visible light photodecompose aromatic azides for the synthesis of versatile carbozoles

Supporting Information

Visible-Light-Promoted Intramolecular C–H Amination in

Aqueous Solution: Synthesis of Carbazoles

Lizheng Yang,[a] Yipin Zhang,[a] Xiaodong Zou,[a] Hongjian Lu*[a] and

Guigen Li[a,b]

hongjianlu@nju.edu.cn

Table of Contents

Table of Contents ............................................................................................................................ S1

Ⅰ. General Information ............................................................................................................... S2

Ⅱ. Scheme 3 Mechanism Studies Results ............................................................................ S3

1. Scheme 3a ........................................................................................................................ S3

2. Scheme 3b ........................................................................................................................ S4

3. Scheme 3c ......................................................................................................................... S5

4. Scheme 3d………………………………………………………………………………………...S9

Ⅲ. Contents of Starting Materials ......................................................................................... S10

Ⅳ. General Procedures for Synthesis of Starting Materials and Spectroscopic Data

of Biaryl Azides ............................................................................................................................ S14

1. Preparation of biaryl azides 1a-h, 1j-u, 1w-z, 3a-d......................................... S14

2. Preparation of biaryl azides 1i, 3e .......................................................................... S26

3. Preparation of biaryl azide 1v .................................................................................. S29

4. Preparation of biaryl azide 1a-D ............................................................................. S31

5. Preparation of biaryl azide 1aa ................................................................................ S33

Ⅴ Experimental Procedure for for Synthesis of Carbazoles ..................................... S35

Ⅵ. Spectroscopic Data of Carbazoles Obtained in this Study .................................... S36

Ⅶ. References ............................................................................................................................... S47

Ⅷ. Spectral Copies of 1H, 13C NMR of All Compounds .................................................. S48

[a] Institute of Chemistry & BioMedical Sciences, Jiangsu Key Laboratory of Advanced Organic

Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, (China)

E-mail: hongjianlu@nju.edu.cn.

[b] Department of Chemistry and Biochemistry，Texas Tech University, Lubbock, TX 79409-1061

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2018

Ⅰ. General Information

Unless otherwise mentioned, all commercial reagents and solvents were used without

further purification. Thin layer chromatography (TLC) was performed on pre-coated

silica gel GF254 plates. Visualization of TLC was achieved by the use of UV light (254

nm). Column chromatography was performed on silica gel (300-400 mesh) using a

proper eluent. 1H NMR was recorded on FT AM 400 (400 MHz). Chemical shifts were

reported in parts per million (ppm) referenced to the appropriate solvent peak or 0.0

ppm for tetramethylsilane or chloroform-d (CDCl3) at 7.26 ppm. The following

abbreviations were used to describe peak splitting patterns: brs = broad, s = singlet, d =

doublet, t = triplet, q = quartet, dd = doublet of doublet, td = triplet of doublet, ddd =

doublet of doublet of doublet, m = multiplet. Coupling constants, J, were reported in

hertz (Hz). The fully decoupled 13C NMR was recorded on FT AM 400 (100 MHz).

Chemical shifts were reported in ppm referenced to the center of a triplet at 77.36 ppm

of chloroform-d. Infrared (IR) spectra were recorded neat in KBr cell. Frequencies are

given in centimeter inverse (cm-1) and only selected absorbance is reported. High

resolution mass spectra were obtained by using the UHD Accurate-Mass Q-TOF.

Ⅱ. Scheme 3 Mechanism Studies Results

1. Scheme 3a

Azides 1b (0.10 mmol, 22.5 mg), 1g (0.10 mmol, 26.7 mg), silica gel 15.0 mg, H2O

(1.5 ml) and Acetone (1.5 ml) were added to a 15 ml glass vial equipped with a stirring

bar. Then the solution was stirred at a distance of ~1 cm from a 23 w fluorescent lamp

at room temperature about 24 hours. The biphasic solution was diluted with 5 mL of

water and 5 mL of CH2Cl2 and separated. The aqueous phase was extracted with an

additional 3 × 5 mL of CH2Cl2, and the combined organic phases were washed 2 × 5

mL of water. The organic phase was dried over Na2SO4 and filtered. The solvents were

removed under reduced pressure, and the crude yield was measured by 1H NMR

spectroscopy using CH2Br2 as an internal standard. 1H NMR of reaction mixture:

2. Scheme 3b

Azides 1p (0.10 mmol, 22.5 mg), 1u (0.10 mmol, 26.7 mg), silica gel 15.0 mg, H2O

(1.5 ml) and Acetone (1.5 ml) were added to a 15 ml glass vial equipped with a stirring

bar. Then the solution was stirred at a distance of ~1 cm from a 23 w fluorescent lamp

at room temperature about 24 hours. The biphasic solution was diluted with 5 mL of

mL of water. The organic phase was dried over Na2SO4 and filtered. The solvents were

removed under reduced pressure, and the crude yield was measured by 1H NMR

spectroscopy using CH2Br2 as an internal standard. 1H NMR of reaction mixture:

3. Scheme3c

1a-D (0.10 mmol, 19.6 mg), silica gel 15.0 mg, H2O (1.5 ml) and Acetone (1.5 ml) were

added to a 15 ml glass vial equipped with a stirring bar. Then the solution was stirred

at a distance of ~1 cm from a 23 w fluorescent lamp at room temperature about 48 hours.

The biphasic solution was diluted with 5 mL of water and 5 mL of CH2Cl2 and separated.

The aqueous phase was extracted with an additional 3 × 10 mL of CH2Cl2, and the

combined organic phases were washed 2 × 5 mL of water. The crude product was

purified by flash chromatography on silica gel (petroleum ether : ethyl acetate gradient:

20:1-10:1) afforded the products (2a + 2a-D): 10.6 mg, 63%; white solid; TLC Rf =

0.36 (petroleum ether : ethyl acetate 10:1).

Kinetic Isotope Effect of Intramolecular was estimated by 1H NMR

1H NMR (400 MHz, DMSO): Carbazole 2a-D

Kinetic Isotope Effect of Intramolecular was estimated by GC-MS

4. Scheme3d

1aa (0.20 mmol, 74.7 mg), silica gel 15.0 mg, H2O (1.5 ml) and Acetone (1.5 ml) were added to a

15 ml glass vial equipped with a stirring bar. Then the solution was stirred at a distance of ~1 cm

from a 23 w fluorescent lamp at room temperature about 24 hours. The biphasic solution was diluted

with 5 mL of water and 5 mL of CH2Cl2 and separated. The aqueous phase was extracted with an

additional 3 × 10 mL of CH2Cl2, and the combined organic phases were washed 2 × 5 mL of water.

The organic phase was dried over Na2SO4 and filtered. The crude product was purified by

chromatography on silica gel (petroleum ether : ethyl acetate gradient: 10:1-1:1) afforded the

mixture products 2aa +2aa′ (39.2 mg, 56%), Rf = 0.12 (petroleum ether : ethyl acetate 10:1). The

ratio of the two products was determined by mixture 1H NMR. Then the mixture was separated by

chromatography on silica gel (petroleum ether : acetone gradient 30:1-3:1) directly to give the

desired product.

Mixture 1H NMR of 2aa and 2aa′

Ⅱ. Contents of Starting Materials

Detailed information for Table 1

Entry[a] Solvent Time(h) Conversion Yield[%][b]

1 Toluene 18 40 70

2 Benzene 17 50 68

3 CCl4 18 49 75

4 MeOH 18 55 70

5 EtOH 24 64 50

6 Ethylene glycol 20 50 26

7 MeCN 18 53 80

8 Acetone 13 40 67

9 DME 20 70 70

10 1,4-dioxane 15 67 76

11 Et2O 14 58 69

12 THF 18 60 85

13 DMF 18 65 68

14 H2O 18 45 100

15 H2O 36 60 100

16[d] H2O 36 45 100

17 H2O / Acetone = 1 / 1 36 75 100

18[e] H2O / Acetone = 1 / 1 36 80(19)[c] 100

19[e] H2O / MeOH = 1 / 1 36 64 100

20[e] H2O / DMF = 1 / 1 36 60 100

21[e] H2O / DCM = 1 / 1 36 58 100

22[e] H2O / EtOH = 1 / 1 36 75 100

23[e] H2O / Acetone = 10 / 1 36 67 100

24[e] H2O / Acetone = 5 / 1 36 69 100

25[e] H2O / Acetone = 2 / 1 36 71 100

23[e] H2O / Acetone = 1 / 5 36 78 100

24[e] H2O / Acetone = 1 / 10 36 75 100

26[f] Acidic buffer solution 36 59 100

27[g] Alkaline buffer solution 36 61 100

28[h] H2O / Acetone = 1 / 1 36 0 0

[a] Reaction conditions: substrate (1a, 0.15 mmol), fluorescent lamp 23 W, solvent (2.0 mL), room temperature. [b]

Yield of 2a were determined by crude 1HNMR and the remaining percent of the starting material is shown in bracket.

[c]. Isolated yield by column chromatography. [d].Fluorescent lamp 18 W. [e] Substrate (1a, 0.15 mmol), fluorescent

lamp 23 W, (1.5 / 1.5 mL), silca gel 15 mg, room temperature [f] Acidic buffer solution (NaAc-HAc, 2.0 mL PH =

4.0 ). [g] Alkaline buffer solution ( Glycine – NaOH, 2.0 mL PH = 8.6 ). [h] no light

IV. General Procedures for Synthesis of Starting Materials

and Spectroscopic Data of Biaryl Azides

1. Preparation of biaryl azides 1a-h, 1j-u, 1w-z, 3a-d.

Unless otherwise noted, the biaryl azides were synthesized from the substituted 2-

bromoanilines and substituted phenylboronic acid using Suzuki reactions.[1] The

resulting biaryl amines were converted to corresponding biaryl azides without

purification using traditional diazotization reaction conditions. Yields were not

optimized.

In a 50 mL round bottom flask, Substituted phenylboronic acid (9 mmol, 3.0 equiv),

Na2CO3 (6 mmol, 2.0 equiv, 635.9 mg), and Pd(OAc)2 (0.06 mmol, 0.02 equiv, 13.5 mg)

were then dissolved in 9 mL of ethylene glycol, 9 mL of H2O. Substituted 2-

bromoaniline (3 mmol, 1.0 equiv) was added, and the resulting mixture was heated

to 80 ˚C for 24 hours. After cooling, the biphasic solution was diluted with 50 mL of

mL of water. The organic phase was dried over Na2SO4 and filtered. The filtrate was

concentrated in vacuo to afford oil. This crude mixture was used for the next step

without any further purification.

For 1l (synthesis of 5-bromo-[1,1'-biphenyl]-2-amine): In a 50mL of round bottom flask,

biphenyl amine (1.0 equiv, 5mmol, 0.85g) was dissolved in 20mL DMF and chilled in

an ice bath. N-Bromosuccinimide(1.2equvi, 6mmol, 1.05g dissolved in 10mL DMF)

was added dropwise. The system reacted for 2h and the solution was then diluted with

50 mL of water and extracted with DCM for 3 times. The organic phase was washed

with water and then dried over Na2SO4.The solution was concentrated in vacuo and

crude was purified by silica gel column using petroleum ether and ethyl acetate as

eluent. Yield: 0.88g, 71%.

For 1m (synthesis of 5-iodo-[1,1'-biphenyl]-2-amine) method was the same as

previous report.[23] Aryl biphenyl amine (0.85 g, 5 mmol, 1 equiv), NaHCO3 (0.63 g,

7.5 mmol, 1.5 equiv) and 15 mL water were added into a 50 mL round-bottom flask

under vigorous stirring, and iodine powder(1.14 g, 4.5 mmol, 0.9 equiv) was added with

several portions in 0.5 h. The reaction mixture was stirred for an additional hour at room

temperature until the color of iodine disappeared. The crude product was obtained by

vacuum filtration and used for next step without purification.

In a 100 mL of round bottom flask, the crude biaryl amine (1.0 equiv) was dissolved in

HOAc and H2O (2:1 v/v, 0.2 M) and chilled in an ice bath. NaNO2 (1.4 equiv, 275.5

mg) was added slowly, and then the resulting mixture was stirred at 0 °C for 2 hours.

NaN3 (1.5 equiv, 310.5 mg) was then added slowly; the resulting mixture was warmed

up to ambient temperature, and stirred overnight. The solution was then diluted with 20

mL of water and 20 mL of CH2Cl2, and basified by slow addition of K2CO3 until the

pH of the mixture was 8. The phases were separated and the aqueous phase was

extracted with an additional 3 × 30 mL of CH2Cl2. The combined organic phase were

dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo and crude was

purified by silica gel column using petroleum ether and ethyl acetate as eluent.

2-azido-1,1'-biphenyl (1a).[2] The general procedure was followed using 0.516 g of 2-

bromoaniline (3.0 mmol). Purification of the reaction mixture using column

chromatography (petroleum ether : ethyl acetate 30:1) afforded the product 1a (584.0

mg, 99%); TLC Rf = 0.69 (petroleum ether : ethyl acetate 20:1). 1H NMR (400 MHz,

CDCl3) δ = 7.64 – 7.57 (m, 4H), 7.56 – 7.45 (m, 3H), 7.42 – 7.30 (m, 2H). 13C NMR

(100 MHz, CDCl3) δ 138.16, 137.09, 133.78, 131.25, 129.48, 128.70, 128.14, 127.53,

124.94, 118.78. IR (neat) v 2124, 1501, 1479, 1431, 1298 cm-1.

2-azido-5-methyl-1,1'-biphenyl (1b).[2] The general procedure was followed using

0.558 g of 2-bromo-4-methylaniline (3.0 mmol). Purification of the reaction mixture

using column chromatography(petroleum ether : ethyl acetate 30:1) afforded the

product 1b (565.0 mg, 90%), Rf = 0.72 (petroleum ether : ethyl acetate 20:1). 1H NMR

(400 MHz, CDCl3) δ = 7.60 –7.40 (m, 5H), 7.35–7.20 (m, 3H), 2.46 (s, 3H). 13C NMR

(100 MHz, CDCl3) δ 138.34, 134.68, 134.36, 133.59, 131.96, 129.48, 129.37, 128.15,

127.51, 118.73, 20.88. IR (neat) v 2117, 1486, 1299, 1157, 697 cm-1.

4'-azido-1,1':3',1''-terphenyl (1c). The general procedure was followed using 0.744 g

of 3-bromo-[1,1'-biphenyl]-4-amine (3.0 mmol). Purification of the reaction mixture

using column chromatography (petroleum ether : ethyl acetate 30:1) afforded the

product 1c (732.0 mg, 90%), Rf = 0.56 (petroleum ether : ethyl acetate 20:1). 1H NMR

(400 MHz, CDCl3) δ = 7.73 – 7.62 (m, 4H), 7.60 – 7.31 (m, 9H). 13C NMR (100 MHz,

CDCl3) δ 140.04, 138.19, 138.06, 136.36, 134.13, 130.05, 129.58, 128.99, 128.30,

127.79, 127.58, 127.37, 127.00, 119.32. IR (neat) v 2110, 1478, 1295, 1270, 696 cm-1.

HRMS (ESI) ([M+H]+) Calcd. for C18H13N3 272.1182, found 272.1178.

2-azido-4-methoxy-1,1'-biphenyl (1d). The general procedure was followed using

0.606 g of 2-bromo-5-methoxyaniline (3.0 mmol). Purification of the reaction mixture

using column chromatography (petroleum ether : dichloromethane 20:1) afforded the

product 1d (648.0 mg, 96%), Rf = 0.24 (petroleum ether : dichloromethane 20:1). 1H

NMR (400 MHz, CDCl3) δ = 7.43 (d, J = 4.4, 4H), 7.36 (dd, J = 8.4, 4.4, 1H), 7.28 (d,

J = 8.4, 1H), 6.81 – 6.75 (m, 2H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3) δ = 160.09,

138.09, 138.06, 132.16, 129.59, 128.22, 127.27, 126.67, 110.69, 104.66, 55.66. IR (neat)

v 2110, 1511, 1486, 1300, 1227, 763 cm-1.

6-azido-[1,1'-biphenyl]-3-carbonitrile (1e). The general procedure was followed

using 0.591 g of ethyl 4-amino-3-bromobenzonitrile (3.0 mmol). Purification of the

reaction mixture using column chromatography (petroleum ether : ethyl acetate 20:1)

afforded the product 1e (346.0 mg, 52%), Rf = 0.32 (petroleum ether : ethyl acetate

20:1). 1H NMR (400 MHz, CDCl3) δ = 7.67 (dd, J = 8.4, 2.0, 1H), 7.59 (d, J = 1.6, 1H),

7.51 – 7.39 (m, 5H), 7.33 (d, J = 8.4, 1H). 13C NMR (100 MHz, CDCl3) δ 142.10,

135.96, 134.93, 134.73, 133.88, 132.33, 129.32, 128.54, 128.50, 119.58, 108.46. IR

(neat) v 2227, 2119, 1482, 1300, 1159, 698 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for

C13H8N4 243.0641, found 243.0639.

ethyl 6-azido-[1,1'-biphenyl]-3-carboxylate (1f).[5] The general procedure was

followed using 0.732 g of ethyl 4-amino-3-bromobenzoate (3.0 mmol). Purification of

the reaction mixture using column chromatography (petroleum ether : ethyl acetate 30:1)

afforded the product 1f (681.0 mg, 85%), Rf = 0.66 (petroleum ether : ethyl acetate

20:1). 1H NMR (400 MHz, CDCl3) δ = 8.18 – 8.05 (m, 2H), 7.58 – 7.39 (m, 5H), 7.29

(d, J = 8.0, 1H), 4.42 (q, J = 7.2, 2H), 1.43 (t, J = 7.2, 3H). 13C NMR (100 MHz, CDCl3)

δ 165.75, 141.64, 137.26, 133.56, 132.60, 129.99, 129.44, 128.24, 127.92, 127.05,

118.63, 61.12, 14.36. IR (neat) v 2123, 1717, 1599, 1483, 1236, 1101, 698 cm-1.

1-(6-azido-[1,1'-biphenyl]-3-yl)ethanone (1g). The general procedure was followed

using 0.642 g of ethyl 1-(4-amino-3-bromophenyl)ethanone (3.0 mmol). Purification of

the reaction mixture using column chromatography (petroleum ether : ethyl acetate 10:1)

afforded the product 1g (702.0 mg, 67%), Rf = 0.23 (petroleum ether : ethyl acetate

25:1). 1H NMR (400 MHz, CDCl3) δ = 8.00 (d, J = 8.4, 1H), 7.95 (s, 1H), 7.50 – 7.37

(m, 5H), 7.32 (d, J = 8.4, 1H), 2.62 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 196.73,

142.05, 137.27, 133.81, 133.77, 131.68, 129.46, 128.88, 128.36, 128.08, 118.86, 26.61.

IR (neat) v 2114, 1681, 1594, 1356, 1296, 1323, 699 cm-1. HRMS (ESI) ([M+Na]+)

Calcd. for C14H11N3O 260.0794, found 260.0815.

6-azido-N-methyl-[1,1'-biphenyl]-3-carboxamide (1h).[6] The general procedure was

followed using 0.687 g of ethyl 4-amino-3-bromo-N-methylbenzamide (3.0 mmol).

Purification of the reaction mixture using column chromatography (petroleum ether :

EtOAc gradient: 3:1-1:1) afforded the product 1h (454.0 mg, 60%), Rf = 0.35

(petroleum ether : ethyl acetate 1:1). 1H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 8.4,

2.0, 1H), 7.76 (d, J = 2.0, 1H), 7.44–7.34 (m, 5H), 7.18 (d, J = 8.4, 1H), 7.12 (brs, 1H),

2.93 (d, J = 4.8, 3H). 13C NMR (100 MHz, CDCl3) δ 167.44, 140.08, 137.25, 133.51,

131.00, 130.01, 129.34, 128.20, 127.88, 127.53, 118.71, 26.88. IR (neat) v 3313, 2120,

1636, 1549, 1482, 1295, 698 cm-1. HRMS (ESI) ([M-H]-) Calcd. for C14H12N4O

251.0938, found 251.0933.

2-azido-5-fluoro-1,1'-biphenyl (1j).[2] The general procedure was followed using

0.570 g of 2-bromo-4-fluoroaniline (3.0 mmol). Purification of the reaction mixture

using column chromatography (petroleum ether : dichloromethane 40:1) afforded the

product 1j (186.0 mg, 29%), Rf = 0.51 (petroleum ether : dichloromethane 20:1). 1H

NMR (400 MHz, CDCl3) δ = 7.56 – 7.45 (m, 5H), 7.28 – 7.22 (m, 1H), 7.19 – 7.11 (m,

2H). 13C NMR (100 MHz, CDCl3) δ = 159.75 (d, JCF = 244.8), 137.11, 135.44 (d, JCF

= 7.6), 132.97 (d, JCF = 2.8), 129.34, 128.31, 128.07, 120.17 (d, JCF = 8.8), 117.94 (d,

JCF = 23.2), 115.42 (d, JCF = 23.2). 19F NMR (376 MHz, CDCl3) δ -117.53. IR (neat) v

2123, 1502, 1485, 1409, 1289, 1187, 697 cm-1.

2-azido-5-chloro-1,1'-biphenyl (1k).[3] The general procedure was followed using

0.619 g of 2-bromo-4-chloroaniline (3.0 mmol). Purification of the reaction mixture

using column chromatography(petroleum ether : ethyl acetate 30:1) afforded the

product 1k (523.0 mg, 76%), Rf = 0.78 (petroleum ether : ethyl acetate 20:1). 1H NMR

(400 MHz, CDCl3) δ = 7.56 – 7.43 (m, 5H), 7.43– 7.37 (m, 2H), 7.24 – 7.19 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 136.88, 135.80, 135.20, 131.08, 130.19, 129.34, 128.54,

128.30, 128.08, 120.06. IR (neat) v 2111, 1479, 1444, 1392, 1300, 697 cm-1.

2-azido-5-bromo-1,1'-biphenyl (1l).[24] Purification of the reaction mixture using

column chromatography(petroleum ether : ethyl acetate 30:1) afforded the product 1l

(960.0 mg, 70%), Rf = 0.68 (petroleum ether : ethyl acetate 20:1). 1H NMR (400 MHz,

CDCl3) δ 7.54 – 7.39 (m, 7H), 7.15 (d, J = 8.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ

= 136.77, 136.40, 135.55, 133.97, 131.46, 129.31, 128.27, 128.07, 120.35, 117.76. IR

(neat) v 2104, 1477, 1445, 1387, 1298, 698 cm -1.

2-azido-5-iodo-1,1'-biphenyl (1m).[24] Purification of the reaction mixture using

column chromatography(petroleum ether : ethyl acetate 30:1) afforded the product 1l

CDCl3) δ 7.70 – 7.64 (m, 2H), 7.46 – 7.37 (m, 5H), 7.00 (d, J = 8.2 Hz, 1H). 13C NMR

(101 MHz, CDCl3) δ = 139.87, 137.40, 137.23, 136.66, 135.85, 129.29, 128.25, 128.04,

120.63.

IR (neat) v 2098, 1474, 1444, 1380, 1296, 697 cm -1.

2-azido-1,1':4',1''-terphenyl (1n). The general procedure was followed using 0.516 g

of ethyl 2-bromoaniline (3.0 mmol). Purification of the reaction mixture using column

chromatography (petroleum ether : ethyl acetate 20:1) afforded the product 1n (447.0

mg, 55%), Rf = 0.58 (petroleum ether : ethyl acetate 20:1). 1H NMR (400 MHz, CDCl3)

δ = 7.78 – 7.64 (m, 4H), 7.58 (d, J = 7.6, 2H), 7.54 – 7.37 (m, 5H), 7.36 – 7.20 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 140.82, 140.51, 137.25, 137.20, 133.40, 131.33, 129.98,

128.91, 128.90, 127.50, 127.26, 127.01, 125.11, 118.88. IR (neat) v 2119, 1479, 1396,

1290, 835 cm-1. HRMS (ESI) ([M+H]+) Calcd. for C18H13N3 272.1182, found 272.1178.

2-azido-4'-fluoro-1,1'-biphenyl (1o).[2] The general procedure was followed using

0.516 g of ethyl 2-bromoaniline (3.0 mmol). Purification of the reaction mixture using

column chromatography (petroleum ether : ethyl acetate 20:1) afforded the product 1o

CDCl3) δ = 7.43 (ddd, J = 11.2, 7.2, 1.9, 3H), 7.33 (dd, J = 7.6, 1.6, 1H), 7.29 – 7.20

(m, 2H), 7.17 – 7.10 (m, 2H). 13C NMR (100 MHz, CDCl3) δ = 162.43 (d, JCF = 247.0),

137.23, 134.18 (d, JCF = 3.2), 132.80, 131.28 (d, JCF = 1.2), 131.19, 128.96, 125.10,

118.89, 115.20 (d, JCF = 21.6). 19F NMR (376 MHz, CDCl3) δ -114.77. IR (neat) v 2126,

1513, 1482, 1291, 1231, 1159, 752 cm-1.

2-azido-4'-methoxy-1,1'-biphenyl (1p).[2] The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate gradient: 20:1-10:1-3:1)

afforded the product 1p (608.0 mg, 90%), Rf = 0.58 (petroleum ether : ethyl acetate

– 6.98 (m, 2H), 3.90 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.15, 137.07, 133.48,

131.19, 130.64, 130.54, 128.36, 124.98, 118.78, 113.66, 55.30. IR (neat) v 2124, 1611,

1516, 1483, 1245, 831 cm-1.

2-azido-2'-methoxy-1,1'-biphenyl (1q).[7] The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate 20:1) afforded the product 1q

CDCl3) δ = 7.48 (td, J = 8.2, 1.6, 2H), 7.39 (dd, J = 7.6, 1.4, 1H), 7.36 – 7.27 (m, 3H),

7.17 – 7.06 (m, 2H), 3.88 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 156.83, 138.30,

131.88, 131.31, 130.91, 129.42, 128.69, 127.29, 124.59, 120.42, 118.64, 111.00, 55.64.

IR (neat) v 2121, 1479, 1296, 1232, 655 cm-1.

2-azido-3'-methoxy-1,1'-biphenyl (1r).[2] The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate 30:1) afforded the product 1r

CDCl3) δ = 7.50 – 7.42 (m, 3H), 7.37 – 7.26 (m, 2H), 7.18 – 7.11 (m, 2H), 7.06 – 7.01

(m, 1H), 3.93 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.32, 139.50, 137.10, 133.63,

131.18, 129.11, 128.77, 124.89, 121.90, 118.79, 115.30, 112.96, 55.20. IR (neat) v 2122,

1475, 1419, 1293, 1210, 697 cm-1.

2-azido-3'-methyl-1,1'-biphenyl (1s).[2] The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate 40:1) afforded the product 1s

(421.0 mg, 67%), Rf = 0.72 (30:1petroleum ether : ethyl acetate). 1H NMR (400 MHz,

CDCl3) δ = 7.49 – 7.39 (m, 3H), 7.38 – 7.25 (m, 5H), 2.51 (s, 3H). 13C NMR (100 MHz,

CDCl3) δ 138.19, 137.78, 137.18, 134.04, 131.31, 130.21, 128.66, 128.39, 128.09,

126.62, 124.94, 118.78, 21.57. IR (neat) v 2123, 1496, 1477, 1296, 1148, 787, 701 cm-

2-azido-3',5'-dimethyl-1,1'-biphenyl (1t). The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate 50:1) afforded the product 1t

CDCl3) δ = 7.52 – 7.43 (m, 2H), 7.38 – 7.34 (m, 1H), 7.34 – 7.28 (m, 1H), 7.21 (s, 2H),

7.16 (s, 1H), 2.53 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 138.16, 137.63, 137.15,

134.18, 131.27, 129.31, 128.54, 127.31, 124.84, 118.69, 21.42. IR (neat) v 2923, 2122,

1602, 1574, 1484, 1295, 834 cm-1.

ethyl 2'-azido-[1,1'-biphenyl]-4-carboxylate (1u).[2] The general procedure was

followed using 0.516 g of ethyl 2-bromoaniline (3.0 mmol). Purification of the reaction

mixture using column chromatography (petroleum ether : ethyl acetate 20:1) afforded

the product 1u (465.0 mg, 58%), Rf = 0.45 (petroleum ether : ethyl acetate 20:1). 1H

NMR (400 MHz, CDCl3) δ = 8.13 (d, J = 8.0, 2H), 7.54 (d, J = 8.0, 2H), 7.43 (t, J =

7.6, 1H), 7.35 (d, J = 7.6, 1H), 7.32 – 7.16 (m, 2H), 4.42 (q, J = 7.2, 2H), 1.43 (t, J =

7.2, 3H). 13C NMR (100 MHz, CDCl3) δ 166.38, 142.69, 137.21, 132.65, 131.11,

129.49, 129.37, 125.07, 118.88, 61.00, 14.40. IR (neat) v 2981, 2126, 1715, 1610,

1482,1276, 750 cm-1.

2-azido-2',4-dimethoxy-1,1'-biphenyl (1w). The general procedure was followed

using 0.606 g of ethyl2-bromo-5-methoxyaniline (3.0 mmol). Purification of the

afforded the product 1w (203.0 mg, 30%), Rf = 0.35 (20:1petroleum ether : ethyl

acetate). 1H NMR (400 MHz, CDCl3) δ = 7.39 – 7.33 (m, 1H), 7.22 – 7.16 (m, 2H),

7.05 – 6.95 (m, 2H), 6.78 – 6.72 (m, 2H), 3.87 (s, 3H), 3.80 (s, 3H). 13C NMR (100

MHz, CDCl3) δ 160.02, 157.06, 139.19, 132.67, 131.68, 129.28, 127.02, 123.39, 120.46,

111.01, 110.39, 104.58, 55.79, 55.60. IR (neat) v 2109, 1512, 1486, 1321, 1295, 1226

2'-azido-5'-methyl-1,1':3',1''-terphenyl (1x).[4] The general procedure was followed

using 0.794 g of 2,6-dibromo-4-methylaniline (3.0 mmol). Purification of the reaction

mixture using column chromatography (petroleum ether : dichloromethane 20:1)

afforded the product 1x (104.0 mg, 12%), Rf = 0.21 (petroleum ether : dichloromethane

(s, 3H). 13C NMR (100 MHz, CDCl3) δ 138.72, 136.51, 135.36, 132.07, 131.21, 129.48,

128.45, 127.72, 20.93. IR (neat) v 2923, 2114, 1457, 1420, 1300, 1242, 1158, 698 cm-

2'-azido-4,4''-dimethoxy-1,1':3',1''-terphenyl (1y). The general procedure was

followed using 1.255 g of ethyl 2,6-dibromoaniline (5.0 mmol). Purification of the

afforded the product 1y (222.0 mg, 14%), Rf = 0.45 (petroleum ether : ethyl acetate

10:1). 1H NMR (400 MHz, CDCl3) δ = 7.49 (d, J = 8.7, 4H), 7.34 – 7.27 (m, 3H), 7.04

(d, J = 8.7, 4H), 3.89 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 159.25, 136.28, 134.79,

130.97, 130.62, 130.19, 125.56, 113.89, 55.36. IR (neat) v 2121, 1564, 1488, 1261,

1031, 801, 667 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C20H17N3O2 354.1213, found

354.1230.

4-(2-azidophenyl)dibenzo[b,d]furan (1z). The general procedure was followed using

column chromatography (petroleum ether : ethyl acetate 30:1) afforded the product 1z

CDCl3) δ = 8.09 – 8.01 (m, 2H), 7.66 – 7.59 (m, 2H), 7.57 – 7.46 (m, 4H), 7.45 – 7.38

(m, 2H), 7.35 (td, J = 7.6, 0.9, 1H). 13C NMR (100 MHz, CDCl3) δ 156.29, 153.69,

138.35, 132.03, 129.52, 128.66, 128.55, 127.32, 124.93, 124.53, 124.35, 122.85,

122.67, 120.81, 120.38, 118.99, 111.92. IR (neat) v 2121, 1449, 1410, 1296, 1191, 667

cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C18H11N3O 308.0794, found 308.0806.

2-azido-2'-methoxy-5-methyl-1,1'-biphenyl (3a).[3] The general procedure was

followed using 0.558 g of 2-bromo-4-methylaniline (3.0 mmol). Purification of the

reaction mixture using column chromatography (petroleum ether : dichloromethane

gradient: 10:1-5:1) afforded the product 3a (480.0 mg, 67%), Rf = 0.12 (petroleum

ether : dichloromethane 10:1). 1H NMR (400 MHz, CDCl3) δ = 7.48 (t, J = 7.6, 1H),

7.33 – 7.18 (m, 4H), 7.17 – 7.04 (m, 2H), 3.90 (s, 3H), 2.47 (s, 3H). 13C NMR (100

MHz, CDCl3) δ = 156.78, 135.53, 134.27, 132.38, 131.23, 130.64, 129.38, 129.34,

127.37, 120.40, 118.50, 110.88, 55.64, 20.88. IR (neat) v 2923, 2119, 1501, 1486, 1298,

1283, 1236, 808 cm-1.

methyl 6-azido-4'-methoxy-[1,1'-biphenyl]-3-carboxylate (3b). The general

procedure was followed using 0.690 g of methyl 4-amino-3-bromobenzoate (3.0 mmol).

Purification of the reaction mixture using column chromatography (petroleum ether :

ethyl acetate 20:1) afforded the product 3b (399.0 mg, 47%), Rf = 0.28 (petroleum ether :

ethyl acetate 20:1). 1H NMR (400 MHz, CDCl3) δ = 8.05 – 7.98 (m, 2H), 7.40 (d, J =

8.8, 2H), 7.25 (d, J = 9.2, 1H), 6.98 (d, J = 8.8, 2H), 3.92 (s, 3H), 3.85 (s, 3H). 13C

NMR (100 MHz, CDCl3) δ 166.23, 159.36, 141.61, 133.23, 132.47, 130.56, 129.52,

129.43, 126.61, 118.60, 113.67, 55.23, 52.12. IR (neat) v 2119, 1719, 1515, 1435, 1294,

1242, 1121 cm-1. HRMS (ESI) ([M+H]+) Calcd. for C15H13N3O3 284.1030, found

284.1037.

methyl 6-azido-4-methoxy-[1,1'-biphenyl]-3-carboxylate (3c). The general

procedure was followed using 0.780 g of methyl 4-amino-5-bromo-2-methoxybenzoate

(3.0 mmol). Purification of the reaction mixture using column chromatography

(petroleum ether : ethyl acetate 20:1) afforded the product 3c (255.0 mg, 30%), Rf =

0.13 (petroleum ether : ethyl acetate 20:1). 1H NMR (400 MHz, CDCl3) δ = 7.88 (s,

1H), 7.47 – 7.32 (m, 5H), 6.77 (s, 1H), 3.97 (s, 3H), 3.88 (s, 3H). 13C NMR (100 MHz,

CDCl3) δ 165.54, 159.73, 141.89, 136.83, 134.90, 129.38, 128.16, 127.50, 125.84,

116.36, 102.29, 56.26, 52.00. IR (neat) v 2113, 1729, 1485, 1434, 1314, 1233 cm-1.

HRMS (ESI) ([M+H]+) Calcd. for C15H13N3O3 284.1030, found 284.1034.

methyl 6-azido-4,4'-dimethoxy-[1,1'-biphenyl]-3-carboxylate (3d). The general

procedure was followed using 0.780 g of methyl 4-amino-5-bromo-2-methoxybenzoate

(3.0 mmol). Purification of the reaction mixture using column chromatography

(petroleum ether : ethyl acetate gradient: 20:1-10:1-3:1) afforded the product 3d (273.0

mg, 29%), Rf = 0.13 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3)

δ = 7.83 (s, 1H), 7.38 – 7.29 (m, 2H), 6.96 – 6.89 (m, 2H), 6.74 (s, 1H), 3.96 (s, 3H),

3.87 (s, 3H), 3.82 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 165.62, 159.44, 159.04,

141.81, 134.73, 130.51, 129.17, 125.58, 116.35, 113.62, 102.30, 56.27, 55.23, 51.99.

IR (neat) v 2112, 1728, 1497, 1317, 1232, 832 cm-1. HRMS (ESI) ([M+H]+) Calcd. for

C16H15N3O4 314.1135, found 314.1132.

2. Preparation of biaryl azides 1i, 3e

Unless otherwise noted, the biaryl azides were synthesized from the 4-amino-3-

bromophenylmethanol[8] reduced from methyl 4-amino-3-bromobenzoate without

purification and substituted phenylboronic acid using Suzuki reactions.[1] The resulting

biaryl amines were converted to correspongding biaryl azides without purification

using traditional diazotization reaction conditions. After purification, the final azides

were obtained by oxidative process. Yields were not optimized.

A solution of 4-amino-3-bromo-benzoic acid methyl ester (3 mmol, 1.0 equiv 690.0 mg)

in THF (4 mL) was added slowly at –10 °C to a suspension of LiAlH4 (6 mmol, 2.0

equiv, 227.0 mg) in THF (6 mL). After warming to 0 °C and stirring for 24 hours at this

temperature the reaction mixture is quenched with aqueous Na2SO4, diluted with

dichloromethane (20 mL) and the aqueous phase was extracted with an additional 3 ×

30 mL of CH2Cl2, and the combined organic phases were washed 2 × 50 mL of water.

The organic phase was dried over Na2SO4 and filtered. The filtrate was concentrated in

vacuo to afford an oil. This crude mixture was used for the next step without any further

purification.

In a 50 mL round bottom flask, substituted phenylboronic acid (9 mmol, 3.0 equiv),

Na2CO3 (6 mmol, 2.0 equiv, 635.9 mg), and Pd(OAc)2 (0.06 mmol, 0.02 equiv, 13.5 mg)

were then dissolved in 9 mL of ethylene glycol, 9 mL of H2O. The amine made by last

step was added, and the resulting mixture was heated to 80 ˚C for 24 hours. After

cooling, the biphasic solution was diluted with 50 mL of water and 30 mL of CH2Cl2

and separated. The aqueous phase was extracted with an additional 3 × 30 mL of CH2Cl2,

and the combined organic phases were washed 2 × 50 mL of water. The organic phase

was dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford an

oil. This crude mixture was used for the next step without any further purification.

mg) was added slowly, then the resulting mixture was stirred at 0 °C for 2 hour. NaN3

(1.5 equiv, 295.2 mg) was then added slowly, the resulting mixture was warmed up to

ambient temperature, and stirred overnight. The solution was then diluted with 20 mL

of water and 20 mL of CH2Cl2, and basified by slow addition of K2CO3 until the pH of

the mixture was 8. The phases were separated and the aqueous phase was extracted with

an additional 3 × 30 mL of CH2Cl2. The combined organic phase were dried over

Na2SO4 and filtered. The filtrate was concentrated in vacuo and crude was purified by

silica gel column using petroleum ether and ethyl acetate as eluent.

In an oven dried schlenk tube, the substituted (6-azido-[1,1'-biphenyl]-3-yl)methanol

(0.5 mmol, 1.0 equiv), 2-iodoxybenzoic acid(IBX) (1.2 equiv) and a stir bar were taken

and the ethyl acetate (2.0 ml) was added. The reaction mixture was heated to 80 ˚C for

24 hours. After cooling, the biphasic solution was filtered and the filtrate was

concentrated in vacuo and crude was purified by silica gel column using petroleum

ether and ethyl acetate as eluent.

(6-azido-[1,1'-biphenyl]-3-yl)methanol (1i′). The general procedure was followed

using 0.69 g of methyl 4-amino-3-bromobenzoate (3.0 mmol). Purification of the

reaction mixture using column chromatography (petroleum ether : ethyl acetate

gradient: 8:1-3:1) afforded the product 1i’ in yield 45%, Rf = 0.28 (petroleum ether :

ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 7.52 – 7.32 (m, 7H), 7.28 – 7.21 (m,

1H), 4.71 (s, 2H), 1.97 (brs, 1H). 13C NMR (100 MHz, CDCl3) δ 137.94, 137.59, 136.35,

133.74, 129.93, 129.41, 128.19, 127.68, 127.33, 118.93, 64.44. IR (neat) v 3319, 2119,

1485, 1296, 1013, 698 cm-1. HRMS (APCI) ([M-H]-) Calcd. for C13H11N3O 224.0829,

found 224.0837.

(6-azido-4'-methoxy-[1,1'-biphenyl]-3-yl)methanol (3e′).The general procedure was

followed using 0.69 g of methyl 4-amino-3-bromobenzoate (3.0 mmol). Purification of

the reaction mixture using column chromatography (petroleum ether : ethyl acetate

gradient: 10:1-3:1) afforded the product 3e’ in yield 12%, Rf = 0.26 (petroleum ether :

ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 7.43 – 7.27 (m, 4H), 7.20 (d, J =8.0,

1H), 7.00 – 6.94 (m, 2H), 4.66 (s, 2H), 3.85 (s, 3H), 2.40 (brs, 1H). 13C NMR (100 MHz,

CDCl3) δ 159.14, 137.64, 136.34, 133.45, 130.59, 130.34, 129.87, 127.00, 118.94,

113.68, 64.61, 55.36. IR (neat) v 3320, 2118, 1608, 1560, 1294, 1029, 831 cm-1. HRMS

(ESI) ([M+Na]+) Calcd. for C14H13N3O2 278.0900, found 278.0912.

6-azido-[1,1'-biphenyl]-3-carbaldehyde (1i). The general procedure was followed

using 0.11 g of methyl (6-azido-[1,1'-biphenyl]-3-yl)methanol (0.5 mmol). Purification

of the reaction mixture using column chromatography (petroleum ether : ethyl acetate

gradient: 20:1-10:1) afforded the product 1i in yield 89%, Rf = 0.28 (petroleum ether :

ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 7.52 – 7.32 (m, 7H), 7.28 – 7.21 (m,

1H), 4.71 (s, 2H), 1.97 (brs, 1H). 13C NMR (100 MHz, CDCl3) δ 137.94, 137.59, 136.35,

133.74, 129.93, 129.41, 128.19, 127.68, 127.33, 118.93, 64.44. IR (neat) v 2121, 1697,

1595, 1479, 1293, 1177, 698 cm-1. HRMS (APCI) ([M-H]-) Calcd. for C13H9N3O

222.0673, found 222.0688.

6-azido-4'-methoxy-[1,1'-biphenyl]-3-carbaldehyde (3e).The general procedure was

followed using 0.1 g of (6-azido-4'-methoxy-[1,1'-biphenyl]-3-yl)methanol (0.45

mmol). Purification of the reaction mixture using column chromatography (petroleum

ether : ethyl acetate gradient: 20:1-10:1) afforded the product 3e in yield 73%, Rf = 0.18

(petroleum ether: ethyl acetate 20:1). 1H NMR (400 MHz, CDCl3) δ = 9.98 (s, 1H), 7.92

– 7.82 (m, 2H), 7.46 – 7.35 (m, 3H), 7.04 – 6.94 (m, 2H), 3.87 (s, 3H). 13C NMR (100

MHz, CDCl3) δ 190.94, 159.68, 143.41, 134.13, 133.29, 132.89, 130.71, 129.64, 129.22,

119.38, 113.94, 55.48. IR (neat) v 2118, 1689, 1594, 1488, 1179 cm-1. HRMS (ESI)

([M+Na]+) Calcd. for C14H11N3O2 276.0743, found 276.0734.

3. Preparation of biaryl azide 1v

Unless otherwise noted, the biaryl azide was synthesized from the 2-bromoanilines and

substituted phenylboronic acid using Suzuki reactions. The resulting biaryl amines after

reduced by LiAlH4 were converted to the biaryl azides without purification using

traditional diazotization reaction conditions. After purification, the final azides were

obtained by oxidative process. Yields were not optimized.

In a 50 mL round bottom flask, 4-(methoxycarbonyl)phenyl boronic acid (9 mmol, 3

equiv, 1.6920 g), Na2CO3 (6 mmol, 2.0 equiv, 635.9 mg), and Pd(OAc)2 (0.06 mmol,

0.02 equiv, 13.5 mg) were then dissolved in 9 mL of ethylene glycol, 9 mL of H2O. The

2-bromoanilines (3mmol, 1.0 equiv, 516.1 mg) was added, and the resulting mixture

was heated to 80 ˚C for 24 hours. After cooling, the biphasic solution was diluted with

50 mL of water and 30 mL of CH2Cl2 and separated. The aqueous phase was extracted

with an additional 3 × 30 mL of CH2Cl2, and the combined organic phases were washed

2 × 50 mL of water. The organic phase was dried over Na2SO4 and filtered. The filtrate

was concentrated in vacuo to afford an oil. This crude mixture was used for the next

step without any further purification.

A solution of the crude mixture made by last step in THF (4 mL) was added slowly at

–10 °C to a suspension of LiAlH4 (6 mmol, 2.0 equiv, 227.7 mg) in THF (6 mL). After

warming to 0 °C and stirring for 24 hours at this temperature the reaction mixture is

quenched with aqueous Na2SO4, diluted with dichloromethane (20 mL) and the aqueous

phase was extracted with an additional 3 × 30 mL of CH2Cl2, and the combined organic

phases were washed 2 × 50 mL of water. The organic phase was dried over Na2SO4 and

filtered. The filtrate was concentrated in vacuo to afford an oil. This crude mixture was

used for the next step without any further purification.

mg) was added slowly, then the resulting mixture was stirred at 0 °C for 2 hours. NaN3

silica gel column using petroleum ether and ethyl acetate as eluent (petroleum ether :

ethyl acetate 5:1) directly to give the desired product 1v′ in 57% yield. Rf = 0.32

(petroleum ether : ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 7.54 – 7.33 (m,

6H), 7.32 – 7.19 (m, 2H), 4.75 (s, 2H), 2.45 (brs, 1H). 13C NMR (100 MHz, CDCl3) δ

140.24, 137.50, 137.14, 133.44, 131.24, 129.68, 128.81, 126.80, 125.01, 118.80, 65.00.

IR (neat) v 3319, 2123, 1483, 1442, 1293, 751 cm-1.

In an oven dried schlenk tube, the (2'-azido-[1,1'-biphenyl]-4-yl)methanol (0.7 mmol,

1.0 equiv), 2-iodoxybenzoic acid(IBX) (1.2 equiv, 235.2 mg) and a stir bar were taken

and the ethyl acetate (2.0 ml) was added. The reaction mixture was heated to 80 ˚C for

24 hours. After cooling, the biphasic solution was filtered and the filtrate was

concentrated in vacuo and crude was purified by silica gel column using petroleum

ether and ethyl acetate as eluent (petroleum ether : ethyl acetate 20:1) directly to give

the desired product 1v in 51% yield, Rf = 0.45 (petroleum ether : ethyl acetate 10:1).

1H NMR (400 MHz, CDCl3) δ = 10.07 (s, 1H), 7.95 (d, J = 8.4, 2H), 7.63 (d, J = 8.4,

2H), 7.46 (td, J = 8.0, 1.6, 1H), 7.36 (dd, J = 7.6, 1.4, 1H), 7.33 – 7.20 (m, 2H). 13C

NMR (100 MHz, CDCl3) δ 192.02, 144.51, 137.36, 135.40, 132.38, 131.19, 130.31,

129.78, 129.62, 125.24, 119.02. IR (neat) v 2125, 1701, 1481, 1296, 1233, 838, 735 cm-

4. Preparation of biaryl azide 1a-D[9]

In a 50 mL round bottom flask, (2-bromophenyl)boronic acid (4 mmol, 3 equiv, 803.3

mg), Na2CO3 (16 mmol, 4.0 equiv, 1.6958 g), and Pd(OAc)2 (1.2 mmol, 0.2 equiv, 269.1

mg) were then dissolved in 9 mL of ethylene glycol, 9 mL of H2O. 2-iodoaniline (12

mmol, 3.0 equiv, 2.6282 g) was added, and the resulting mixture was heated to 90 ˚C

for 48 hours. After cooling, the biphasic solution was diluted with 50 mL of water and

30 mL of CH2Cl2 and separated. The aqueous phase was extracted with an additional 3

× 30 mL of CH2Cl2, and the combined organic phases were washed 2 × 50 mL of water.

The organic phase was dried over Na2SO4 and filtered. The filtrate was concentrated in

vacuo and crude was purified by silica gel column using column chromatography

(petroleum ether : ethyl acetate 20:1) afforded the product 1a-D′′ (0.248 g, 25%), TLC

Rf = 0.13 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 7.72

(d, J = 8.0, 1H), 7.44 – 7.33 (m, 2H), 7.31 – 7.18 (m, 2H), 7.06 (dd, J = 7.5, 1.4, 1H),

6.92 – 6.78 (m, 2H), 3.54 (brs, 2H). 13C NMR (100 MHz, CDCl3) δ 143.61, 140.06,

133.17, 131.88, 130.31, 129.32, 129.19, 127.92, 127.17, 124.33, 118.33, 115.59.

Aniline 1a-D′′ (0.65 mmol, 1.0 equiv, 161.3 mg) was dissolved in dry THF (10 mL)

and the solution was cooled to -78 °C under nitrogen. A solution of n-BuLi (2.5 M in

hexane, 1.56 mL, 3.9 mmol) was added dropwise to the reaction mixture. After one

hour at -78 °C, CD3OD (1.5 mL) was added and then quenched with demin. water. The

aqueous fraction was extracted twice with diethyl ether (10 mL). The organic phases

were dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford

the crude product. Purification by column chromatography on silica gel (petroleum

ether : ethyl acetate 10:1) afforded the corresponding product 1a-D′ (109.0 mg, 99%),

H NMR showed 60 % deuterium incorporation. Rf = 0.45 (petroleum ether : ethyl

acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 7.59 – 7.48 (m, 3H), 7.41 (t, J = 6.5, 1H),

7.27 – 7.16 (m, 2H), 6.95 – 6.77 (m, 2H), 3.91 (brs, 2H). IR (KBr) v 1614, 1541, 1434,

1261, 1008, 748, 667 cm-1. HRMS (ESI) ([M+H]+) Calcd. for C12H10DN 171.0721,

found 171.1023.

In a 100 mL of round bottom flask, the crude 4-amino-3-bromobenzoate (0.7 mmol)

was dissolved in HOAc and H2O (2:1 v/v, 0.2 M) and chilled in an ice bath. NaNO2

(1.4 equiv, 62.3 mg) was added slowly, then the resulting mixture was stirred at 0 °C

for 2 hours. NaN3 (1.5 equiv, 68.9 mg) was then added slowly, the resulting mixture

was warmed up to ambient temperature, and stirred overnight. The solution was then

diluted with 20 mL of water and 20 mL of CH2Cl2, and basified by slow addition of

K2CO3 until the pH of the mixture was 8. The phases were separated and the aqueous

phase was extracted with an additional 3 × 30 mL of CH2Cl2. The combined organic

phase were dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo and

crude was purified by silica gel column using column chromatography (petroleum

ether : ethyl acetate 30:1) afforded the product 1a-D (116.0 mg, 84%), Rf = 0.78

(petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 7.56 – 7.38 (m,

6H), 7.35 – 7.23 (m, 2H). IR (neat) v 2124, 1579, 1431, 1299, 1009, 750, 657 cm-1.

HRMS (ESI) ([M+H]+) Calcd. for C12H8DN3 197.0937, found 197.0954.

5. Preparation of biaryl azide 1aa[3]

To a dry 100 mL round bottom flask equipped with a stir bar were added 2,6-

dibromoaniline (6 mmol, 1.0 equiv, 1.5054 g), (4-(ethoxycarbonyl)phenyl)boronic acid

(7.20 mmol, 1.2 equiv, 1.3967 g), K2CO3 (24 mmol, 4.0 equiv, 3.3170 g), and Pd(PPh3)4

(0.60 mmol, 0.1 equiv, 693.3 mg) under N2 atmosphere. Toluene (36 mL), 24 mL of

H2O, and 12 mL of EtOH were 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 organic phase was 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 of the reaction mixture using column chromatography

(petroleum ether : ethyl acetate 20:1) afforded the product 1aa′ (1.340 g, 70%), Rf =

0.42 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.15 – 8.07

(m, 2H), 7.58 – 7.47 (m, 2H), 7.43 (d, J = 8.0, 1H), 7.04 (d, J = 7.5, 1H), 6.68 (t, J =

7.8, 1H), 4.40 (q, J = 7.1, 2H), 4.21 (brs, 2H), 1.42 (t, J = 7.1, 3H). 13C NMR (100 MHz,

CDCl3) δ 166.28, 143.75, 141.31, 132.42, 130.26, 129.74, 129.43, 129.04, 127.50,

119.04, 110.06, 61.16, 14.45. IR (neat) v 1714, 1608, 1540, 1452, 1263, 1100, 667 cm-

1. HRMS (ESI) ([M+H]+) Calcd. for C15H14BrNO2 320.0281, found 320.0286.

In a 50 mL round bottom flask, (4-methoxyphenyl)boronic acid (4.5 mmol, 3 equiv,

873.0 mg), Na2CO3 (6 mmol, 2.0 equiv, 635.9 mg), and Pd(OAc)2 (0.06 mmol, 0.02

equiv, 13.5 mg) were then dissolved in 9 mL of ethylene glycol, 9 mL of H2O. Aniline

1aa′ (1.5 mmol, 1.0 equiv, 480.3 mg) was added, and the resulting mixture was heated

to 80 ˚C for 24 hours. After cooling, the biphasic solution was diluted with 50 mL of

mL of water. The organic phase was dried over Na2SO4 and filtered. The filtrate was

concentrated in vacuo to afford an oil. This crude mixture was used for the next step

without any further purification.

mg) was added slowly, then the resulting mixture was stirred at 0 °C for 2 hours. NaN3

silica gel column using column chromatography (petroleum ether : ethyl acetate 20:1)

afforded the product 1aa (222.0 mg, 14%), Rf = 0.45 (petroleum ether : ethyl acetate

10:1). 1H NMR (400 MHz, CDCl3) δ = 7.49 (d, J = 8.7, 4H), 7.34 – 7.27 (m, 3H), 7.04

130.97, 130.62, 130.19, 125.56, 113.89, 55.36. IR (neat) v 2121, 1564, 1488, 1261,

1031, 801, 667 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C20H17N3O2 354.1213, found

354.1230.

Ⅱ Experimental Procedure for for Synthesis of Carbazoles

1, General procedure

Corresponding azide (0.15 mmol), silica gel 15.0 mg, H2O (1.5 ml) and Acetone (1.5

ml) were added to a 15 ml glass vial equipped with a stirring bar. Then the solution was

stirred at a distance of ~1 cm from a 23 w fluorescent lamp at room temperature about

48 hours or 4 days. The biphasic solution was diluted with 5 mL of water and 5 mL of

CH2Cl2 and separated. The aqueous phase was extracted with an additional 3 × 10 mL

of CH2Cl2, and the combined organic phases were washed 2 × 5 mL of water. The

organic phase was dried over Na2SO4 and filtered. The organic phase was dried over

Na2SO4 and filtered. The crude product was purified by flash chromatography on silica

gel (petroleum ether : ethyl acetate gradient: 30:1-3:1) directly to give the desired

product.

2, Large scale reaction

A spiral quartz tube (8 round, inner diameter: 8 mm) was made. A 40 W white LED

corn-light was hanged at the middle of the circle (the light is about 1.5 cm far to quartz

tubes). The whole facility was drove by an 8 W chemical pump.

0.585 g (3.0 mmol) of 2-azido biphenyl 1a, 0.3 g silica gel, 20 mL water and 20 mL of

acetone was added in a 150 mL conical flask, stir evenly and transform to the spiral

quartz tube. Additional 15 mL of water and 15 mL of acetone was used to wash the

flask and was then transformed to spiral quartz tube. The mixture was kept flowing for

72 hours with the light irradiation. The reaction mixture was extracted by 30 mL ethyl

acetate. The organic phase was washed by brine, dried over Na2SO4 and concentrated

in vacuo to afford yellow solid. The conversion of the reaction was 69% based on 1H

NMR of reaction mixture. The obtained solid was washed with 10 mL n-hexane for

three times. The remained solid was desired product 2a (320.6 mg, 64%, pure based on 1H NMR). The obtained n-hexane solution was concentrated in vacuo, 0.146 g

(containing 10% product 2a) of azide 1a was recycled (25% recovered) as a yellow

solid.

Ⅵ. Spectroscopic Data of Carbazoles Obtained in this Study

Yield of (2a)[10]:20.1 mg, 80 %, white solid, M.p.=245℃, Rf = 0.36 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.27 (brs, 1H), 8.11 (d, J = 8.0,

2H), 7.48 (d, J = 8.0, 2H), 7.38 (t, J = 7.6, 2H), 7.15 (t, J = 7.6, 2H). 13C NMR (100

MHz, DMSO) δ 139.71, 125.52, 122.39, 120.18, 118.49, 110.94. HRMS (ESI) ([M+H]+)

Calcd. for C12H9N 168.0808, found 168.0804.

Yield of (2b)[11]:22.0 mg, 81%, white solid, M.p. = 208℃, Rf = 0.48 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.05 (d, J = 7.6, 1H), 7.94 (brs,

1H), 7.89 (s, 1H), 7.40 (d, J = 3.6, 2H), 7.32 (d, J = 8.0, 1H), 7.28 – 7.17 (m, 2H), 2.54

(s, 3H). 13C NMR (100 MHz, CDCl3) δ 139.92, 137.82, 128.86, 127.30, 125.77, 123.63,

123.34, 120.38, 120.36, 119.33, 110.68, 110.37, 21.58. IR (neat) v 3404, 2921, 1459,

1333, 1217, 747, 728 cm-1. HRMS (ESI) ([M-H]-) Calcd. for C13H11N 180.0814, found

180.0822.

Yield of (2c): 27.4 mg, 75%, white solid, M.p. = 216℃, Rf = 0.41 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.34 (brs, 1H), 8.44 (d, J=0.8,

1H), 8.21 (d, J = 7.6, 1H), 7.77 (d, J = 7.6, 2H), 7.70 (dd, J = 8.4, 1.7, 1H), 7.56 (d, J =

8.4, 1H), 7.49 – 7.40 (m, 3H), 7.40 (t, J = 7.2, 1H), 7.32 (t, J = 7.2, 1H), 7.18 (t, J = 7.6,

1H). 13C NMR (100 MHz, DMSO) δ 141.34, 140.24, 139.29, 130.97, 128.88, 126.69,

126.37, 125.77, 124.64, 123.10, 122.61, 120.48, 118.67, 118.32, 111.32, 111.10. IR

(neat) v 3410, 2927, 1459, 1356, 1255, 750 cm-1. HRMS (ESI) ([M-H]-) Calcd. for

C18H13N 242.0975, found 242.0982.

Yield of (2d): 24.6 mg, 83% (4 d), white solid, M.p. = 234℃, Rf = 0.28 (petroleum

ether : ethyl acetate 10:1). 1H NMR (400 MHz, Acetone) δ = 10.21 (brs, 1H), 7.98 (dd,

J = 10.8, 8.0, 2H), 7.44 (d, J = 8.0, 1H), 7.32 – 7.24 (m, 1H), 7.18 – 7.08 (m, 1H), 7.03

(d, J = 2.4, 1H), 6.80 (dd, J = 8.4, 2.4, 1H), 3.86 (s, 3H). 13C NMR (100 MHz, Acetone)

δ 160.04, 142.31, 140.96, 125.01, 124.19, 121.56, 119.97, 119.68, 117.68, 111.36,

108.76, 95.30, 55.68. IR (neat) v 3404, 2921, 1459, 1333, 1195, 747 cm-1. HRMS (ESI)

([M-H]-) Calcd. for C13H11NO 196.0768, found 196.0784.

Yield of (2e)[14]: 25.9 mg, 90% (4 d), white solid, M.p. = 184℃, Rf = 0.25 (petroleum

ether : ethyl acetate 5:1). 1H NMR (400 MHz, DMSO) δ = 11.89 (brs, 1H), 8.72 (s, 1H),

8.24 (d, J = 8.0, 1H), 7.75 (d, J = 8.4, 1H), 7.63 (d, J = 8.4, 1H), 7.57 (d, J = 8.0, 1H),

7.49 (t, J = 7.6, 1H), 7.26 (t, J = 7.6, 1H). 13C NMR (100 MHz, DMSO) δ 141.71,

140.28, 128.66, 127.06, 125.69, 122.67, 121.63, 121.03, 120.67, 119.93, 112.09,

111.64, 100.21. IR (neat) v 3293, 2923, 2222, 1465, 1326, 1242, 1127, 736 cm-1. HRMS

(ESI) ([M+Na]+ ) Calcd. for C13H8N2 215.0585, found 215.0575.

Yield of (2f)[13]: 33.0 mg, 92%, white solid, M.p. = 160℃, Rf = 0.48 (petroleum ether :

ethyl acetate 5:1). 1H NMR (400 MHz, CDCl3) δ = 8.83 (s, 1H), 8.40 (brs, 1H), 8.21 –

8.10 (m, 2H), 7.46 – 7.41 (m, 3H), 7.32 – 7.31 (m, 1H), 4.45 (q, J = 7.2, 2H), 1.46 (t, J

= 7.2, 3H). 13C NMR (100 MHz, CDCl3) δ 167.58, 142.36, 140.04, 127.59, 126.67,

123.47, 123.23, 122.98, 121.87, 120.80, 120.44, 111.02, 110.23, 60.91, 14.65. IR (neat)

v 3294, 2925, 1685, 1460, 1332, 1245, 745, 727 cm-1. HRMS (ESI) ([M+Na]+) Calcd.

for C15H13NO2 262.0838, found 262.0837.

Yield of (2g)[12]: 26.1 mg, 83%, white solid, M.p. = 178℃, Rf = 0.28 (petroleum ether :

ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 8.74 (d, J=1.5, 1H), 8.59 (brs, 1H),

8.17 – 8.05 (m, 2H), 7.48 – 7.42m, 3H), 7.35 – 7.27 (m, 1H), 2.74 (s, 3H). 13C NMR

(100 MHz, CDCl3) δ 198.13, 142.57, 140.17, 129.41, 126.79, 126.69, 123.54, 123.23,

122.02, 120.70, 120.54, 111.19, 110.44, 26.85. IR (neat) v 3294, 2924, 1446, 1329,

1246, 736 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C14H11NO 2 232.0733, found

232.0729.

Yield of (2h): 28.6 mg, 85% (4 d), white solid, M.p. = 242℃, Rf = 0.18 (petroleum

ether : ethyl acetate 1:1). 1H NMR (400 MHz, DMSO) δ = 11.52 (brs, 1H), 8.65 (s, 1H),

8.41 – 8.39(m, 1H), 8.13 (d, J = 7.6, 1H), 7.91 (dd, J = 8.4, 1.6, 1H), 7.51 (t, J = 8.0,

2H), 7.46 – 7.37 (m, 1H), 7.21 (t, J = 7.2, 1H), 2.83 (d, J = 4.4, 3H). 13C NMR (100

MHz, DMSO) δ 167.33, 141.27, 140.31, 126.04, 125.13, 124.94, 122.54, 121.91,

120.20, 119.63, 119.17, 111.30, 110.33, 26.37. IR (neat) v 3295, 2925, 1603, 1495, 1330,

1245, 745 cm-1. HRMS (ESI) ([M+Na]+ ) Calcd. for C14H12N2O 247.0847, found

247.0857.

Yield of (2i): 17.6 mg, 60%; 22.0 mg, 75% (4 d), yellow solid, M.p. = 163℃, Rf =

0.36 (petroleum ether : ethyl acetate 3:1). 1H NMR (400 MHz, Acetone) δ = 10.90

(brs, 1H), 10.10 (s, 1H), 8.74 – 8.67 (m, 1H), 8.26 (d, J = 7.8, 1H), 8.05 – 7.93 (m,

1H), 7.63 (dd, J = 24.4, 8.4, 2H), 7.54 – 7.43 (m, 1H), 7.34 – 7.25 (m, 1H). 13C NMR

(100 MHz, Acetone) δ 192.05, 144.71, 141.70, 130.07, 127.60, 127.30, 124.90,

124.15, 124.04, 121.49, 121.06, 112.46, 112.26. IR (neat) v 3293, 2924, 1678, 1456,

1331, 1244, 745 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C13H9NO 218.0576, found

218.0572.

Yield of (2j)[12]: 16.7 mg, 60% (34%); 19.4 mg, 70% (4d), white solid, M.p. = 208℃,

Rf = 0.32 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.04

– 8.02 (m, 2H), 7.73 (dd, J = 9.2, 2.4, 1H), 7.48 – 7.40 (m, 2H), 7.34 (dd, J = 8.8, 4.2,

1H), 7.28 – 7.21 (m, 1H), 7.16 (td, J = 9.2, 2.4, 1H). 13C NMR (100 MHz, CDCl3) δ =

157.61 (d, JCF = 235.6), 140.62, 135.85, 126.55, 123.99 (d, JCF = 9.6), 123.20 (d, JCF =

4.0), 120.68, 119.58, 113.75 (d, JCF = 25.6), 111.22 (d, JCF = 9.2), 110.98, 106.13 (d,

JCF = 23.6). 19F NMR (376 MHz, CDCl3) δ -124.44. HRMS (ESI) ([M-H]-) Calcd. for

C12H8FN 184.0568, found 184.0582.

Yield of (2k)[10]: 20.9 mg, 69%, white solid, M.p. = 198℃, Rf = 0.34 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.42 (brs, 1H), 8.28 – 8.06 (m,

2H), 7.58 – 7.28 (m, 4H), 7.19 – 7.15 (m, 1H). 13C NMR (100 MHz, DMSO) δ 140.31,

138.11, 126.34, 125.29, 123.74, 122.82, 121.57, 120.73, 119.81, 118.89, 112.41, 111.23.

IR (neat) v 3405, 2923, 1488, 1268, 1089, 747 cm-1. HRMS (ESI) ([M+H]+) Calcd. for

C12H8NCl 202.0418, found 202.0421.

Yield of (2l)[24]: 28.4 mg, 77%, yellow solid. M.p. = 198℃, R f = 0.34 (petroleum ether :

ethylacetate 10:1). 1H NMR (400 MHz, Acetone) δ 10.54 (s, 1H), 8.34 (s, 1H), 8.20 (d,

J = 7.9 Hz, 1H), 7.60 – 7.50 (m, 3H), 7.50 – 7.43 (m, 1H), 7.25 (t, J = 7.5 Hz, 1H). 13C

NMR (101 MHz, Acetone) δ(s) 140.53, 138.74, 128.03, 126.41, 125.01, 122.71, 122.05,

120.42 , 119.26 , 112.65 , 111.11, 111.07. IR (neat) v 3405, 2920, 1468, 1444, 1271,

747 cm -1 . HRMS (ESI) ([M-H]+) Calcd. for C12H8NBr 243.9762, found 243.9766.

Yield of (2m)[24]: 31.9 mg, 73%, white solid. M.p. = 196℃, Rf = 0.39 (petroleum ether :

ethylacetate 10:1). 1H NMR (400 MHz, Acetone) δ 10.54 (s, 1H), 8.53 (d, J = 1.4 Hz,

1H), 8.20 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.5, 1.7 Hz, 1H), 7.57 (d, J = 8.2 Hz, 1H),

7.50 – 7.40 (m, 2H), 7.26 (dd, J = 11.1, 3.9 Hz, 1H). 13C NMR (101 MHz, Acetone) δ

(s) 140.16, 139.20, 133.68, 128.91, 126.37, 125.79, 121.78, 120.38, 119.32, 113.19,

111.04, 80.68. IR (neat) v 3403, 2919, 2849, 1468, 1443, 747 cm -1 . HRMS (ESI) ([M-

H]+) Calcd. for C12H8NI 291.9623, found 291.9626.

Yield of (2n)[10]: 29.2 mg, 80%, brown solid, M.p. = 241℃, Rf = 0.47 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.34 (brs, 1H), 8.16 (dd, J = 20.4,

8.0, 2H), 7.82 – 7.65 (m, 3H), 7.51 – 7.43 (m, 4H), 7.38 (q, J = 7.6, 2H), 7.17 (t, J =

7.6, 1H). 13C NMR (100 MHz, DMSO) δ 141.22, 140.36, 140.27, 137.84, 128.96,

127.09, 127.02, 125.64, 122.16, 121.81, 120.63, 120.28, 118.70, 117.84, 111.00, 108.87.

IR (neat) v 3404, 2923, 1459, 1434, 1273, 1126, 745, 728 cm-1. HRMS (ESI) ([M+H]+)

Calcd. for C18H13N 244.1121, found 244.1112.

Yield of (2o): 16.7 mg, 60%; 21.7 mg, 78%, white solid, M.p. = 230℃, Rf = 0.49

(petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.38 (brs, 1H),

8.15 – 8.05 (m, 2H), 7.49 (d, J = 8.1, 1H), 7.40 – 7.34 (m, 1H), 7.26 (dd, J = 10.1, 2.3,

1H), 7.20 – 7.11 (m, 1H), 6.98 (ddd, J = 9.8, 8.6, 2.4, 1H). 13C NMR (100 MHz, DMSO)

δ = 161.14 (d, JCF = 238.4), 140.31 (d, JCF = 9.2), 140.25, 125.21, 122.04, 121.42 (d,

JCF = 10.7), 119.93, 119.16, 118.96, 110.98, 106.45 (d, JCF = 24.1), 97.30 (d, JCF =

26.0).19F NMR (376 MHz, DMSO) δ -116.01. HRMS (ESI) ([M-H]-) Calcd. for

C12H8FN 184.0568, found 184.0584.

Yield of (2p): 18.6 mg, 63%, white solid, M.p. = 230℃, Rf = 0.23 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, Acetone) δ = 10.21 (brs, 1H), 7.98 (dd, J =

10.8, 8.2, 2H), 7.44 (d, J = 8.0, 1H), 7.35 – 7.25 (m, 1H), 7.20 – 7.10 (m, 1H), 7.03 (d,

J = 2.4, 1H), 6.80 (dd, J = 8.4, 2.4, 1H), 3.86 (s, 3H). 13C NMR (100 MHz, Acetone) δ

160.04, 142.31, 140.96, 125.02, 124.19, 121.56, 119.97, 119.68, 117.68, 111.36, 108.76,

95.31, 55.68. IR (neat) v 3187, 2925, 1456, 1266, 1158, 741 cm-1. HRMS (ESI) ([M-

H]-) Calcd. for C13H11NO 196.0768, found 196.0777.

Yield of (2q)[12]: 27.8 mg, 94%, white solid, M.p. = 134℃, Rf = 0.23 (petroleum ether :

1H), 7.43 – 7.32 (m, 3H), 7.27 (ddd, J = 8.0, 5.9, 2.1, 1H), 7.03 (d, J = 8.0, 1H), 6.70

126.79, 125.03, 123.16, 122.75, 119.73, 112.71, 110.05, 103.63, 100.48, 55.54. IR (neat)

v 3405, 2926, 1506, 1454, 1346, 1260, 1099, 751, 719 cm-1. HRMS (ESI) ([M-H]-)

Calcd. for C13H11NO 196.0768, found 196.0784.

Yield of (2r)[17]: 10.4 mg, 35 %; 13.3 mg, 45 % (4 d), white solid, M.p.= 70℃, Rf =

0.23 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.27 (brs,

1H), 8.07 (d, J = 8.0, 1H), 7.70 (d, J = 8.0, 1H), 7.48 – 7.40 (m, 2H), 7.29 – 7.12 (m,

2H), 6.92 (d, J = 8.0, 1H), 4.02 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 145.80, 139.29,

129.91, 125.82, 124.43, 123.78, 120.69, 119.87, 119.50, 112.98, 111.05, 106.02, 55.66.

IR (neat) v 3405, 2924, 1507, 1435, 1311, 1234, 742 cm-1. HRMS (ESI) ([M+Na]+ )

Calcd. for C13H11NO 220.0738, found 220.0738.

Yield of (2r′)[12]: 10.4 mg, 35%; 13.3 mg, 45% (4 d), white solid, M.p.= 140℃, Rf =

0.21 (petroleum ether : ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.04 (d, J

= 8.0, 1H), 7.92 (brs, 1H), 7.56 (d, J = 2.4, 1H), 7.41 (d, J = 3.6, 2H), 7.33 (d, J = 8.8,

1H), 7.21 (dt, J = 8.0, 4.1, 1H), 7.07 (dd, J = 8.8, 2.4, 1H), 3.94 (s, 3H). 13C NMR (100

MHz, CDCl3) δ 153.99, 140.37, 134.46, 125.92, 123.89, 123.46, 120.38, 119.17, 115.19,

111.43, 110.87, 103.25, 56.20. IR (neat) v 3404, 2925, 1460, 1255, 1170, 746 cm-1.

HRMS (ESI) ([M+Na]+ ) Calcd. for C13H11NO 220.0738, found 220.0725.

Yield of mixture (2s + 2s′)[18]: 17.9 mg, 66%; 22.0 mg, 81% (4 d) (1.5 : 1). Yellow solid.

Rf = 0.43 (petroleum ether : ethyl acetate 10:1). 2r: 1H NMR (400 MHz, CDCl3) δ =

8.09 (d, J = 7.9, 1H), 7.97 (brs, 1H), 7.95 (d, J = 7.8, 1H), 7.51 – 7.42 (m, 2H), 7.22 –

7.14 (m, 3H), 2.58 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 139.50, 138.95, 126.53,

125.75, 123.95, 122.93, 120.60, 119.84, 119.70, 119.60, 118.06, 110.81, 17.01. 2r′: 1H

NMR (400 MHz, CDCl3) δ = 8.05 (d, J = 7.6, 1H), 7.94 (brs, 1H), 7.89 (s, 1H), 7.40 (d,

J = 3.6, 2H), 7.32 (d, J = 8.0, 1H), 7.28 – 7.17 (m, 2H), 2.54 (s, 3H). 13C NMR (100

MHz, CDCl3) δ 139.92, 137.82, 128.86, 127.30, 125.77, 123.63, 123.34, 120.38, 120.36,

119.33, 110.68, 110.37, 21.58. The mixture of IR (neat) v 3405, 2924, 1507, 1457, 1327,

1275, 746, 727cm-1. The mixture of HRMS (ESI) ([M+Na]+) Calcd. for C13H11N

204.0789, found 204.0798.

Yield of (2t)[13]: 25.5 mg, 87%, white solid, M.p. = 90℃, Rf = 0.49 (petroleum ether :

1H), 7.75 (s, 1H), 7.46 – 7.38 (m, 2H), 7.27 – 7.20 (m, 1H), 7.09 (s, 1H), 2.53 (d, J =

4.4, 6H). 13C NMR (100 MHz, CDCl3) δ 139.93, 137.29, 129.09, 128.14, 125.67,

123.93, 123.23, 120.58, 119.57, 119.46, 117.97, 110.87, 21.59, 17.02. IR (neat) v 3432,

2921, 1452, 1305, 1229, 745 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C14H13N

218.0940, found 218.0951.

Yield of (2u)[15]: 32.3 mg, 90%, white solid, M.p.= 180℃ Rf = 0.45 (petroleum ether :

ethyl acetate 5:1). 1H NMR (400 MHz, DMSO) δ = 11.55 (brs, 1H), 8.22 (dd, J = 12.0,

8.0, 2H), 8.11 (d, J = 0.8, 1H), 7.78 (dd, J = 8.0, 1.4, 1H), 7.57 –7.42 (m, 2H), 7.21 (t,

J = 7.2, 1H), 4.36 (q, J = 7.2, 2H), 1.37 (t, J = 7.2, 3H). 13C NMR (100 MHz, DMSO)

δ 166.43, 141.07, 139.04, 127.06, 126.58, 126.15, 121.61, 121.13, 120.14, 119.24,

119.16, 112.29, 111.43, 60.63, 14.32. IR (neat) v 3312, 2924, 1690, 1445, 1344, 1272,

749 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C15H13NO2 262.0838, found 262.0845.

Yield of (2v)[16]: 14.6 mg, 50% (4 d), yellow solid, M.p.= 150℃ Rf = 0.36 (petroleum

ether : ethyl acetate 3:1). 1H NMR (400 MHz, CDCl3) δ = 10.13 (s, 1H), 8.45 (brs, 1H),

8.17 (dd, J = 23.6, 7.9, 2H), 7.99 (s, 1H), 7.77 (dd, J = 8.0, 1.2, 1H), 7.59 – 7.46 (m,

2H), 7.32 – 7.29 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 192.72, 141.37, 139.19,

134.18, 128.76, 127.95, 122.50, 121.70, 121.51, 120.72, 120.35, 112.08, 111.24. IR

(neat) v 3403, 1497, 1440, 1348, 1242, 1140, 742 cm-1. HRMS (ESI) ([M+Na]+) Calcd.

for C13H9NO 218.0576, found 218.0574.

Yield of (2w): 22.5 mg, 66% (4 d), white solid, M.p. = 135℃ Rf = 0.39 (petroleum

ether : ethyl acetate 5:1). 1H NMR (400 MHz, CDCl3) δ = 8.19 (d, J = 8.8, 1H), 7.86

(brs, 1H), 7.30 – 7.23 (m, 1H), 6.96 (d, J = 8.0, 1H), 6.88 (dd, J = 8.8, 2.2, 1H), 6.80

(d, J = 2.4, 1H), 6.68 (d, J = 8.0, 1H), 4.06 (s, 3H), 3.87 (s, 3H). 13C NMR (100 MHz,

CDCl3) δ 158.42, 155.60, 140.98, 140.06, 125.55, 123.75, 116.66, 112.72, 108.27,

103.57, 100.68, 94.41, 55.68, 55.52. IR (neat) v 3405, 2926, 1446, 1333, 1266, 1157,

1100, 722 cm-1. HRMS (ESI) ([M+Na]+ ) Calcd. for C14H13NO2 250.0844, found

250.0823.

Yield of (2x): 35.9 mg, 93%, yellow oil, M.p.= 92℃ Rf = 0.51 (petroleum ether : ethyl

acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.22 (brs, 1H), 8.12 (d, J = 7.6, 1H),

7.92 (s, 1H), 7.77 – 7.68 (m, 2H), 7.59 (t, J = 7.6, 2H), 7.49 – 7.41 (m, 3H), 7.32 (s,

1H), 7.30 – 7.24 (m, 1H), 2.63 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 139.89, 139.27,

135.61, 129.33, 128.46, 127.58, 127.25, 125.89, 124.79, 124.03, 123.51, 120.50, 119.57,

119.44, 110.77, 77.48, 76.84, 21.58. IR (neat) v 3440, 2922, 1452, 1316, 1324, 1156,

747, 734 cm-1. HRMS (ESI) ([M+H]+ ) Calcd. for C19H15N 258.1283, found 258.1266.

Yield of (2y): 42.2 mg 93%, white solid, M.p.= 179℃ Rf = 0.31 (petroleum ether :

2H), 7.63 (d, J=8.7, 2H), 7.31 – 7.17 (m, 2H), 7.13 (d, J=8.7, 2H), 7.05 (d, J=2.2, 1H),

6.79 (dd, J=8.6, 2.3, 1H), 3.85 (s, 3H), 3.83 (s, 3H). 13C NMR (100 MHz, DMSO) δ

158.59, 158.41, 141.61, 136.92, 131.02, 129.47, 124.17, 123.97, 123.40, 120.80, 119.17,

117.98, 116.35, 114.40, 107.80, 95.04, 55.21, 55.13. IR (neat) v 3672, 2962, 1568, 1541,

1031, 802, 667 cm-1. HRMS (ESI) ([M-H]-) Calcd. for C20H17NO2 302.1186, found

302.1176.

Yield of (2z): 30.9 mg 80% (4 d), light brown solid, M.p. = 210℃, Rf = 0.24 (petroleum

ether : ethyl acetate 10:1). 1H NMR (400 MHz, Acetone) δ = 10.83 (brs, 1H), 8.42 (d,

J = 8.0, 1H), 8.15 – 8.03 (m, 2H), 7.78 (d, J = 8.0, 1H), 7.62 (dd, J = 18.8, 8.4, 2H),

7.53 – 7.31 (m, 4H). 13C NMR (100 MHz, Acetone) δ 156.73, 151.87, 141.66, 140.54,

126.43, 126.12, 126.05, 123.90, 122.81, 121.36, 120.53, 120.52, 118.81, 116.08, 112.26,

111.98, 108.93, 107.93. IR (neat) v 3403, 2925, 1456, 1324, 1243, 1141, 742 cm-1.

HRMS (ESI) ([M-H]-) Calcd. for C18H11NO 256.0768, found 256.0779.

Yield of (4a)[19]: 25.4 mg, 80%, white solid, M.p.= 155℃ Rf = 0.31 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, CDCl3) δ = 8.15 (s, 1H), 7.89 (brs, 1H), 7.33

(t, J = 8.0, 1H), 7.26 – 7.21 (m, 2H), 7.00 (d, J = 8.0, 1H), 6.68 (d, J = 8.0, 1H), 4.09

(s, 3H), 2.55 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 156.33, 141.30, 136.98, 128.99,

126.57, 126.31, 123.03, 122.90, 112.53, 109.71, 103.66, 100.25, 55.51, 21.59. IR (neat)

v 3405, 2928, 1506, 1458, 1346, 1260, 1100, 748 cm-1. HRMS (ESI) ([M+Na]+ ) Calcd.

for C14H13NO 234.0895, found 234.0893.

Yield of (4b)[20]: 31.4 mg, 82%; 36.0 mg, 94% (4 d), white solid, M.p. = 198℃, Rf =

0.65 (petroleum ether : ethyl acetate 1:1). 1H NMR (400 MHz, DMSO) δ = 11.59 (brs,

1H), 8.67 (d, J = 1.2, 1H), 8.11 (d, J = 8.4, 1H), 7.94 (dd, J = 8.4, 1.6, 1H), 7.50 (d, J =

8.4, 1H), 7.02 (d, J = 2.4, 1H), 6.83 (dd, J = 8.4, 2.2, 1H), 3.87 (s, 3H), 3.85 (s, 3H). 13C NMR (100 MHz, DMSO) δ 167.06, 159.07, 142.68, 141.84, 125.50, 122.56, 121.52,

121.34, 119.90, 116.05, 110.46, 108.76, 94.87, 55.34, 51.74. IR (neat) v 3279, 1697,

1438, 1328, 1265, 1159, 742 cm-1. HRMS (ESI) ([M+Na]+ ) Calcd. for C15H13NO3

278.0793, found 278.0783.

Yield of (4c)[21]: 33.7 mg, 88% (4 d), white solid, M.p. = 172℃, Rf = 0.49 (petroleum

ether : ethyl acetate 1:1). 1H NMR (400 MHz, CDCl3) δ = 8.70 (brs, 1H), 8.62 (s, 1H),

7.99 (d, J = 7.6, 1H), 7.41 – 7.31 (m, 2H), 7.27 – 7.23 (m, 1H), 6.74 (s, 1H), 3.97 (s,

3H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 167.37, 159.21, 143.60, 140.11,

125.48, 124.94, 123.35, 120.33, 119.84, 116.42, 112.05, 110.87, 93.62, 56.08, 52.07.

IR (neat) v 3297, 2951, 1704, 1462, 1349, 1237, 1083, 765, 748, 727 cm-1. HRMS (ESI)

([M+Na]+ ) Calcd. for C15H13NO3 278.0793, found 278.0780.

Yield of (4d)[22]: 37.2 mg, 87% (4 d), white solid, M.p. = 186℃, Rf = 0.29 (petroleum

ether : ethyl acetate 3:1). 1H NMR (400 MHz, Acetone) δ = 10.39 (brs, 1H), 8.41 (s,

1H), 7.95 (d, J = 8.4, 1H), 7.11 (s, 1H), 7.03 (d, J = 2.4, 1H), 6.83 (dd, J = 8.4, 2.4, 1H),

3.90 (s, 3H), 3.84 (d, J = 9.6, 6H). 13C NMR (100 MHz, Acetone) δ 167.41, 159.70,

158.94, 144.66, 142.80, 123.88, 121.12, 117.73, 117.19, 113.49, 109.21, 95.95, 94.90,

56.40, 55.75, 51.66. IR (neat) v 3303, 2925, 1704, 1462, 1266, 1235, 1157, 747 cm-1.

HRMS (ESI) ([M+Na]+ ) Calcd. for C16H15NO4 308.0899, found 308.0881.

Yield of (4e): 25.3 mg, 75%, yellow solid, M.p. = 185℃, Rf = 0.12 (petroleum ether :

ethyl acetate 5:1). 1H NMR (400 MHz, DMSO) δ = 11.73 (brs, 1H), 10.01 (s, 1H), 8.60

(s, 1H), 8.11 (d, J = 8.4, 1H), 7.85 (dd, J = 8.4, 1.1, 1H), 7.57 (d, J = 8.4, 1H), 7.04 (d,

J = 2.0, 1H), 6.87 (dd, J = 8.4, 2.2, 1H), 3.86 (s, 3H). 13C NMR (100 MHz, DMSO) δ

192.03, 159.23, 143.65, 141.95, 128.30, 125.48, 123.02, 122.90, 121.61, 116.12, 111.09,

109.13, 95.09, 55.40. IR (neat) v 3286, 2925, 1673, 1456, 1321, 1266, 1158, 741 cm-1.

HRMS (ESI) ([M+Na]+ ) Calcd. for C14H11NO2 248.0687, found 248.0673.

Yield of (2aa): 13.8 mg, 20 %, yellow solid, M.p. = 84℃, Rf = 0.12 (petroleum ether :

ethyl acetate 10:1). 1H NMR (400 MHz, DMSO) δ = 11.07 (brs, 1H), 8.14 (d, J = 8.3,

2H), 8.04 (dd, J = 17.4, 8.1, 2H), 7.86 (d, J = 8.3, 2H), 7.38 (d, J = 6.7, 1H), 7.25 (t, J

= 7.6, 1H), 7.02 (d, J = 2.2, 1H), 6.81 (dd, J=8.6, 2.2, 1H), 4.38 (q, J = 7.1, 2H), 3.83

(s, 3H), 1.37 (t, J = 7.1, 3H). 13C NMR (100 MHz, DMSO) δ = 165.62, 158.60, 143.48,

141.68, 136.79, 129.78, 128.70, 128.50, 124.32, 123.76, 123.12, 121.00, 119.41,

119.30, 116.14, 108.13, 94.95, 60.76, 55.17, 14.23. IR (neat) v 3365, 2980, 1698, 1398,

1129, 769, 747 cm-1. HRMS (ESI) ([M+Na]+) Calcd. for C22H19NO3 368.1263, found

368.1262.

Yield of (2aa′): 12.4 mg, 18 %, white solid, M.p.= 129℃ Rf = 0.12 (petroleum ether :

3H), 7.79 (d, J = 8.1, 1H), 7.66 (d, J = 7.9, 2H), 7.45 (d, J = 7.1, 1H), 7.30 (t, J = 7.5,

1H), 7.16 (d, J = 8.1, 2H), 4.35 (d, J = 7.0, 2H), 3.86 (s, 3H), 1.36 (t, J=6.9, 3H). 13C

NMR (100 MHz, DMSO) δ = 166.44, 158.85, 139.53, 138.39, 130.51, 129.58, 126.66,

126.24, 124.94, 122.38, 120.09, 119.81, 119.39, 114.55, 113.08, 99.54, 60.58, 55.30,

14.29. IR (neat) v 3368, 2932, 1696, 1515, 1300, 1243, 763 cm-1. HRMS (ESI)

([M+Na]+) Calcd. for C22H19NO3 368.1263, found 368.1257.

VII. References

[1] Liu, L.; Zhang, Y.; Wang, Y. J. Org. Chem. 2005, 70, 6122–6125.

[2] Stokes, B. J.; Jovanovic´, B.; Dong, H.; Richert, K. J.; Riell, R. D. Driver, T. G. J.

Org. Chem. 2009, 74, 3225–3228.

[3] Gritsan, N.P.; Polshakov, D. A.; Tsaoa, M.; Platz, M. S. Photoch Photobio Sci, 2005,

4, 23–32.

[4] Stokes, B. J. ; K. Richert, J.; Driver , T. G. J. Org. Chem. 2009,74, 6442–6451.

[5] Liu, C.; Knochel, P. J. Org. Chem. 2007, 72, 7106–7115.

[6] Saneyoshi, H.; Ito, Y.; Abe, H. J. Am. Chem. Soc. 2013, 135, 13632–13635.

[7] Ullah, E.; McNulty, J.; Robertson, A. Eur. J. Org. Chem. 2012, 2127–2131.

[8] Manolikakes, G.; Schade, M. A.; Hernandez, C. M.; Mayr, H.; Knochel, P. Org.

Lett. 2008, 10, 2765–2768.

[9] Alt, I. T.; Plietker, B. Angew. Chem., Int. Ed. 2016, 55, 1519–1522.

[10] Takamatsu, K.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16, 2892–2895.

[11] Zhang, L.; Wang, W.; Fan, R. Org. Lett. 2013, 15, 2018–2021.

[12] Jiang, Q.; Mu, D.; Zhong, W.; Chen, H.; Yan, H. Chem. Eur. J. 2013, 19, 1903–

[13] Ackermann, L.; Althammer, A.; Mayer, P. Synthesis 2009, 20, 3493–3503.

[14] Guerra, W. D.; Rossi, R. A.; Pierini, A. B.; Barolo, S. M. J. Org. Chem. 2015, 80,

928−941.

[15] Sun, K.; Sachwani, R.; Richert, K. J. Driver, T. G. Org. Lett. 2009, 11, 3598–3601.

[16] Freeman, A. W.; Urvoy, M.; Criswell, M. E. J. Org. Chem. 2005, 70, 5014–5019.

[17] Bedford, R. B.; Betham, M. J. Org. Chem. 2006, 71, 9403–9410.

[18] Chakrabarty, S.; Chatterjee, I.; Tebben, L.; Studer, A. Angew. Chem. Int. Ed. 2013,

52, 2968–2971.

[19] Bautista, R.; P. Montoya, A.; Rebollar, A.; Burgueño, E.; Tamariz, J. Molecules

2013, 18, 10334–10351.

[20] Kuethea, J. T.; Childers, K. G. Adv. Synth. Catal. 2008, 350, 1577–1586.

[21] Rasheed, S.; Rao, D. N.; Reddy, K. R.; Aravinda, S.; Vishwakarma, R. A. RSC Adv.

2014, 4, 4960–4969.

[22] Krahl, M.; Kataeva, P. O.; Schmidt, A. W. H.; Knölker, J. Eur. J. Org. Chem. 2013,

1, 59–64.

[23] Huang, J.; Sun, N.; Chen, P.; Tang, R.; Li, Q.; Ma, D.; Li, Z. Chem. Commun.,

2014, 50, 2136-2138.

[24] Shou, W. G.; Li, J.; Guo, T.; Lin Z.; Jia, G. Organometallics, 2009, 28, 6847-6854.

Ⅷ. Spectral Copies of 1H, 13C NMR of All Compounds

Compound 1a

Compound 1b

Compound 1c

Compound 1d

Compound 1e

Compound 1f

Compound 1g

Compound 1h

Compound 1i′

Compound 1i

Compound 1j

Compound 1k

Compound 1l

Compound1m

Compound 1n

Compound 1o

Compound 1p

Compound 1q

Compound 1r

Compound 1s

Compound 1t

Compound 1u

Compound 1v′

Compound 1v

Compound 1w

Compound 1x

Compound 1y

Compound 1z

Compound 1aa

Compound 3a

Compound 3b

Compound 3c

Compound 3d

Compound 3e

Compound 3e′

Compound 1a-D′′

Compound 1a-D′

Compound 1a-D

Compound2a

Compound 2b

Compound 2c

Compound 2d

Compound 2e

Compound 2f

Compound 2g

Compound 2h

Compound 2i

Compound 2j

Compound 2k

Compound 2l

Compound 2m

Compound 2n

Compound 2o

Compound 2p

Compound 2q

Compound 2r

Compound 2r′

Compound 2s

Compounds 2s

Compound 2t

Compound 2u

Compound 2v

Compound 2w

Compound 2x

Compound 2y

Compound 2z

Compound 4a

Compound 4b

Compound 4c

Compound 4d

Compound 4e

Compound 2aa

Compound 2aa′

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