes).
1H NMR (CDCl3, 500 MHz): δ 7.73 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 8.0 Hz, 2H), 7.21 (dt, J1 = 8.0 Hz, J2 = 1.0
Hz, 1H), 7.10 (dd, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.86 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.79 (d, J = 8.0 Hz, 1H),

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13
3.75 (br s, 2H); C NMR (CDCl3, 125 MHz): δ 144.6 (C), 143.4 (C), 132.7 (CH), 130.3 (CH), 129.9 (CH),
129.7 (CH), 125.5 (C), 119.0 (CH), 118.9 (C), 116.1 (CH), 110.9 (C); IR (thin film): 2223 cm–1. HRMS (EI)
m / z calcd for C13H10N2 (M+): 194.0844, found: 194.0846.
Me
NH2
s24
Aniline s24.6 The general procedure was followed with 0.612 g of 2-bromoaniline (3.56 mmol), 0.629 g of
o-tolylboronic acid (4.63 mmol), 0.412 g of Pd(PPh3)4 (0.356 mmol), and 1.97 g of K2CO3 (14.2 mmol) in 20
mL of toluene, 7.0 mL of ethanol and 8.0 mL of H2O. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
afforded aniline s24 as tan oil (0.610 g, 94 %). The characterization for s24 was previously reported by Shudo
and co-workers:6 1H NMR (CDCl3, 500 MHz): δ 7.29-7.23 (m, 3H), 7.21-7.19 (m, 1H), 7.16 (td, J1 = 8.0 Hz, J2
= 1.5 Hz, 1H), 7.00 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 6.81-6.78 (m, 1H), 6.75 (d, J = 8.0 Hz, 1H), 3.46 (s, 2H),
13
2.16 (s, 3H); C NMR (CDCl3, 125 MHz): δ 143.6 (C), 138.6 (C), 137.0 (C), 130.2 (CH), 130.0 (CH), 128.3
(CH), 127.7 (CH), 127.4 (C), 126.1 (CH), 118.2 (CH), 115.0 (CH), 19.6 (CH3).
Cl
NH2
s25
Aniline s25.11 The general procedure was followed with 0.645 mL of 2-bromoaniline (5.70 mmol), 1.16 g of
2-chlorophenylboronic acid (7.45 mmol), 0.660 g of Pd(PPh3)4 (0.570 mmol), and 3.15 g of K2CO3 (23.0 mmol)
in 30 mL of toluene, 10 mL of ethanol and 20 mL of H2O. Purification by MPLC (0:100 – 30:70
EtOAc:hexanes) afforded aniline s25 as a white solid (1.02 g, 88%), Rf = 0.39 (20:80 EtOAc:hexanes). The
spectral data matched that reported by Ohwada and coworkers:11 1H NMR (CDCl3, 500 MHz): δ 7.55 (dd, J1 =
6.5 Hz, J2 = 2.0 Hz, 1H), 7.42-7.34 (m, 3H), 7.26 (dt, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.12 (dd, J1 = 7.5 Hz, J2 =
1.5 Hz, 1H), 6.89 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.82 (dd, J1 = 8.0 Hz, J2 = 0.5 Hz, 1H), 3.59 (br s, 2H); 13C
NMR (CDCl3, 125 MHz): δ 143.9 (C), 138.0 (C), 134.0 (C), 132.0 (CH), 130.5 (CH), 130.0 (CH), 129.2 (CH),
129.1 (CH), 127.3 (CH), 125.3 (C), 118.4 (CH), 115.6 (CH); IR (thin film): 3463, 3380, 1618, 1501, 1469,
1450, 1430, 1300 cm–1. HRMS (EI) m / z calcd for C12H10NCl (M+): 203.0502, found: 203.0501.
F
NH2
s26
Aniline s26.11 The general procedure was followed with 0.240 mL of 2-bromoaniline (2.07 mmol), 0.377 g of
2-fluorophenylboronic acid (2.69 mmol), 0.240 g of Pd(PPh3)4 (0.207 mmol), and 1.150 g of K2CO3 (8.28 mmol)
in 25 mL of toluene, 5 mL of ethanol and 10 mL of H2O. Purification by MPLC (0:100 – 30:70
1
EtOAc:hexanes) afforded aniline s26 as a white solid (0.262 g, 68 %), Rf = 0.38 (20:80 EtOAc:hexanes). H
NMR (CDCl3, 500 MHz): δ 7.44-7.36 (m, 2H), 7.28-7.15 (m, 4H), 6.88 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 6.82
(dd, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H), 3.69 (br s, 2H); 13C NMR (CDCl3, 125 MHz): δ 159.9 (d, JCF = 245 Hz, C),
144.2 (C), 132.1 (d, JCF = 2.5 Hz, CH), 131.1 (CH), 129.4 (d JCF = 6.3 Hz, CH), 129.2 (CH), 126.7 (d, JCF = 16.3
19
Hz, C), 124.6 (CH), 121.6 (C), 118.5 (CH), 116.1 (d, JCF = 22.5 Hz, CH), 115.8 (CH); F NMR (CDCl3, 282
MHz): δ –114.6; IR (thin film): 3478, 3390, 1619, 1501, 1480, 1442, 1200, 1105 cm-1; HRMS (EI) m / z calcd

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Page 11 of 32
for C12H10NF (M+): 187.0797, found: 187.0795.
II.
Preparation of 2-Azidobiaryls
A. General Procedure for the Preparation of 2-Azidobiaryls
Unless otherwise noted, the 2-vinyl-substituted azides were synthesized from the corresponding substituted
2-bromoanilines using traditional diazotization followed by nucleophilic aromatic substitution by sodium azide
(s2).13 Yields were not optimized.
R2
R2
R1
R1
1. NaNO2
2. NaN3
(s2)
N3
NH2
In a 20 mL scintillation vial, 2-aminobiphenyl (0.250 g, 1.48 mmol, 1.0 equiv) was dissolved in 10 mL of
HOAc and 5 mL of H2O and chilled in an ice bath. NaNO2 (0.142 g, 2.07 mmol, 1.4 equiv) was added slowly,
and the resulting mixture was stirred at 0 °C for one hour. NaN3 (0.144 g, 2.22 mmol, 1.5 equiv) was then
added slowly, and the resulting mixture was warmed to ambient temperature, and stirred for 30 minutes. The
solution was diluted with 20 mL of water and 20 mL of CH2Cl2 and basified by the slow addition of K2CO3 until
bubbling ceased. The phases were separated and the aqueous phase was extracted with an additional 2 × 20
mL of CH2Cl2. The combined organic phases were washed 1 × 20 mL of water and 1 × 20 mL of brine. The
resulting organic phase and dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford an
oil. Purification by MPLC (EtOAc:hexanes) afforded the product, which was stored in the freezer.
B. Syntheses of 2-Azidobiaryls
MeO
H
N3
6a
Azide 6a.5 The general procedure was followed with 0.353 g of aniline s2 (1.77 mmol), 0.171 g of NaNO2 (2.48
mmol), and 0.172 g of NaN3 (2.65 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6a as a yellow oil (0.313 g, 70%): Rf = 0.63 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.55-7.48 (m, 4H), 7.46-7.42 (m, 1H), 7.22 (d, J = 8.5 Hz,
1H), 7.00 (dd, J1 = 8.5 Hz, J2 = 3.0 Hz, 1H), 6.97 (d, J = 8.0 Hz, 1H), 3.87 (s, 3H); 13C NMR (CDCl3, 125 MHz):
δ 156.9 (C), 138.2 (C), 134.9 (C), 129.7 (C), 129.5 (CH), 128.3 (CH), 127.8 (CH), 120.0 (CH), 116.6 (CH),
114.4 (CH), 55.7 (CH3); IR (thin film): 2119, 1483 cm–1; HRMS (EI) m / z calcd for C13H11ON3 (M+): 225.0902,
found: 225.0900.
Me
H
N3
6b
Azide 6b.5 The general procedure was followed with 0.170 g of aniline s3 (0.928 mmol), 0.090 g of NaNO2
(1.30 mmol), and 0.091 g of NaN3 (1.40 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification

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Page 12 of 32
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6b as tan oil (0.137 g, 71%). Azide 6b was
previously reported by Smith and Hall.5 1H NMR (CDCl3, 500 MHz): δ 7.46-7.42 (m, 4H), 7.39-7.37 (m, 1H),
7.22-7.20 (m, 1H), 7.17-7.15 (m, 2H), 2.38 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 138.3, 134.7, 134.4, 133.6,
131.9, 129.4, 129.3, 128.1, 127.5, 118.7, 20.8; IR (thin film): 2118, 1486, 1444, 1299, 808, 767 cm–1; HRMS
(EI) m / z calcd for C13H11N3 (M+): 209.0953, found: 209.0952.
H
N3
6c
Azide 6c.14 The general procedure was followed with 3.00 g of 2-aminobiphenyl (17.73 mmol), 1.61 g of
NaNO2 (23.34 mmol), and 1.63 g of NaN3 (25.12 mmol) in 60.00 mL of acetic acid and 30.00 mL of H2O.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6c as tan wax (3.50 g, 100%).
Characterization data of azide 6c matched that reported by Platz and coworkers.14 1H NMR (CDCl3, 500 MHz):
δ 7.51-7.38 (m, 7H), 7.31-7.23 (m, 2H); 13C NMR (CDCl3, 125 MHz): δ 138.2 (C), 137.2 (C), 133.9 (C), 131.3
(CH), 129.5 (CH), 128.8 (CH), 128.2 (CH), 127.6 (CH), 125.0 (CH), 118.8 (CH); IR (thin film): 2087, 1587,
1472, 1295, 1183, 882, 751 cm–1; HRMS (EI) m / z calcd for C12H9N3: 195.0796, found: 195.0795.
F
H
N3
6d
Azide 6d. The general procedure was followed with 0.100 g of aniline s4 (0.534 mmol), 0.053 g of NaNO2
(0.748 mmol), and 0.052 g of NaN3 (0.801 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6d as a waxy yellow oil (0.073 g, 62%), Rf = 0.64
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.49-7.39 (m, 5H), 7.24-7.18 (m, 1H), 7.15-7.08 (m,
13
2H); C NMR (CDCl3, 125 MHz): δ 159.8 (d, JCF = 243 Hz, C), 137.1 (C), 135.5 (d, JCF = 7.63 Hz, C), 133.0
(C), 129.4 (CH), 128.4 (CH), 128.1 (CH), 120.1 (d, JCF = 8.63 Hz, CH), 118.0 (d, JCF = 23.88 Hz, CH), 115.4 (d,
JCF = 22.25, CH); IR (thin film): 2122, 2092, 2074, 1502, 1485, 1445, 1410, 1311, 1290, 1267, 1187 cm–1;
HRMS (EI) m / z calcd for C12H8N3F (M+): 213.07022, found: 213.07015.
F3C
H
N3
6e
Azide 6e. The general procedure was followed with 0.279 g of aniline s5 (1.17 mmol), 0.113 g of NaNO2
(1.64 mmol), and 0.113 g of NaN3 (1.75 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification
1
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6e as an off-white solid (0.287 g, 93%): H NMR
(CDCl3, 500 MHz): δ 7.67-7.62 (m, 2H), 7.51-7.42 (m, 5H), 7.36-7.34 (m, 1H); 13C NMR (CDCl3, 125 MHz): δ
140.8 (C), 136.8 (C), 134.1 (C), 129.3 (CH), 128.3 (CH), 128.2 (CH), 127.0 (q, JCF =135 Hz, C), 125.57 (CH),
125.55 (CH), 123.9 (q, JCF =1075 Hz, CF3), 119.0 (CH); 19F NMR (CDCl3, 282 MHz): δ –62.69; IR (thin film):
2117, 1335, 1120, 700 cm–1; HRMS (EI) m / z calcd for C13H8F3N3 (M+): 263.0670, found: 263.0671.

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Page 13 of 32
Me
Br
N3
6f
Azide 6f. The general procedure was followed with 1.000 g of aniline s6 (3.81 mmol), 0.380 g of NaNO2
(5.30 mmol), and 0.380 g of NaN3 (5.72 mmol) in 30 mL of AcOH. Purification by MPLC (10:90
benzene:hexanes) afforded azide 6f as a yellow oil (0.914 g, 83%), Rf = 0.52 (10:90 benzene:hexanes,
visualized by 254 nm UV light). 1H NMR (CDCl3, 500 MHz): δ 7.53-7.44 (m, 6H), 7.11 (m, 1H), 2.38 (s, 3H);
13C NMR (CDCl3, 125 MHz): δ 137.8 (2C), 136.9 (C), 133.2 (CH), 133.1 (C), 131.3 (CH), 129.2 (CH), 128.6
(CH), 128.2 (CH), 117.8 (C), 20.7 (CH3); IR (thin film): 3053, 2984, 2924, 2129, 1455, 1433, 1314, 1290, 1265
cm-1. HRMS (EI) m / z calculated for C13H10N3Br (M+): 287.0058, found: 287.0057.
Me
H
N3
6g
Azide 6g.15 The general procedure was followed with 0.120 g of aniline s7 (0.655 mmol), 0.063 g of NaNO2
(0.913 mmol), and 0.064 g of NaN3 (0.984 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6g as tan oil (0.090 g, 66%). Aryl azide 6g was
previously reported by Meth-Cohn and co-workers.15 1H NMR (CDCl3, 500 MHz): δ 7.43-7.39 (m, 1H),
13
7.32-7.22 (m, 4H), 7.20-7.19 (m, 2H), 7.14-7.13 (m, 1H), 2.14 (s, 3H); C NMR (CDCl3, 125 MHz): δ 138.0
(C), 137.9 (C), 136.4 (C), 133.7 (C), 131.3 (CH), 129.8 (2CH), 128.7 (CH), 128.0 (CH), 125.6 (CH), 124.7
(CH), 118.4 (CH), 20.0 (CH3); IR (thin film): 2123, 1577, 1478, 1292, 1008, 752 cm–1; HRMS (EI) m / z calcd
for C13H11N3 (M+): 209.0953, found: 209.0952.
Cl
H
N3
6h
Azide 6h. The general procedure was followed with 0.201 g of aniline s8 (0.988 mmol), 0.098 g of NaNO2
(1.38 mmol), and 0.096 g of NaN3 (0.148 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6h as a pale yellow oil (0.162 g, 72%): Rf = 0.69
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.55-7.51 (m, 1H), 7.51-46 (m, 1H), 7.39-7.34 (m,
13
2H), 7.32-7.27 (m, 3H), 7.27-7.23 (m, 1H); C NMR (CDCl3, 125 MHz): δ 138.3 (C), 137.2 (C), 133.7 (C),
131.6 (CH), 131.4 (CH), 131.3 (C), 129.5 (CH), 129.4 (CH), 129.3 (CH), 126.6 (CH), 124.7 (CH), 118.5 (CH);
IR (thin film): 2121, 2097, 1499, 1468, 1442, 1429, 1293 cm–1; HRMS (EI) m / z calcd for C12H8N3Cl (M+):
229.0407, found: 229.0405.
F
H
N3
6i
Azide 6i. The general procedure was followed with 0.090 g of aniline s9 (0.482 mmol), 0.047 g of NaNO2
(0.675 mmol), and 0.047 g of NaN3 (0.724 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification

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Page 14 of 32
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6i as a beige solid (0.079 g, 77%): Rf = 0.67 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.45 (dt, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.42-7.36 (m, 1H),
7.35-7.27 (m, 3H), 7.26-7.21 (m, 2H), 7.17 (t, J = 8.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δ 159.7 (d, JCF =
245 Hz, C), 138.3 (C), 131.7 (2CH), 129.8 (d, JCF = 7.5 Hz, CH), 129.4 (CH), 127.8 (C), 125.8 (d, JCF = 15 Hz,
C), 124.7 (CH), 123.9 (d, JCF = 3.75 Hz, CH), 118.6 (CH), 115.7 (d, JCF = 22.5 Hz, CH); 19F NMR (CDCl3, 282
MHz): δ –114.6; IR (thin film): 3054, 2987, 2129, 1422, 1266, 896, 738, 708 cm–1; HRMS (EI) m / z calcd for
C12H8N3F (M+): 213.0702, found: 213.0703.
OMe
H
N3
6j
Azide 6j.16 The general procedure was followed with 0.247 g of aniline s10 (1.24 mmol), 0.124 g of NaNO2
(1.74 mmol), and 0.121 g of NaN3 (1.86 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6j as yellow needles (0.203 g, 71%): Rf = 0.63 (20:80
EtOAc:hexanes). The spectral data matched that reported by Knepper and coworkers:16 1H NMR (CDCl3, 500
MHz): δ 7.45-7.42 (m, 2H), 7.41-7.38 (m, 1H), 7.37-7.35 (m, 1H), 7.28-7.26 (m, 1H), 7.24-7.21 (m, 1H),
7.03-7.00 (m, 2H), 3.88 (s , 3H); 13C NMR (CDCl3, 125 MHz): δ 159.1 (C), 137.1 (C), 133.5 (C), 131.2 (CH),
130.6 (CH), 130.5 (C), 128.4 (CH), 124.9 (CH), 118.8 (CH), 113.7 (CH), 55.3 (CH3); IR (thin film): 2954, 2935,
2835, 2121, 2086, 1610, 1516, 1482, 1294, 1244, 1178, 1036, 831, 752 cm–1; HRMS (EI) m / z calcd for
C13H11ON3 (M+): 225.09022, found: 225.09038.
t-Bu
H
N3
6k
Azide 6k. The general procedure was followed with 0.251 g of aniline s11 (1.11 mmol), 0.107 g of NaNO2
(1.55 mmol), and 0.109 g of NaN3 (1.67 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6k as tan wax (0.227 g, 81%): 1H NMR (CDCl3, 500
MHz): δ 7.52-7.50 (m, 2H), 7.46-7.44 (m, 2H), 7.41-7.38 (m, 2H), 7.29 (dd, J1 = 8 Hz, J1 = 1 Hz, 1H), 7.24 (dt,
13
J1 = 7.5 Hz, J1 = 1.5 Hz, 1H), 1.41 (s, 9H); C NMR (CDCl3, 125 MHz): δ 150.4 (C), 137.0 (C), 135.1 (C),
133.6 (C), 131.2 (CH), 129.0 (CH), 128.4 (CH), 125.1 (CH), 124.9 (CH), 118.6 (CH), 34.6 (C), 31.3 (CH3); IR
(thin film): 2962, 2123, 1484, 1296, 834, 756 cm–1; HRMS (EI) m / z calcd for C16H17N3 (M+): 251.1422, found:
251.1422.
Et
H
N3
6l
Azide 6l. The general procedure was followed with 0.306 g of aniline s12 (1.55 mmol), 0.149 g of NaNO2
(2.17 mmol), and 0.151 g of NaN3 (2.33 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6l as tan oil (0.185 g, 53%): H NMR (CDCl3, 500
1
13
MHz): δ 7.37-7.31 (m, 4H), 7.27-7.16 (m, 4H), 2.70 (q, J = 7.5 Hz, 2H), 1.28 (t, J = 7.5 Hz, 3H); C NMR
(CDCl3, 125 MHz): δ 143.7 (C), 137.2 (C), 135.5 (C), 133.8 (C), 131.3 (CH), 129.4 (CH), 128.5 (CH), 127.7
(CH), 125.0 (CH), 118.8 (CH), 28.6 (CH2), 15.5 (CH3) ; IR (thin film): 2945, 2125, 1483, 1296, 833, 753 cm–1;

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Page 15 of 32
HRMS (EI) m / z calcd for C14H13N3 (M+): 223.1109, found: 223.1109.
Me
H
N3
6m
Azide 6m. The general procedure was followed with 0.265 g of aniline s13 (1.45 mmol), 0.140 g of NaNO2
(2.03 mmol), and 0.141 g of NaN3 (2.17 mmol) in 8.00 mL of acetic acid and 8.00 mL of H2O. Purification by
1
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6m as colorless oil (0.258 g, 85%): H NMR (CDCl3,
500 MHz): δ 7.45-7.39 (m, 4H), 7.33-7.30 (m, 3H), 7.26 (td, J1 = 7.5 Hz, J2 = 1 Hz, 1H), 2.48 (s, 3H); 13C NMR
(CDCl3, 125 MHz): δ 137.3, 137.0, 135.2, 133.7 131.1, 129.2, 128.8, 128.4, 124.8, 118.6, 21.2; IR (thin film):
2124, 1658, 1482, 1290, 817, 750 cm–1; HRMS (EI) m / z calcd for C13H11N3 (M+): 209.0953, found: 209.0955.
H
N3
6n
Azide 6n. The general procedure was followed with 0.160 g of aniline s14 (0.817 mmol), 0.081 g of NaNO2
(0.114 mmol), and 0.080 g of NaN3 (0.123 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6n as a waxy yellow oil (0.114 g, 63%): Rf = 0.71
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.56-7.47 (m, 4H), 7.44 (dt, J1 = 8.0 Hz, J2 = 2.0 Hz,
1H), 7.40 (dd, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 7.31 (dd, J1 = 8.0 Hz, J2 = 0.5 Hz, 1H), 7.26 (dt, J1 = 7.5 Hz, J2 =
1.5 Hz, 1H), 6.83 (dd, J1 = 17.5 Hz, J2 = 11.0 Hz, 1H), 5.87 (dd, J1 = 17.5 Hz, J2 = 1.0 Hz, 1H), 5.35 (dd, J1 =
11.0 Hz, J2 = 1.0 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δ 137.7 (C), 137.2 (C), 136.9 (C), 136.5 (CH), 133.5
(C), 131.2 (CH), 129.7 (CH), 128.8 (CH), 126.1 (CH), 125.1 (CH), 118.9 (CH), 114.3 (CH2); IR (thin film):
3087, 3074, 2125, 2094, 1483, 1298, 1244, 841, 781, 673, 654 cm–1; HRMS (EI) m / z calcd for C14H11N3 (M+):
221.0953, found: 221.0953.
F
H
N3
6o
Azide 6o. The general procedure was followed with 0.255 g of aniline s15 (1.36 mmol), 0.135 g of NaNO2
(1.90 mmol), and 0.130 g of NaN3 (2.00 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6o as a white solid (0.241 g, 82%), Rf = 0.68 (20:80
1
EtOAc:hexanes). H NMR (CDCl3, 500 MHz): δ 7.47-7.40 (m, 3H), 7.33 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H),
7.28 (d, J = 8.0 Hz, 1H), 7.23 (t, J = 7.5 Hz, 1H), 7.14 (t, J = 8.5 Hz, 2H); 13C NMR (CDCl3, 125 MHz): δ 162.4
(d, JCF = 245 Hz, C), 137.2 (C), 134.1 (C), 132.7 (C), 131.2 (d, JCF = 2.5 Hz, CH), 131.1 (CH), 125.0 (CH),
118.8 (CH), 115.2 (CH), 115.0 (CH); 19F NMR (CDCl3, 282 MHz): δ –115.0; IR (thin film): 2126, 2090, 1513,
1482 cm–1; HRMS (EI) m / z calcd for C12H8N3F (M+): 213.0702, found: 213.0700.

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Page 16 of 32
CO2Et
H
N3
6p
Azide 6p. The general procedure was followed with 0.115 g of aniline s16 (0.477 mmol), 0.046 g of NaNO2
(0.668 mmol), and 0.047 g of NaN3 (0.716 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6p as a waxy yellow solid (0.082 g, 64%): Rf = 0.59
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 8.11 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H),
7.43 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.35 (dd, J1 = 8.0 Hz, J2 = 2.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 7.23 (t,
J = 8.0 Hz, 1H) 4.41 (q, J = 7.0 Hz, 2H), 7.42 (t, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 125 MHz): δ 166.4 (C),
142.7 (C), 137.2 (C), 132.7 (C), 131.1 (CH), 129.5 (CH), 129.4 (C, 2CH), 125.1 (CH), 118.9 (CH), 61.2 (CH2),
14.4 (CH3); IR (thin film): 3056, 2986, 2129, 2096, 1713, 1281, 1102, 737 cm–1; HRMS (EI) m / z calcd for
C15H13O2N3 (M+): 267.1008, found: 267.1007.
CF3
H
N3
6q
Azide 6q. The general procedure was followed with 0.250 g of aniline s17 (1.05 mmol), 0.100 g of NaNO2
(1.48 mmol), and 0.103 g of NaN3 (1.58 mmol) in 10 mL of acetic acid and 5 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6q as a clear oil (0.233 g, 84%): Rf = 0.71 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.71 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.0 Hz, 2H), 7.46 (t, J
= 8.0 Hz, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H); 13C NMR (CDCl3,
125 MHz): δ 141.8 (C), 137.3 (C), 132.2 (C), 131.2 (CH), 129.9 (CH), 129.6 (q, JCF = 31.25 Hz, C), 129.5 (CH),
19
124.3 (q, JCF = 270 Hz, C), 125.1 (2CH), 118.9 (CH); F NMR (CDCl3, 282 MHz): δ –63.07; IR (thin film):
3055, 2127, 2096, 1618, 1581, 1485, 1444, 1404, 1327, 1294, 1167, 1126, 1068, 1022, 1006, 843 cm–1; HRMS
(EI) m / z calcd for C13H8N3F3 (M+): 263.06703, found: 263.06723.
NO2
H
N3
6r
Azide 6r. The general procedure was followed with 0.128 g of aniline s18 (0.598 mmol), 0.058 g of NaNO2
(0.841 mmol), and 0.058 g of NaN3 (0.892 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6r as a brown solid (0.110 g, 77%): H
1
NMR (CDCl3, 500 MHz): δ 8.31-8.26 (m, 2H), 7.66-7.61 (m, 2H), 7.49-7.46 (m, 1H), 7.36-7.34 (m, 1H),
13
7.31-7.24 (m, 2H); C NMR (CDCl3, 125 MHz): δ 147.0 (C), 144.8 (C), 137.3 (C), 131.2 (C), 131.0 (CH),
130.4 (CH), 130.1 (CH), 125.2 (CH), 123.3 (CH), 118.9 (CH); IR (thin film): 2125, 1599, 1515, 1341, 852, 749
cm–1; HRMS (EI) m / z calcd for C12H8N4O2 (M+): 240.0647, found: 240.0645.
CN
H
N3
6s
Azide 6s. The general procedure was followed with 0.107 g of aniline s19 (0.550 mmol), 0.053 g of NaNO2

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Page 17 of 32
(0.770 mmol), and 0.053 g of NaN3 (0.820 mmol) in 6.00 mL of acetic acid and 3.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 6s as a pale yellow powder (0.112 g, 88%): Rf = 0.51
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.71 (d, J = 8.0 Hz, 2H), 5.57 (d, J = 8.0 Hz, 2H),
7.46 (dt, J1 = 8.0 Hz, J2 = 2.0 Hz, 1H), 7.33 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.25 (t,
13
J = 7.5 Hz, 1H); C NMR (CDCl3, 125 MHz): δ 142.9 (C), 137.2 (C), 131.9 (CH), 131.6 (C), 131.1 (CH),
130.3 (CH), 129.9 (CH), 125.3 (CH), 119.0 (CH), 119.9 (C), 111.3 (C); IR (thin film): 3074, 3032, 2227, 2127,
2102, 1483, 1234, 1221 cm–1; HRMS (EI) m / z calcd for C13H8N4 (M+): 220.07489, found: 220.07489.
OMe
OMe
H
N3
6t
Azide 6t. The diazotransfer procedure reported by Goddard-Borger and Stick17 was followed with 0.034 g of
aniline s20 (0.147 mmol), 0.037 g of imidazole-1-sulfonyl azide hydrochloride (0.177 mmol), 0.035 g of K2CO3
(0.251 mmol), and 0.001 g of Cu(SO)4·5H2O (0.001 mmol) in 0.735 mL of methanol. Purification by MPLC
(0:100 – 30:70 EtOAc:hexanes) afforded azide 6t as a clear oil (0.015 g, 41%): Rf = 0.59 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.40 (dt, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.35 (dd, J1 = 7.5 Hz,
J2 = 1.5 Hz, 1H), 7.27-7.23 (m, 1H), 7.20 (t, J = 7.5 Hz, 1H), 6.59 (d, J = 2.0 Hz, 2H), 6.52-6.48 (m, 1H), 3.83
(s, 6H); C NMR (CDCl3, 125 MHz): δ 160.5 (C), 140.1 (C), 137.2 (C), 133.7 (C), 131.1 (CH), 128.9 (CH),
13
124.9 (CH), 118.8 (CH), 107.8 (CH), 99.6 (CH) 55.4 (CH3); IR (thin film): 3055, 2960, 2939, 2839, 2123, 2094,
1593, 1495, 1475, 1419, 1298, 1273, 1205, 1155, 1065, 1028 cm–1; HRMS (EI) m / z calcd for C14H13O2N3 (M+):
255.1008, found: 255.1011.
OMe
H
N3
8a
Azide 8a.18 The general procedure was followed with 0.261 g of aniline s21 (1.30 mmol), 0.128 g of NaNO2
(1.80 mmol), and 0.125 g of NaN3 (1.80 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8a as a yellow oil (0.225 g, 77%): Rf = 0.59 (20:80
1
EtOAc:hexanes). The spectral data matched that reported by Swenton and coworkers: H NMR (CDCl3, 500
MHz): δ 7.44-7.36 (m, 3H), 7.28 (dd, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H), 7.23 (dt, J1 = 6.5 Hz, J2 = 1.0 Hz, 1H),
13
7.08-7.05 (m, 1H), 7.04-7.02 (m, 1H), 6.96 (ddd, J1 = 8.5 Hz, J2 = 2.5 Hz, J3 = 1.0 Hz, 1H), 3.88 (s, 3H); C
NMR (CDCl3, 125 MHz): δ 159.3 (C), 139.6 (C), 137.2 (C), 133.7 (C), 131.3 (CH), 129.2 (CH), 128.9 (CH),
125.0 (CH), 122.0 (CH), 118.8 (CH), 115.3 (CH), 113.0 (CH), 55.3 (CH3); IR (thin film): 2252, 2125, 1475,
1381 cm–1; HRMS (EI) m / z calcd for C13H11ON3 (M+): 225.09022, found: 225.0902.
Me
H
N3
8b
Azide 8b. The general procedure was followed with 0.257 g of aniline s22 (1.40 mmol), 0.135 g of NaNO2

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Page 18 of 32
(1.96 mmol), and 0.136 g of NaN3 (2.09 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8b as tan oil (0.246 g, 84%): H NMR (CDCl3, 500
1
13
MHz): δ 7.41-7.38 (m, 1H), 7.35-7.32 (m, 2H), 7.26-7.25 (m, 3H), 7.22-7.19 (m, 2H), 2.43 (s, 3H); C NMR
(CDCl3, 125 MHz): δ 138.1, 137.8, 137.1, 134.0, 131.3, 130.2, 128.6, 128.4, 128.0, 126.6, 124.9, 118.7, 21.5;
IR (thin film): 2123, 1296, 751 cm–1; HRMS (EI) m / z calcd for C13H11N3 (M+): 209.0953, found: 209.0952.
F
H
N3
8c
Azide 8c. The general procedure was followed with 0.100 g of aniline s23 (0.534 mmol), 0.053 g of NaNO2
(0.748 mmol), and 0.052 g of NaN3 (0.801 mmol) in 4.00 mL of acetic acid and 2.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8c as a pale yellow oil (0.104 g, 92%): Rf = 0.74
(20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.47-7.40 (m, 2H), 7.37 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz,
1H), 7.32-7.21 (m, 4H), 7.11 (ddt, J1 = 8.5 Hz, J2 = 2.5 Hz, J3 = 1.0 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δ
162.5 (d, JCF = 244 Hz, C), 140.3 (d, JCF = 7.5 Hz, C), 137.2 (C), 132.5 (C), 131.2 (CH), 129.7 (d, JCF = 7.5 Hz,
CH), 129.3 (CH), 125.3 (CH), 125.1 (CH), 118.9 (CH), 116.6 (d, JCF = 22.5 Hz, CH), 114.5 (d, JCF = 20.0 Hz,
19
CH); F NMR (CDCl3, 282 MHz): δ –113.7; IR (thin film): 2125, 2089, 1589, 1473, 1298, 883 cm–1; HRMS
(EI) m / z calcd for C12H8N3F (M+): 213.0702, found: 213.0701.
Cl
H
N3
8d
Azide 8d. The general procedure was followed with 0.260 g of aniline s24 (0.128 mmol), 0.127 g of NaNO2
(0.179 mmol), and 0.125 g of NaN3 (0.192 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8d as a tan oil (0.257 g, 87 %): Rf = 0.66 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.50-7.47 (m, 1H), 7.44 (dd, J1 = 7.0 Hz, J2 = 1.5 Hz, 1H),
7.39-7.36 (m, 3H), 7.34 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.28 (dd, J1 = 8.0 Hz, J2 = 0.5 Hz, 1H), 7.23 (dd, J1 =
7.5 Hz, J2 = 1.0 Hz, 1H); C NMR (CDCl3, 125 MHz): δ 139.9 (C), 137.2 (C), 134.0 (C), 132.3 (C), 131.2
13
(CH), 129.6 (CH), 129.4 (CH), 129.3 (CH), 127.8 (CH), 127.7 (CH), 125.1 (CH), 118.9 (CH); IR (thin film):
2123, 1292 cm–1; HRMS (EI) m / z calcd for C12H8N3Cl (M+): 229.04067, found: 229.04059.
CF3
H
N3
8e
Azide 8e. The general procedure was followed with 0.240 g of aniline s25 (1.01 mmol), 0.100 g of NaNO2
(1.42 mmol), and 0.105 g of NaN3 (1.62 mmol) in 10.00 mL of acetic acid and 5.00 mL of H2O. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8e as colorless oil (0.199 g, 75%): Rf = 0.77 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.74 (s, 1H), 7.66 (t, J = 8.0 Hz, 2H), 7.55 (t, J = 8.0 Hz, 1H),
7.44 (t, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.26 (t, J = 8.0 Hz, 1H); 13C NMR

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Page 19 of 32
(CDCl3, 125 MHz): δ 138.9 (C), 137.3 (C), 132.9 (CH), 132.2 (C), 131.2 (CH), 130.6 (q, JCF = 33.25 Hz, C),
129.5 (CH), 128.6 (CH), 126.3 (CH), 125.2 (CH), 124.3 (d, JCF = 3.00 Hz, CH), 124.2 (q, J = 270 Hz, C), 118.8
(CH); F NMR (CDCl3, 282 MHz): δ –63.04; IR (thin film): 3055, 2987, 2122, 1576, 1499, 1484, 1425, 1335,
19
1287, 1266, 1249, 1167, 1128, 1095, 1076 cm–1; HRMS (EI) m / z calcd for C13H8N3F3 (M+): 263.0670, found:
263.0671.
Me
F
H
N3
8f
Azide 8f. The general procedure was followed with 0.250 g of aniline s26 (1.24 mmol), 0.124 g of NaNO2 (1.74
mmol), and 0.121 g of NaN3 (1.86 mmol) in 8.00 mL of acetic acid and 4.00 mL of H2O. Purification by
MPLC (0:100 – 30:70 EtOAc:hexanes) afforded azide 8f as a pale yellow oil (0.219 g, 78%): Rf = 0.78 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 7.44 (dt, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.36 (dd, J1 = 8.0 Hz,
J2 = 1.5 Hz, 1H), 7.34-7.27 (m, 3H), 7.25 (dt, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 7.14-7.09 (m, 1H), 2.39 (s, 3H); 13C
NMR (CDCl3, 125 MHz): δ 161.0 (d, JCF = 244 Hz, C), 137.2 (C), 133.9 (d, JCF = 2.5 Hz, C), 133.0 (C), 132.6
(d, JCF = 3.75 Hz, CH), 131.3 (CH), 128.8 (CH), 128.5 (d, JCF = 7.5 Hz, CH), 125.0 (CH), 124.7 (d, JCF = 17.5
Hz, C), 118.8 (CH) 114.7 (d, JCF = 22.5 Hz, CH), 14.7 (CH3); 19F NMR (CDCl3, 282 MHz): δ –119.3; IR (thin
film): 2125, 2089, 1506, 1483, 1444, 1396, 1294, 1228, 1169, 1120, 889, 823, 752, 650 cm–1; HRMS (EI) m / z
calcd for C13H10N3F (M+): 227.08587, found: 227.08579.
III.
Metal-Catalyzed Synthesis of Carbazoles from Aryl Azides
A. General Procedure for the Screening of Catalysts to Promote the Decomposition of Aryl
Azides
metal salt
(s3)
PhMe, 16 h
H
N
H
N3
5
4
To a mixture of 0.020 g of aryl azide 4 (0.120 mmol), 0-100 % w/w of crushed 4 Å mol sieves, and metal salt (0
– 20 mol %) in a conical vial with teflon septum was added 0.240 mL of solvent. The resulting mixture was
heated and, after 16 h, the heterogenous mixture was filtered through SiO2. The filtrate was concentrated in
vacuo. The resulting solid (oil) was dissolved in 1.5 mL of CDCl3 and 0.007 mL of dibromomethane (0.1
mmol). The area of the N-H peak in carbazole 5 was compared with the area of the peak of dibromomethane to
derive a 1H NMR yield.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Table s1. Optimization of reaction conditions
Page 20 of 32
wt %, 4 Å
MS
entry
metal salt
mol %
solvent
temp. (°C)
yield, %a
1
2
none
none
n.a.
n.a.
10
5
xylenes
PhMe
PhMe
PhMe
PhMe
(CH2Cl)2
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
CH2Cl2
PhMe
PhMe
PhMe
0
0
150
55
60
60
35
40
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
>95
-
3
Rh2(O2CCH3)4
Rh2(O2CCF3)4
Rh2(O2CC3F7)4
Rh2(O2CC3F7)4
Rh2(O2CC3F7)4
Rh2(O2CC3F7)4
Rh2(O2CC7H15)4
Rh2(O2Ct-Bu)4
Rh2(cap)4
0
-
4
0
-
5
3
0
33
6
3
0
-
7
2
100
100
100
100
100
0
>95
8
5
98
96
-
9
5
10
11
12
13
14
15
16
17
18
19
20
21
5
5
-
5
-
Rh2(cap)4Br
Rh2(cap)4Br•AgOTf
Ag(OTf)2
5
0
-
20
5
0
-
Pd(O2CCF3)2
Ag(OTf)/AuCl
ZnI2
0
-
5/5
5
0
-
0
-
ZnI2
5
0
-
Fe(TPP)
5
0
-
FeCl3
5
0
-
Cu(OTf)2
5
0
-
a As determined using 1H NMR spectroscopy. b Two hour reaction time.
B. Optimized General Procedure
To a mixture of 0.069 g of aryl azide 4 (0.354 mmol) and 0.007 g of Rh2(O2CC3F4)4 (5 mol %) was added 0.710
mL of toluene (0.5 M). The resulting mixture was stirred at 60 C for 16 h. The heterogenous mixture was
o
filtered through SiO2. The filtrate was concentrated in vacuo. Purification via MPLC (0:100 – 30:70
EtOAc:hexanes) provided 0.059 g (98%) of carbazole 5.
Rh2(O2CC3F7)4
(5 mol %)
(s4)
H
4Å MS, PhMe
60 °C, 16 h
N
H
N3
5
4

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 21 of 32
C. Scope and limitations of Rh2(II)-mediated carbazole formation
MeO
N
H
7a
Carbazole 7a.19 The general procedure was followed with 0.049 g of azide 6a (0.217 mmol) and 0.013 g of
Rh2(O2CC3F7)4 (0.019 mmol), and 0.049 g of crushed 4 Å molecular sieves in 0.47 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7a as a white powder (0.031 g, 71%), mp
147-148 ˚C, Rf = 0.32 (20:80 EtOAc:hexanes). The spectral data matched that reported by Bedford and
co-workers:19 1H NMR (CDCl3, 500 MHz): δ 8.05 (d, J = 7.5 Hz, 1H), 7.87 (br s, 1H), 7.58 (d, J = 2.5 Hz, 1H),
7.44-7.36 (m, 2H), 7.30 (d, J = 9.0 Hz, 1H), 7.23 (t, J = 7.5 Hz, 1H), 7.08 (dd, J1 = 9.0 Hz, J2 = 2.5 Hz, 1H),
3.95 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 153.9 (C), 140.3 (C), 134.4 (C), 125.8 (CH), 123.8 (C), 123.4 (C),
120.3 (CH), 119.1 (CH), 115.1 (CH), 111.4 (CH), 110.8 (CH), 103.2 (CH), 56.13 (CH3); IR (thin film): 3403,
2361, 1459 cm–1; HRMS (EI) m / z calcd for C13H11ON (M+): 197.0841, found: 197.0840.
Me
N
H
7b
Carbazole 7b.20 The general procedure was followed with 0.080 g of azide 6b (0.382 mmol), 0.020 g of
Rh2(O2CC3F7)4 (0.019 mmol), and 0.080 g crushed 4 Å molecular sieves in 0.760 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7b as a white solid (0.058 g, 86 %): mp 204-205
°C. The spectral data matched that reported by Miller and co-workers:20 1H NMR (CDCl3, 500 MHz): δ 8.05 (d,
J = 7.5 Hz, 1H), 7.93 (br s, 1H), 7.88 (s, 1H), 7.41-7.40 (m, 2H), 7.33-7.31 (m, 1H), 7.26-7.20 (m, 2H), 2.54 (s,
3H);13C NMR (CDCl3, 125 MHz): δ 139.8 (C), 137.7 (C), 128.8 (C), 127.2 (CH), 125.7 (CH), 123.5 (C), 123.2
(C), 120.3 (C, CH), 119.2 (CH), 110.6 (CH), 110.3 (CH), 21.5 (CH3); IR (thin film): 3403, 1459, 1332, 1292,
805, 745, 727 cm–1; HRMS (EI) m / z calcd for C13H11N (M+): 181.0891, found: 181.0891.
N
H
7c
Carbazole 7c.21 The general procedure was followed with 0.069 g of azide 6c (0.354 mmol), and 0.018 g of
Rh2(O2CC3F7)4 (0.017 mmol) in 0.710 mL of toluene. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
afforded carbazole 7c as a white solid (0.059 g, 98 %): mp 237-239 °C. The spectral data matched that reported
by Hartwig and co-workers:21 1H NMR (CDCl3, 500 MHz): δ 8.09 (d, J = 7.5 Hz, 2H), 8.04 (br s, 1H), 7.43-7.42
(m, 4H), 7.26-7.23 (m, 2H); 13C NMR (CDCl3, 125 MHz): δ 139.5 (C), 125.8 (CH), 123.4 (C), 120.4 (CH),
119.5 (CH), 110.6 (CH); IR (thin film): 3053, 1450, 1256, 746, 725 cm–1.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 22 of 32
F
N
H
7d
Carbazole 7d.22 The general procedure was followed with 0.074 g of azide 6d (0.345 mmol), and 0.019 g of
Rh2(O2CC3F7)4 (0.017 mmol) in 0.690 mL of toluene. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes)
afforded carbazole 7d as a white solid (0.055 g, 86 %). The spectral data matched that reported by Forbes and
co-workers:22 1H NMR (CDCl3 + DMSO-d6, 500 MHz): δ 10.19 (s, 1H), 7.68 (d, J = 7.8 Hz, 1H), 7.39 (dd, J1 =
9.1 Hz, J2 = 2.5 Hz, 1H), 7.14 (d, J = 7.0 Hz, 1H), 7.10-7.07 (m, 2H), 6.87-6.79 (m, 2H);13C NMR (CDCl3 +
DMSO-d6, 125 MHz): δ 156.7 (d, JCF = 233 Hz, C), 140.8 (C), 136.2 (C), 125.9 (CH), 123.1 (d, JCF = 10.5 Hz,
C), 122.4 (d, JCF = 4.9 Hz, C), 120.1 (CH), 118.4 (CH), 112.9 (d, JCF = 25.6 Hz, CH), 111.3 (d, JCF = 9.13 Hz,
19
CH), 111.0 (CH), 105.3 (d, JCF = 23.3 Hz, CH); F NMR (CDCl3, 282 MHz): δ –125.8; IR (thin film): 3420
cm–1.
F3C
N
H
7e
Carbazole 7e.22 The general procedure was followed with 0.080 g of azide 6e (0.300 mmol) and 0.016 g of
Rh2(O2CC3F7)4 (0.015 mmol), and 0.080 g of crushed 4 Å molecular sieves in 0.600 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7e as a white solid (0.058 g, 83%).
This compound was previously reported by Forbes and co-workers:22 mp 157-159 ˚C, Rf = 0.20 (20:80
EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 8.35 (s, 1H), 8.23 (br s, 1H), 8.11 (d, J = 7.5 Hz, 1H), 7.66
13
(d, J = 8.5 Hz, 1H), 7.51-7.44 (m, 3H), 7.31 (t, J = 7.0 Hz, 1H); C NMR (CDCl3, 125 MHz): δ 140.9 (C),
140.0 (C), 126.9 (CH), 125.2 (q, JCF = 125 Hz, C), 123.0 (C), 122.9 (C), 122.7 (d, JCF = 1.25 Hz, CH), 121.8 (q,
19
JCF = 32.5 Hz, C), 120.6 (CH), 120.3 (CH), 117.9 (d, JCF = 1.25 Hz, CH), 111.0 (CH), 110.7 (CH); F NMR
(CDCl3, 282 MHz): δ –60.75; IR (thin film): 3432, 1652, 1341, 1322, 1112, 1102, 825 cm–1; HRMS (EI) m / z
calcd for C13H8NF3 (M+): 235.0609, found: 235.0610.
Me
N
H
Br
7f
Carbazole 7f. The general procedure was followed with 0.914 g of azide 6f (3.17 mmol), 0.067 g of
Rh2(O2CC3F7)4 (0.061 mmol), and 0.500 g of crushed 4 Å molecular sieves in 5 mL of toluene. Purification by
MPLC (10:0:90 – 10:10:90 benzene:EtOAc:hexanes) afforded carbazole 7f as a white powder (0.702 g, 85%),
mp 68 oC, Rf = 0.53 (10:10:80 benzene:EtOAc:hexanes, visualized by 254 nm UV light). 1H NMR (CDCl3, 500
MHz): δ 8.14 (s, 1H), 8.02 (d, J = 7.9 Hz, 1H), 7.80 (s, 1H), 7.48-7.43 (m, 2H), 7.42 (s, 1H), 7.25 (ddd, J = 8.6,
5.7, 1.5, 1H), 2.52 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 139.5 (C), 136.4 (C), 130.4 (C), 129.1 (CH), 126.4
(CH), 124.7 (C), 123.6 (C), 120.8 (CH), 119.9 (CH), 119.4 (CH), 111.0 (CH), 103.7 (C), 21.2 (CH3); IR (thin
film): 2360, 2342, 1642, 1267 cm-1. HRMS (EI) m / z calculated for C13H10NBr (M+): 258.9997, found:
258.9999.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 23 of 32
Me
N
H
7g
Carbazole 7g.20 The general procedure was followed with 0.080 g of azide 6g (0.382 mmol), 0.020 g of
Rh2(O2CC3F7)4 (0.019 mmol), and 0.080 g crushed 4 Å molecular sieves in 0.760 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7g as a white solid (0.025 g, 60%): mp 120-122
°C. The spectral data matched that reported by Miller and co-workers:20 1H NMR (CDCl3, 500 MHz): δ 8.20
(d, J = 8.0 Hz, 1H), 8.02 (br s, 1H), 7.46-7.43 (m, 2H), 7.36-7.33 (m, 1H), 7.29-7.26 (m, 2H), 7.04 (dd, J1 = 7
13
Hz, J2 = 0.5 Hz, 1H), 2.90 (s, 3H); C NMR (CDCl3, 125 MHz): δ 139.5 (C), 133.4 (C), 125.7 (CH), 125.2
(CH), 124.0 (C), 122.6 (CH), 121.9 (2C), 121.0 (CH), 119.4 (CH), 110.4 (CH), 108.1(CH), 20.9 (CH3); IR (thin
film): 2924, 1658, 1336, 1230, 1122 cm–1; HRMS (EI) m / z calcd for C13H11N (M+): 181.0891, found: 181.0889.
Cl
N
H
7h
Carbazole 7h.23 The general procedure was followed with 0.093 g of azide 6h (0.404 mmol) and 0.022 g of
Rh2(O2CC3F7)4 (0.020 mmol), and 0.093 g of crushed 4 Å molecular sieves in 0.807 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7h as a white powder (0.076 g, 93%),
mp 88-90 ˚C, Rf = 0.33 (20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 8.65 (d, J = 8.0 Hz, 1H), 7.92
(br s, 1H), 7.50 (dd, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 7.38-7.31 (m, 3H), 7.27-7.22 (m, 2H); 13C NMR (CDCl3, 125
MHz): δ 140.5 (C), 139.5 (C), 128.7 (C), 126.5 (CH), 126.2 (CH), 123.1 (CH), 122.3 (C), 120.6 (C), 120.3
(CH), 119.9 (CH), 110.5 (CH), 109.0 (CH); IR (thin film): 3439, 1453, 1432, 780, 750, 719 cm–1. HRMS (EI) m
/ z calcd for C12H8NCl (M+): 201.03452, found: 201.03478.
F
N
H
7i
Carbazole 7i.24 The general procedure was followed with 0.050 g of azide 6i (0.236 mmol) and 0.013 g of
Rh2(O2CC3F7)4 (0.012 mmol), and 0.050 g of crushed 4 Å molecular sieves in 470 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7i as white powder (0.040 g, 92%), mp 206 ˚C, Rf
1
= 0.21 (20:80 EtOAc:hexanes): H NMR (CDCl3, 500 MHz): δ 8.21 (d, J = 8.0 Hz, 1H), 8.13 (br s, 1H),
13
7.47-7.42 (m, 2H), 7.38-7.26 (m, 2H), 7.20 (d, J = 8.5 Hz, 1H), 6.91 (dd, J1 = 10.0 Hz, J2 = 8.0 Hz, 1H); C
NMR (CDCl3, 125 MHz): δ 158.6 (d, JCF = 246 Hz, C), 141.6 (d, JCF = 11.0 Hz, C), 139.0 (C), 126.5 (d, JCF =
9.25 Hz, CH), 126.1 (CH), 122.9 (d, JCF = 3.63 Hz, CH), 120.8 (C), 120.2 (CH), 111.9 (d, JCF = 20.38 Hz, C),
110.5 (CH), 105.9 (d, JCF = 131 Hz, CH), 105.3 (CH);19F NMR (CDCl3, 282 MHz): δ –119.5; IR (thin film):
3460, 3054, 2986, 1640, 1613, 1581, 1507, 1455, 1446, 1422, 1330, 1266, 1049, 896, 738 cm–1; HRMS (EI) m /
z calcd for C12H8NF (M+): 185.0641, found: 185.0640.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 24 of 32
OMe
N
H
7j
Carbazole 7j.25,26 The general procedure was followed with 0.082 g of azide 6j (0.364 mmol) and 0.020 g of
Rh2(O2CC3F7)4 (0.018 mmol), and 0.082 g of crushed 4 Å molecular sieves in 0.730 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7j as a white powder (0.059 g, 82%),
mp 233-235 ˚C, Rf = 0.26 (20:80 EtOAc:hexanes). Carbazole 7j was previously reported by Knölker and
co-workers.26 The spectral data matched that reported by Smitrovich and coworkers:25 1H NMR (DMSO-d6, 500
MHz): δ 11.10 (s, 1H), 7.97-7.90 (m, 2H), 7.41 (d, J = 9.0 Hz, 1H), 7.26 (t, J = 8.2 Hz, 1H), 7.08 (t, J = 8.2 Hz,
1H), 6.95 (s, 1H), 6.75 (d, J = 9.0 Hz, 1H), 3.80 (s, 3H); 13C NMR (DMSO-d6, 125 MHz): δ 158.5 (C), 141.1
(C), 139.7 (C), 124.1 (CH), 122.7 (C), 120.9 (CH), 119.3 (CH), 118.5 (CH), 116.2 (C), 110.6 (CH), 107.7 (CH),
94.4 (CH), 55.2 (CH3); IR (thin film): 3386 cm–1. HRMS (EI) m / z calcd for C13H11ON (M+): 197.0841, found:
197.0841.
t-Bu
N
H
7k
Carbazole 7k.27 The general procedure was followed with 0.061 g of azide 6k (0.242 mmol) and 0.013 g of
Rh2(O2CC3F7)4 (0.012 mmol), and 0.061 g of crushed 4 Å molecular sieves in 0.48 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7k as a white powder (0.039 g, 72%), mp
210-214 ˚C, Rf = 0.51 (20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 8.04 (d, J = 7.0 Hz, 1H), 8.00
(d, J = 7.5 Hz, 1H), 7.94 (br s, 1H), 7.44 (s, 1H), 7.42-7.36 (m, 2H), 7.32 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H),
7.22 (dt, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 1.43 (s, 9H); 13C NMR (CDCl3, 125 MHz): δ 149.6 (C), 139.8 (C), 139.7
(C), 125.3 (CH), 123.4 (C), 121.0 (C), 120.1 (CH), 119.8 (CH), 119.3 (CH), 117.6 (CH), 110.5 (CH), 107.1
(CH), 35.1 (C), 31.8 (CH3); IR (thin film): 3423, 1437 cm–1; HRMS (EI) m / z calcd for C16H17N (M+): 223.1361,
found: 223.1362.
Et
N
H
7l
Carbazole 7l. The general procedure was followed with 0.060 g of azide 6l (0.271 mmol) and 0.015 g of
Rh2(O2CC3F7)4 (0.014 mmol), and 0.060 g of crushed 4 Å molecular sieves in 0.540 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7l as a white solid (0.046 g, 87%),
mp 211-215 ˚C, Rf = 0.42 (20:80 EtOAc:hexanes). 1H NMR (CDCl3, 500 MHz): δ 8.05 (d, J = 7.5 Hz, 1H),
7.99 (d, J = 8.0 Hz, 1H), 7.88 (br s, 1H), 7.44-7.36 (m, 2H), 7.24 (dt, J1 = 6.5 Hz, J2 = 1.5 Hz, 1H), 7.21 (s, 1H),
7.12 (d, J = 7.5 Hz, 1H), 2.83 (q, J = 7.5 Hz, 2H), 1.35 (t, J = 8.0 Hz, 3H); C NMR (CDCl3, 125 MHz): δ
13
142.7 (C), 140.0 (C), 139.6 (C), 125.3 (CH), 123.5 (C), 121.3 (C), 120.1 (CH), 120.0 (CH), 119.9 (CH), 119.4
(CH), 110.5 (CH), 109.6 (CH), 29.5 (CH2), 16.2 (CH3); IR (thin film): 3399, 1461, 1441, 817, 730 cm–1; HRMS
(EI) m / z calcd for C14H13N (M+): 195.1048, found: 195.1048.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 25 of 32
Me
N
H
7m
Carbazole 7m.26,28 The general procedure was followed with 0.045 g of azide 6m (0.215 mmol), 0.011 g of
Rh2(O2CC3F7)4 (0.011 mmol), and 0.045 g crushed 4 Å molecular sieves in 0.430 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7m as a white solid (0.017 g, 44 %): mp 174-175
°C. Carbazole 7m was previously reported by Knölker and co-workers.26 The characterization for 7m was
previously reported by Yamamoto and co-workers.28 1H NMR (CDCl3, 500 MHz): δ 8.04 (d, J = 8.0 Hz, 1H),
7.96 (d, J = 8.0 Hz, 1H), 7.89 (br s, 1H), 7.39-7.38 (m, 2H), 7.26-7.20 (m, 2H), 7.07 (d, J = 7.5 Hz, 1H), 2.53 (s,
3H); 13C NMR (DMSO-d6, 125 MHz): δ 140.6 (C), 140.2 (C), 135.4 (C), 125.4 (CH), 123.0 (C), 120.6 (C),
120.5 (CH), 120.3 (CH), 120.2 (CH), 118.8 (CH), 111.4 (CH), 111.3 (CH), 22.2 (CH3); IR (thin film): 3452,
1610, 1464, 1327, 1057, 1028, 821, 760 cm–1; HRMS (EI) m / z calcd for C13H11N (M+): 181.0891, found:
181.0890.
N
H
7n
Carbazole 7n. The general procedure was followed with 0.070 g of azide 6n (0.317 mmol) and 0.017 g of
Rh2(O2CC3F7)4 (0.016 mmol), and 0.070 g of crushed 4 Å molecular sieves in 0.633 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7n as an off-white powder (0.043 g,
1
71%), mp 210-212 ˚C, Rf = 0.41 (20:80 EtOAc:hexanes). H NMR (CDCl3-DMSO-d6, 500 MHz): δ 10.67 (s,
1H), 7.91 (dd, J1 = 15.0 Hz, J2 = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 1H), 7.28 (dt, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H),
7.20 (m, 2H), 7.07 (dt, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H), 6.78 (dd, J1 = 18.0 Hz, J2 = 11.0 Hz, 1H), 5.75 (dd, J1 =
18.0 Hz, J2 = 1.0 Hz, 1H), 5.18 (dd, J1 = 11.0 Hz, J2 = 1.0 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δ 140.3 (C),
140.1 (C), 137.4 (CH), 134.9 (C), 125.3 (CH), 122.6 (2 C), 119.8 (2 CH), 118.6 (CH), 116.9 (CH), 112.7 (CH),
110.7 (CH2), 108.6 (CH); IR (thin film): 3398, 1441 cm–1; IR (thin film): 3398, 1441 cm–1. HRMS (EI) m / z
calcd for C14H11N (M+): 193.0891, found: 193.0893.
F
N
H
7o
Carbazole 7o.27 The general procedure was followed with 0.106 g of azide 6o (0.495 mmol), 0.011 g of
Rh2(O2CC3F7)4 (0.010 mmol), and 0.106 g crushed 4 Å molecular sieves in 1.00 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7o as a white solid (0.081 g, 88%), mp 225-227
°C, Rf = 0.41 (20:80 EtOAc:hexanes). The spectral data matched that reported by Freeman and co-workers:27
1H NMR (CDCl3-DMSO-d6, 500 MHz): δ 10.36 (br s, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.61 (dd, J1 = 8.5 Hz, J2 =
5.5 Hz, 1H), 7.12 (d, J = 8.0 Hz, 1H), 7.02 (t, J = 8.0 Hz, 1H), 6.86-6.82 (m, 2H), 6.57 (dt, J1 = 9.5 Hz, J2 = 2.0
Hz, 1H);13C NMR (CDCl3-DMSO-d6, 125 MHz): δ 161.5 (d, JCF = 239 Hz, C), 140.5 (d, JCF = 12.5 Hz, C)
140.3 (C), 124.9 (CH), 122.3 (C), 120.7 (d, JCF = 11.3 Hz, CH), 119.5 (CH), 119.2 (C), 118.9 (CH), 110.8 (CH),
106.5 (d, JCF = 23.8 Hz, CH), 97.3 (d, JCF = 26.3 Hz, CH); 19F NMR (CDCl3-DMSO-d6, 282 MHz): δ –116.7; IR
(thin film): 3413, 3076, 3035, 3024, 1284, 1246 cm–1; HRMS (EI) m / z calcd for C13H11N (M+): 185.0641,
found: 185.0642.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 26 of 32
CO2Et
N
H
7p
Carbazole 7p.29 The general procedure was followed with 0.031 g of azide 6p (0.114 mmol) and 0.006 g of
Rh2(O2CC3F7)4 (0.006 mmol), and 0.031 g of crushed 4 Å molecular sieves in 0.170 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7p as a beige solid (0.025 g, 91%),
mp 181-182 ˚C, Rf = 0.22 (20:80 EtOAc:hexanes). The spectral data matched that reported by Moody and
coworkers:29 1H NMR (CDCl3, 500 MHz): δ 8.30 (br s, 1H), 8.19 (s, 1H), 8.15-8.09 (m, 2H), 7.96 (dd, J1 = 8.0
Hz, J2 = 1.5 Hz, 1H), 7.52-7.46 (m, 2H), 7.31-7.27 (m, 1H), 4.45 (q, J = 7.0 Hz, 2H), 1.45 (t, J = 7.0 Hz, 3H);
13C NMR (CDCl3, 125 MHz): δ 167.3 (C), 138.9 (2C), 127.7 (C), 127.2 (CH), 127.1 (C), 127.0 (C), 121.1 (CH),
120.7 (CH), 120.0 (CH), 119.9 (CH), 112.4 (CH), 111.0 (CH), 61.0 (CH2), 14.5 (CH3); IR (thin film): 3305,
1690, 754 cm–1. HRMS (EI) m / z calcd for C15H13O2N (M+): 239.0946, found: 239.0949.
CF3
N
H
7q
Carbazole 7q.30 The general procedure was followed with 0.080 g of azide 6q (0.304 mmol), 0.016 g of
Rh2(O2CC3F7)4 (0.015 mmol), and 0.080 g crushed 4 Å molecular sieves in 0.610 mL of toluene. Purification
by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7q as a pale white solid (0.065 g, 91%): mp
207-208 °C. The characterization for 7q was previously reported by Fagnou and co-workers.30 1H NMR
(DMSO-d6, 500 MHz): δ 8.31 (d, J = 8.0 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 7.80 (s, 1H), 7.58-7.57 (m, 1H),
7.48-7.43 (m, 2H), 7.22 (t, J = 7.0 Hz, 1H), N-H lies beyond the viewable region;13C NMR (DMSO-d6, 125
MHz): δ 141.3 (C), 139.2 (C), 127.5 (CH), 126.0 (q, JCF = 125 Hz, C), 125.8 (C), 126.6 (q, JCF =1080 Hz, CF3),
121.9 (C), 121.5 (CH), 119.8 (CH), 115.2 (CH), 112.0 (CH), 108.44 (CH), 108.41 (CH); 19F NMR (CDCl3, 282
MHz): δ –61.54; IR (thin film): 3423, 1443, 1170, 1128, 878, 732 cm–1; HRMS (EI) m / z calcd for C13H8F3N
(M+): 235.0609, found: 235.0610.
NO2
N
H
7r
Carbazole 7r.5 The general procedure was followed with 0.057 g of azide 6r (0.237 mmol), 0.005 g of
o
Rh2(O2CC3F7)4 (0.005 mmol), and 0.057 g crushed 4 Å molecular sieves in 0.470 mL of toluene at 25 C.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7r as a yellow solid (0.065 g, 91%):
mp 174-175 °C; 1H NMR (DMSO-d6, 500 MHz): δ 8.38-8.34 (m, 2H), 8.28-8.27 (m, 1H), 8.05-8.03 (m, 1H),
7.64-7.62 (m, 1H), 7.56-7.53 (m, 1H), 7.28-7.26 (m, 1H), N-H lies beyond the viewable region; 13C NMR
(DMSO-d6, 125 MHz): δ 145.0 (C), 142.1 (C), 138.4 (C), 128.0 (CH), 127.6 (C), 121.7(CH), 121.1 (C), 120.7
(CH), 119.8 (CH), 113.6 (CH), 111.8 (CH), 106.9 (CH); IR (thin film): 3527, 1341, 1323, 1241 cm–1; HRMS
(EI) m / z calcd for C12H8N2O2 (M+): 212.0586, found: 212.0583.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 27 of 32
CN
Rh2(O2CC3F7)4
(5 mol %)
CN
(s5)
4Å MS, PhMe
H
55 °C, 16 h
N
H
N3
6s
7s
Carbazole 7s. The general procedure was followed with 0.048 g of azide 6s (0.200 mmol) and 0.011 g of
Rh2(O2CC3F7)4 (0.010 mmol) in 0.400 mL of toluene. After filtration through SiO2 and removal of solvent in
vacuo, 1H NMR spectroscopy showed only starting material.
OMe
OMe
N
H
7t
Carbazole 7t.31 The general procedure was followed with 0.019 g of azide 6t (0.074 mmol) and 0.006 g of
Rh2(O2CC7H15)4 (0.004 mmol), and 0.019 g of crushed 4 Å molecular sieves in 0.147 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7t as pale wax (0.011 g, 65%): Rf =
0.36 (20:80 EtOAc:hexanes). The spectral data matched that reported by Hewlins and coworkers:31 1H NMR
(CDCl3, 500 MHz): δ 8.12 (br s, 1H), 8.02 (dd, J1 = 7.9 Hz, J2 = 1.2 Hz, 1H), 7.45 (dd, J1 = 8.2 Hz, J2 = 1.1 Hz,
1H), 7.40 (dt, J1 = 8.1 Hz, J2 = 1.1 Hz, 1H), 7.21 (dt, J1 = 7.9 Hz, J2 = 1.1 Hz, 1H), 7.15 (d, J = 2.1 Hz, 1H),
6.61 (d, J = 2.1 Hz, 1H), 3.99 (s, 3H), 3.95 (s, 3H); 13C NMR (CDCl3, 125 MHz): δ 155.3 (C), 146.7 (C), 140.1
(C), 126.1 (CH), 125.5 (C), 124.2 (C), 124.1 (C), 120.9 (CH), 119.5 (CH), 111.7 (CH), 98.1 (CH), 94.6 (CH),
56.6 (CH3), 56.2 (CH3); IR (thin film): 3459, 3054, 3002, 2986, 2961, 2940, 2837, 1633, 1595, 1507, 1456,
1433, 1395, 1307, 1267, 1228, 1203, 1161, 1150, 1140, 1107, 1046, 1032, 933 cm–1.
OMe
N
H
N
OMe
H
9a
10a
Carbazoles 9a and 10a.19 The general procedure was followed with 0.016 g of azide 8a (0.063 mmol) and
0.004 g of Rh2(O2CC3F7)4 (0.003 mmol), and 0.016 g of crushed 4 Å molecular sieves in 0.140 mL of toluene.
The reaction mixture was filtered through SiO2 and concentrated. The resulting mixture was dissolved in 1.5
mL of CDCl3 and 0.007 mL of dibromomethane (0.1 mmol) was added. The area of the OMe peaks was
compared to the area of the peak of dibromomethane to derive the 1H NMR yield (33%) and the regioselectivity
(52:48 9a : 10a). The spectral data matched that reported below, and by Bedford and coworkers.
Me
N
H
N
H
Me
9b
10b
Carbazoles 9b and 10b.28 The general procedure was followed with 0.067 g of azide 8b (0.017 mmol) and
0.005 g of Rh2(O2CC3F7)4 (0.016 mmol), and 0.067 g of crushed 4 Å molecular sieves in 0.635 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded an inseparable mixture of regioisomers (0.015
g, 25%, 66:34; 9b : 10b), Rf = 0.44. The selected spectral data for the major isomer 9b matched that reported
by Yamamoto and coworkers:28 1H NMR (CDCl3-DMSO-d6, 500 MHz): δ 9.06 (br s, 1H), 7.96 (d, J = 7.5 Hz,

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 28 of 32
1H), 7.79 (s, 1H), 2.46 (s, 3H), other peaks obscured by minor isomer; 13C NMR (CDCl3, 125 MHz): 140.1 (C),
138.0 (C), 128.2 (C), 127.0 (CH), 125.4 (CH), 123.3 (C), 123.0 (C), 120.1 (2CH), 118.7 (CH), 110.7 (CH),
110.4 (CH), 21.41 (CH3). The selected spectral data for the minor isomer 10b matched that reported by
Yamamoto and coworkers:28 1H NMR (CDCl3-DMSO-d6, 500 MHz): δ 9.12 (br s, 1H), 7.99 (d, J = 8.0 Hz,
1H), 7.85 (d, J = 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 2.52 (s, 3H) other peaks obscured by minor isomer; 13C
NMR (CDCl3, 125 MHz): 139.8 (C), 139.1 (C), 126.2 (CH), 125.6 (C), 125.4 (CH), 123.6 (C), 122.6 (C), 120.3
(CH), 119.1 (CH), 119.0 (CH), 117.7 (CH), 110.9 (CH), 17.05 (CH3). Selected spectral data for the mixture:
IR (thin film): 3406 cm–1.
F
N
N
F
H
H
9c
10c
Carbazoles 9c and 10c.30,32 The general procedure was followed with 0.104 g of azide 8c (0.487 mmol) and
0.027 g of Rh2(O2CC3F7)4 (0.024 mmol), and 0.104 g of crushed 4 Å molecular sieves in 0.975 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded a separable mixture of regioisomers (89:11; 9c :
10c). Major product 9c was obtained as a white solid (0.052 g, 58%), mp 208-210 ˚C, Rf = 0.32 (20:80
EtOAc:hexanes). The spectral data matched that reported by Campeau and coworkers:30 1H NMR (CDCl3, 500
MHz): δ 8.03 (d, J = 7.5 Hz, 2H), 7.72 (dd, J1 = 9.0 Hz, J2 = 2.5 Hz, 1H), 7.48-7.42 (m, 2H), 7.34 (dd, J1 = 9.0
Hz, J2 = 4.0 Hz, 1H), 7.27-7.22 (m, 1H), 7.16 (dt, J1 = 9.0 Hz, J2 = 2.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δ
152.9 (d, JCF = 234 Hz, C), 135.9 (C), 131.2 (C), 121.7 (CH), 119.4 (d, JCF = 10 Hz, C), 118.5 (C), 115.8 (CH),
114.9 (CH), 108.9 (d, JCF = 25 Hz, CH), 106.5 (d, JCF = 8.75 Hz, CH), 106.3 (CH), 101.3 (d, JCF = 23.75 Hz,
CH); IR (thin film): 3419, 1653, 1456 cm–1. HRMS (EI) m / z calcd for C12H8NF (M+): 185.0641, found:
185.0640. Selected spectral for minor isomer 10c (0.007 g, 7%), Rf = 0.57, matching that reported by Shannon
and coworkers:32 1H NMR (CDCl3, 500 MHz): 8.18 (br s, 1H), 8.07 (d, J = 7.5 Hz, 1H), 7.86-7.83 (m, 1H),
7.51-7.45 (m, 2H), 7.30-7.27 (m, 1H), 7.19-7.14 (m, 2H); 13C NMR (CDCl3, 125 MHz): δ 149.1 (d, JCF = 241
Hz, C), 139.6 (C), 126.9 (C), 126.6 (CH), 123.3 (C), 120.7 (CH), 120.0 (CH), 119.7 (d, JCF = 6.25 Hz, CH),
116.0 (CH), 111.1 (CH), 111.0 (d, JCF = 16.25 Hz, CH), one C obscured.
Cl
N
H
9d
Carbazole 9d.25 The general procedure was followed with 0.033 g of azide 8d (0.142 mmol) and 0.008 g of
Rh2(O2CC3F7)4 (0.007 mmol), and 0.033 g of crushed 4 Å molecular sieves in 0.284 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 9d as a white solid (0.024 g, 82%),
mp 191-192 ˚C, Rf = 0.32 (20:80 EtOAc:hexanes). The spectral data matched that reported by Smitrovich
and coworkers:25 1H NMR (CDCl3, 500 MHz): δ 8.06-8.02 (m, 3H), 7.45-7.42 (m, 2H), 7.39-7.34 (m, 2H),
13
7.27-7.24 (m, 1H); C NMR (CDCl3, 125 MHz): δ 140.0 (C), 137.7 (C), 126.6 (CH), 125.9 (CH), 125.0 (C),
124.6 (C), 122.5 (C), 120.5 (CH), 120.1 (CH), 119.9 (CH), 111.6 (CH), 110.8 (CH); IR (thin film): 3405 cm–1.

Supporting Information 1: Stokes, Jovanović, Dong, Richert, Riell, and Driver
Page 29 of 32
CF3
N
H
9e
Carbazole 9e.22 The general procedure was followed with 0.094 g of azide 8e (0.36 mmol) and 0.019 g of
Rh2(O2CC3F7)4 (0.018 mmol), and 0.094 g of crushed 4 Å molecular sieves in 0.715 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 9e as a white powder (0.071 g, 84%),
mp 158-159 ˚C Rf = 0.34 (20:80 EtOAc:hexanes). This compound was previously reported by Forbes and
co-workers:22 1H NMR (CDCl3 + DMSO-d6, 500 MHz): δ 10.62 (s, 1H), 8.03 (s, 1H), 7.81 (d, J = 9.4 Hz, 1H),
7.31 (d, J = 9.4 Hz, 1H), 7.27-7.18 (m, 2H), 7.13 (t, J = 9.4 Hz, 1H), 6.83 (t, J = 9.4 Hz, 1H); 13C NMR (CDCl3
+ DMSO-d6, 125 MHz): δ 141.3 (C), 140.3 (C), 126.1 (CH), 125.1 (q, JCF = 268 Hz, C), 122.1 (2C), 121.7 (d,
JCF = 2.75 Hz, CH), 120.1 (q, JCF = 31.38 Hz, C), 120.0 (CH), 119.2 (CH), 117.1 (d, JCF = 3.13 Hz, CH), 111.1
(CH), 110.8 (CH); 19F NMR (CDCl3, 282 MHz): δ –60.32; IR (thin film): 3456, 3055, 2987, 1344, 1333, 1274,
1163, 1114, 1056 cm–1.
Me
F
Me
F
N
H
N
H
9f
10f
Carbazoles 9f and 10f. The general procedure was followed with 0.054 g of azide 8f (0.238 mmol), 0.013 g of
Rh2(O2CC3F7)4 (0.012 mmol), and 0.054 g of crushed 4 Å molecular sieves in 0.475 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded an inseparable mixture of regioisomers (0.028
g, 59%, 39:61; 9f : 10f), Rf = 0.45. Similar results were observed employing Rh2(O2CC7H15)4 as a catalyst: the
general procedure was followed with 0.037 g of azide 9f (0.171 mmol), 0.007 g of Rh2(O2CC7H15)4 (0.009
mmol), and 0.037 g of crushed 4 Å molecular sieves in 0.340 mL of toluene. Purification by MPLC (0:100 –
30:70 EtOAc:hexanes) afforded an inseparable mixture of regioisomers (0.021 g, 62%, 44:56; 9f : 10f), Rf =
0.45. Selected spectral data for the major isomer 9f:1H NMR (CDCl3-DMSO-d6, 500 MHz): δ 10.20 (br s, 1H),
7.56 (d, J = 8.0 Hz, 1H), 7.42 (d, J = 7.5 Hz, 1H), 7.05 (d, J = 8.0 Hz, 1H), 6.95 (d, J = 7.5 Hz, 1H), 6.80-6.73
13
(m, 2H), 2.02 (s, 3H); C NMR (CDCl3, 125 MHz): 160.0 (d, JCF = 239 Hz, C), 140.2 (C), 138.7 (C), 124.7
(CH), 122.2 (C), 121.4 (d, JCF = 6.25 Hz, CH), 119.3 (CH), 118.9 (C), 118.6 (CH), 115.3 (d, J = 20.0 Hz, C),
19
110.7 (CH), 97.00 (d, J = 27.5 Hz, CH), 14.70 (CH3); F NMR (CDCl3, 282 MHz): δ –118.7. Selected
spectral data for the minor isomer 10f: 1H NMR (CDCl3-DMSO-d6, 500 MHz): δ 10.36 (br s, 1H), 7.58 (d, J =
8.0 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.12 (d, J = 8.0 Hz, 1H), 6.51 (t, J = 8.0 Hz, 1H), 2.11 (s, 3H), other
peaks obscured by major isomer; 13C NMR (CDCl3, 125 MHz): 159.2 (d, JCF = 239 Hz, C), 140.4 (C), 138.8 (C),
122.8 (C), 119.4 (CH), 118.8 (CH), 118.5 (C), 117.7 (d, JCF = 10.0 Hz, CH), 110.9 (CH), 106.5 (d, JCF = 25.0 Hz,
19
CH), 106.3 (C), 9.15 (CH3), one CH obscured; F NMR (CDCl3, 282 MHz): δ –122.4. IR (thin film): 3388,
3098, 3076, 3033, 1284, 1241 cm-1. Selected spectral data for the mixture: HRMS (EI) m / z calcd for C13H10NF
(M+): 199.0797, found: 199.0796.

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Page 30 of 32
D. Comparison of reactivity between Rh2(O2CC3F7)4 and Rh2(O2CC7H15)4
Cl
Cl
Rh2(O2CC7H15
)
(5 mol %)
(s6)
H
4Å MS, PhMe
60 °C, 16 h
N
N3
6h
H
(34%)
7h
Carbazole 7h.23 To a mixture of 0.084 g of azide 6h (0.364 mmol) and 0.014 g of Rh2(O2CC7H15)4 (0.018
mmol), and 0.084 g of crushed 4 Å molecular sieves was added 0.584 mL of toluene. The resulting mixture was
stirred at 60 oC for 16 h. The heterogenous mixture was filtered through SiO2 and the filtrate was concentrated
in vacuo. Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded carbazole 7h as a white powder
(0.025 g, 34%), mp 88-90 ˚C, Rf = 0.33 (20:80 EtOAc:hexanes). The spectral data matched that reported
above.
OMe
OMe
H
Rh2(O2CC7H15)4
(5 mol %)
(s7)
4Å MS, PhMe
T (°C), 16 h
H
OMe
N
N
H
10a
N3
8a
H
9a
9a : 10a
T (°C)
55 °C 51% 92 : 8
60 °C 71% 94 : 6
Carbazole 9a and 10a.19 The general procedure was followed with 0.076 g of azide 8a (0.339 mmol), 0.013 g
of Rh2(O2CC7H15)4 (0.017 mmol), and 0.076 g of crushed 4 Å molecular sieves in 0.680 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded a separable mixture of regioisomers (92:8, 9a :
10a). Major product 9a was obtained as a white solid (0.031 g, 47%), mp 144-146 ˚C, Rf = 0.34 (20:80
EtOAc:hexanes). The spectral data matched that reported above for 9a and by Bedford and co-workers:19 1
H
NMR (CDCl3, 500 MHz): δ 8.07 (d, J = 8.0 Hz, 1H), 7.84 (br s, 1H), 7.59 (d, J = 2.5 Hz, 1H), 7.43 (t, J = 7.5
Hz, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.30-7.22 (m, 2H), 7.10 (dd, J1 = 9.0 Hz, J2 = 2.5 Hz, 1H), 3.96 (s, 3H); 13C
NMR (CDCl3, 125 MHz): δ 153.9 (C), 140.3 (C), 134.4 (C), 125.9 (CH), 123.8 (C), 123.4 (C), 120.3 (CH),
119.1 (CH), 115.1 (CH), 111.4 (CH), 110.8 (CH), 103.2 (CH), 56.1 (CH3); IR (thin film): 3403, 1461 cm–1.
Selected spectral for minor isomer 10a (0.001 g, 4%), Rf = 0.48, matched that reported by Bedford and
coworkers: 1H NMR (CDCl3, 500 MHz): 8.26 (br s, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 7.5 Hz, 1H), 7.46
(d, J = 8.0 Hz, 1H), 7.41 (dt, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H), 7.26-7.20 (m, 1H), 7.16 (t, J = 8.0 Hz, 1H), 6.91 (d,
J = 7.5 Hz, 1H), 4.02 (s, 3H).
The aforementioned procedure was repeated at 60 °C with 0.027 g of azide 8a (0.124 mmol), 0.005 g of
Rh2(O2CC7H15)4 (0.006 mmol), and 0.027 g of crushed 4 Å molecular sieves in 0.240 mL of toluene.
Purification by MPLC (0:100 – 30:70 EtOAc:hexanes) afforded a separable mixture of regioisomers (94:6; 9a :
10a). Major product 9a was obtained as a white solid (0.016 g, 66%), and the spectral data matched that
reported above and by Bedford and co-workers.19 Minor product 10a was obtained as an oil (0.001 g, 4%), Rf =
0.48 (20:80 EtOAc:hexanes), and the spectral data matched that reported above and by Bedford and
coworkers.19