Table Of ContentElectronic Supplementary Material (ESI) for Green Chemistry.
This journal is © The Royal Society of Chemistry 2018
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]
[email protected]
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: [email protected].
[b] Department of Chemistry and Biochemistry，Texas Tech University, Lubbock, TX 79409-1061
(USA)
S1
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 (CDCl ) at 7.26 ppm. The following
3
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.
S2
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, H O
2
(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 CH Cl and separated. The aqueous phase was extracted with an
2 2
additional 3 × 5 mL of CH Cl , and the combined organic phases were washed 2 × 5
2 2
mL of water. The organic phase was dried over Na SO and filtered. The solvents were
2 4
removed under reduced pressure, and the crude yield was measured by 1H NMR
spectroscopy using CH Br as an internal standard.
2 2
1H NMR of reaction mixture:
S3
2. Scheme 3b
Azides 1p (0.10 mmol, 22.5 mg), 1u (0.10 mmol, 26.7 mg), silica gel 15.0 mg, H O
2
(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 CH Cl and separated. The aqueous phase was extracted with an
2 2
additional 3 × 5 mL of CH Cl , and the combined organic phases were washed 2 × 5
2 2
mL of water. The organic phase was dried over Na SO and filtered. The solvents were
2 4
removed under reduced pressure, and the crude yield was measured by 1H NMR
spectroscopy using CH Br as an internal standard.
2 2
1H NMR of reaction mixture:
S4
3. Scheme3c
1a-D (0.10 mmol, 19.6 mg), silica gel 15.0 mg, H O (1.5 ml) and Acetone (1.5 ml) were
2
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 CH Cl and separated.
2 2
The aqueous phase was extracted with an additional 3 × 10 mL of CH Cl , and the
2 2
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 R =
f
0.36 (petroleum ether : ethyl acetate 10:1).
Kinetic Isotope Effect of Intramolecular was estimated by 1H NMR
S5
1H NMR (400 MHz, DMSO): Carbazole 2a-D
S6
Kinetic Isotope Effect of Intramolecular was estimated by GC-MS
S7
S8
4. Scheme3d
1aa (0.20 mmol, 74.7 mg), silica gel 15.0 mg, H O (1.5 ml) and Acetone (1.5 ml) were added to a
2
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 CH Cl and separated. The aqueous phase was extracted with an
2 2
additional 3 × 10 mL of CH Cl , and the combined organic phases were washed 2 × 5 mL of water.
2 2
The organic phase was dried over Na SO and filtered. The crude product was purified by
2 4
chromatography on silica gel (petroleum ether : ethyl acetate gradient: 10:1-1:1) afforded the
mixture products 2aa +2aa′ (39.2 mg, 56%), R = 0.12 (petroleum ether : ethyl acetate 10:1). The
f
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′
S9
Ⅱ. Contents of Starting Materials
S10
Description:Ⅳ. General Procedures for Synthesis of Starting Materials and Spectroscopic Data of Biaryl . The fully decoupled 13C NMR was recorded on FT AM 400 (100 MHz). Chemical shifts were additional 3 × 10 mL of CH2Cl2, and the combined organic phases were washed 2 × 5 mL of water. The organic
