[Fe(F20TPP)Cl]-catalyzed amination with arylamines and {[Fe(F20TPP)(NAr)](PhI=NAr)}+. Intermediate assessed by high-resolution ESI-MS and DFT calculations

Article abstract of DOI:10.1002/asia.201402580

Amination of C-H bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for C-N bond formation, and the use of iminoiodinanes, or their in situ generated forms from 'PhI-(OAc)₂ + primary amides (such as sulfonamides, sulfamates, and carbamates)', as nitrogen sources for the amination reaction has been well documented. In this work, a 'metal catalyst + PhI(OAc)₂ + primary arylamines' amination protocol has been developed using [Fe(F₂₀TPP)Cl] (H₂F₂₀TPP = meso-tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra- and intermolecular amination of sp² and sp³ C-H bonds (> 27 examples), affording the amination products, including natural products such as rutaecarpine, in moderate-to-good yields. ESI-MS analysis and DFT calculations lend support for the involvement of {[Fe(F₂₀TPP)(NC₆H₄-p-NO₂)](PhI=NC₆H₄-p-NO₂)}⁺. intermediate in the catalysis.

Full text of DOI:10.1002/asia.201402580

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
[
Fe ACHTREUNG( F TPP)Cl]-Catalyzed Amination with Arylamines and
+
2
0
C
{
[Fe ACHTREUNG( F TPP) HCATREUNG( NAr)] ACHTREUN(G PhI=NAr)} Intermediate Assessed by High-
2
0
Resolution ESI-MS and DFT Calculations
[
a]
[a, b]
[a]
[a]
[b]
Yungen Liu, Guo-Qiang Chen,
Chun-Wai Tse, Xianguo Guan, Zheng-Jiang Xu,
[a] [a, b]
Jie-Sheng Huang, and Chi-Ming Che*
asia_201402580_sm_miscellaneous_information.pdf

Table of Contents
General
S2
S3
Table S1. Optimization of reaction conditions by using the synthesis of
methyl indole-2-carboxylate as a model reaction
Table S2. Test of different oxidants using the synthesis of methyl indole-
S4
S4
S5
S5
2
-carboxylate as a model reaction
General procedure for [Fe(F TPP)Cl]-catalyzed intramolecular
2
0
2
amination of sp C–H bonds
General procedure for [Fe(F TPP)Cl]-catalyzed intramolecular
2
0
3
amination of sp C–H bonds
General procedure for [Fe(F TPP)Cl]-catalyzed intermolecular
2
0
amination reactions
ESI-MS experiments
DFT calculations
S5
S6
Peak assignments of Figure 2
Cartesian coordinates
S7
S8
Characterization of amination products
NMR spectra
S18
S27
S1

General: Analytical grade chemicals (purchased from Sigma-Aldrich Chemical Co.) and
analytical grade organic solvents were used throughout the experiments, unless otherwise
specified. All manipulations were carried out using standard Schlenk line under an
atmosphere of argon. Solvents were pre-dried over activated 4 Å molecular sieves and
refluxed over sodium (toluene) or calcium hydride (1,2-dichloroethane and acetonitrile)
1
13
under an argon atmosphere and collected by distillation. H and C NMR spectra were
1
13
recorded on a Bruker DPX-300, AV-400, or DRX-500 NMR spectrometer. H and C
1
13
NMR spectra were referenced internally to residual protio-solvent ( H) or solvent ( C)
resonances and are reported relative to tetramethylsilane. The following abbreviations are
used to indicate the multiplicity in NMR spectra: s – singlet; d – doublet; t – triplet; q –
quartet; quint. – quintet; dd – double doublet; dt – double triplet; m – multiplet; brs –
broad signal. EI mass spectra (including HRMS) were measured on a Finnigan MAT 95
mass spectrometer (Thermo Electron, San Jose, US). Positive-ion ESI mass spectra were
obtained on a Waters Micromass Q-TOF Premier quadrupole-time of flight tandem mass
spectrometer (Waters Corporation, Milford, USA).
S2

Table S1. Optimization of reaction conditions by using the synthesis of methyl indole-2-
carboxylate as a model reaction
Entry
1
X
Y
8
Solvent
DCE
T [°C ].
80
t [h]
3
Conversion [%] Yield [%]
1.5
100%
29%
[
a]
2
1.5
8
DCE
80
3
100%
29%
[
b]
3
4
1.5
1.5
8
8
DCE
80
80
3
3
72%
58%
17%
17%
MeCN
5
6
7
8
1.5
1.5
1.5
1.5
8
2
8
8
Toluene
Toluene
Toluene
Toluene
110
110
rt
3
86%
90%
85%
78%
46%
7%
3
[
[
[
c]
c]
d]
12
3
34%
40%
110
9
1
2.0
2.0
8
8
Toluene
Toluene
110
110
3
3
100%
100%
65%
68%
[
e]
0
Reaction conditions: [a] PhI(OAc) added in three portions (0.5 equiv / 0.5 h). [b]
2
Substrate and PhI(OAc) were added simultaneously by syringe pump in 3 h. [c] 1.5
2
equiv of K CO was added. [d] PhI(OAc) was added in two portions (1.0 equiv / 0.5 h).
2
3
2
[
e] 4 Å MS (120 mg) was added and PhI(OAc) was added in five portions (0.08 mmol /
2
0
.5 h). DCE: 1,2-dichloroethane.
S3

Table S2. Test of different oxidants using the synthesis of methyl indole-2-carboxylate as
a model reaction
Entry
Oxidant
Time [h]
Conversion [%]
Yield [%]
1
2
3
4
PhI(OAc)2
30% H O
3
3
3
3
100
20
65
<5
/
2
2
NaIO4
DDQ
<5
100
/
The reactions were performed with 0.20 mmol substrate and 0.004 mmol [Fe(F TPP)Cl]
2
0
(
2 mol %) in 8 mL of anhydrous toluene under N . The mixture was heated to reflux and
2
then 0.4 mmol of oxidant was added in five portions (0.08 mmol / 0.5 h).
2
General procedure for [Fe(F TPP)Cl]-catalyzed intramolecular amination of sp
2
0
C–H bonds (Table 1)
A. Synthesis of indoles
To a mixture of substrate (0.20 mmol), [Fe(F TPP)Cl] (0.004 mmol, 2 mol%), and 4 Å
2
0
molecular sieves (120 mg) in refluxing anhydrous toluene (8 mL) under N , PhI(OAc)
2
2
(0.4 mmol, 129 mg) was added in five portions (0.08 mmol / 0.5 h). The reactions were
monitored by thin layer chromatography (TLC) and completed within 3 h. After
removing toluene in reduced pressure, the residue was purified by flash column
chromatography to give the desired product.
B. Synthesis of phenyl benzimidazoles
A mixture of phenylenediamine (0.2 mmol), benzaldehyde (0.2 mmol), [Fe(F TPP)Cl]
2
0
(0.004 mmol, 2 mol%), and 4 Å molecular sieves (180 mg) in anhydrous toluene (8 mL)
under N was stirred at room temperature for 3 h. Then the mixture was heated to reflux
2
and PhI(OAc) (0.4 mmol, 129 mg) was added in five portions (0.08 mmol / 0.5 h) and
2
the reactions were further stirred for an hour. After removing toluene in reduced pressure,
the residue was purified by flash column chromatography to give the desired product.
S4

3
General procedure for [Fe(F TPP)Cl]-catalyzed intramolecular amination of sp
2
0
C–H bonds (Table 2)
To a mixture of substrate (0.20 mmol), [Fe(F TPP)Cl] (0.004 mmol, 2 mol%), and 4 Å
2
0
molecular sieves (120 mg) in refluxing anhydrous toluene (8 mL) under N , PhI(OAc)
2
2
(0.4 mmol, 129 mg) was added in five portions (0.08 mmol / 0.5 h). The reactions were
monitored by thin layer chromatography (TLC) and completed within 3 h. After
removing toluene in reduced pressure, the residue was purified by flash column
chromatography to give the desired product.
General procedure for [Fe(F TPP)Cl]-catalyzed intermolecular amination
2
0
reactions (Table 3)
To a mixture of substrate (10 mmol), [Fe(F TPP)Cl] (0.004 mmol, 2 mol%), and 4 Å
2
0
molecular sieves (120 mg) in toluene (1.5 mL) at 120 °C, nitrogen source (0.2 mmol) and
PhI(OAc) (0.4 mmol, 129 mg) were jointly added in five portions (0.004 mmol / 0.5 h
2
and 0.08 mmol / 0.5 h, respectively). The reactions were monitored by thin layer
chromatography (TLC) and completed within 3 h. After removing toluene in reduced
pressure, the residue was purified by flash column chromatography to give the desired
product. For tetralin and indan, the reactions were performed with 10 mmol of substrate
without toluene under similar conditions.
ESI-MS experiments
Positive-ion ESI mass spectra were obtained on a Waters Micromass Q-Tof Premier
quadrupole time-of-flight tandem mass spectrometer. For the detection of m/z 1504.1 ion,
an acetonitrile solution of [Fe(F TPP)Cl] (1 mM) was treated with 10 equiv of p-
2
0
nitroaniline and PhI(OAc) (both were 20 mM solutions in MeCN). The final
2
concentration of iron in the reaction mixture was 0.5 mM. After heating at ca. 60 °C for
3
5
0 s, the mixture was introduced into the ESI source by using a syringe pump (flow rate:
μL min ). The mass resolution was fixed at about 8000 (full width at half-height).
-1
S5

DFT calculations
Optimization of the geometry of the proposed intermediate {[Fe(F TPP)(NC H -p-
2
0
6
4
+
·
NO )](PhI=NC H -p-NO )} (complex A) was carried out with the density functional
2
6
4
2
M06L and double-zeta quality basis set (6-31G* for C, H, N, F atoms, SDD for Fe atom,
and SDD conjunction with a 0.266 d polarization for I atom) through Gaussian09
[
1]
programm.
The free energy difference (G) between the complex A and the separated
+
∙
[
Fe(F TPP)(NC H -p-NO )] unit and [PhI=NC H -p-NO ] unit was calculated based on
20 6 4 2 6 4 2
[
2]
the geometries optimized by M06L/6-31G* (SDD), B3LYP-D3 together with triplet-
zeta quality basis set (6-311G* (SDD)) used for single point energy correction. The
solvation energies were computed using the PCM solvation model, employing
acetonitrile as the solvent.
References
[
1] Gaussian 09, Revision C.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J.
L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R.
Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G.
A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian, Inc., Wallingford, CT, 2011.
[
2] a) S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104; b)
S. Grimme, J. Comput. Chem. 2006, 27, 17871799.
S6

Peak assignments of Figure 2
All detected signals are mono-cationic:
m/z
Proposed composition
Fe(F TPP)
1
1
1
1
1
1
028.1
069.1
081.1
317.2
488.2
504.1
2
0
Fe(F TPP) + MeCN
2
0
Fe(F TPP) + H O + Cl
2
0
2
Fe(F TPP) + NHAr + O=NAr
2
0
Fe(F TPP) + H NAr + PhI(OAc)
2
2
0
2
Fe(F TPP) + NAr + PhI=NAr
2
0
Ar = C H -p-NO
2
6
4
S7

Cartesian coordinates
Fe(F TPP)(NC H -p-NO )(PhI=NC H -p-NO )] (S = 1/2, )
+
∙
[
2
0
6
4
2
6
4
2
Standard orientation:
--------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type
--------------------------------------------------------------------
-
X
Y
Z
-
1
2
3
4
5
6
7
8
9
6
6
6
1
7
6
6
1
6
0
0
0
0
0
0
0
0
0
3.450199 -1.472508 1.419390
2.068923 -1.519462 1.061126
3.830243 -0.172564 1.346923
4.063954 -2.334829 1.650138
1.590272 -0.252779 0.796376
1.361358 -2.705505 0.888903
2.670580 0.584092 0.979206
4.821378 0.235693 1.499320
2.057375 -3.979585 1.192996
0.047249 -2.753340 0.437732
2.673239 1.968026 0.791990
2.464733 -4.862083 0.191990
2.343815 -4.334781 2.513017
-0.769349 -1.657595 0.214769
-0.657885 -3.965149 0.162189
1.543739 2.690536 0.413503
3.950222 2.688804 0.993755
3.121927 -6.051843 0.480938
1
0
1
2
3
4
5
6
7
8
6
0
1
1
1
1
1
1
1
1
6
6
6
7
6
6
6
6
0
0
0
0
0
0
0
0
S8

1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
9
6
9
6
6
1
7
6
6
6
6
9
9
6
1
6
6
1
6
9
6
9
9
6
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.232280 -4.564169 -1.096236
3.000954 -5.518454 2.828857
1.984572 -3.520774 3.508012
-1.991954 -2.191249 -0.147318
-1.914804 -3.616758 -0.212966
-0.236889 -4.959989 0.239798
0.296330 2.161445 0.157934
1.519313 4.117999 0.301293
4.577303 3.365907 -0.055387
4.624214 2.665991 2.218255
3.389466 -6.380514 1.807284
3.497342 -6.869609 -0.498600
3.253499 -5.832343 4.093011
-3.165332 -1.467106 -0.349771
-2.727271 -4.268429 -0.511024
-0.513860 3.254235 -0.062889
0.243625 4.467751 0.005633
2.369639 4.769864 0.457646
5.838520 3.930385 0.073783
3.970910 3.454320 -1.252394
5.879054 3.242587 2.380853
4.066175 2.061961 3.271389
4.012409 -7.512991 2.097863
-4.422470 -2.205291 -0.603663
-3.214199 -0.075002 -0.320854
S9

4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
6
1
6
9
9
6
6
7
6
6
6
9
6
9
6
9
6
1
6
6
6
9
9
1
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-1.894477 3.217244 -0.254179
-0.159575 5.463202 -0.131507
6.495957 3.864067 1.298269
6.423232 4.504623 -0.969845
6.489334 3.200059 3.559358
-5.139634 -2.034761 -1.790955
-4.965795 -3.085616 0.337674
-2.118965 0.757665 -0.204009
-4.414998 0.688651 -0.454523
-2.635628 2.040101 -0.281726
-2.604525 4.502238 -0.459660
7.698185 4.396964 1.431716
-6.328330 -2.705648 -2.044500
-4.673287 -1.211060 -2.744627
-6.155530 -3.768333 0.111448
-4.339230 -3.285564 1.505097
-4.055349 1.997227 -0.442293
-5.410246 0.273127 -0.552967
-3.521197 5.003055 0.466640
-2.368405 5.267369 -1.603702
-6.838754 -3.577056 -1.086353
-6.970091 -2.526090 -3.194107
-6.644850 -4.591955 1.029304
-4.697202 2.863365 -0.543396
-4.179469 6.211429 0.268405
S10

6
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
9
6
9
9
6
9
9
9
26
7
6
6
6
6
1
6
1
6
1
1
7
8
8
1
6
0
0
0
0
0
0
0
0
-3.784801 4.308929 1.581314
-3.008383 6.480592 -1.823186
-1.499189 4.831833 -2.523040
-7.969766 -4.225242 -1.314640
-3.919713 6.951681 -0.882066
-5.045644 6.662674 1.168350
-2.762714 7.185089 -2.922446
-4.541615 8.103853 -1.081841
-0.338138 0.261992 0.558517
-0.830551 0.514925 2.167333
-2.037849 0.462903 2.766320
-2.806070 -0.730106 2.859499
-2.548989 1.665358 3.329244
-4.047647 -0.707456 3.462650
-2.399100 -1.654573 2.456441
-3.802042 1.683697 3.906497
-1.950632 2.570285 3.254461
-4.535355 0.499016 3.962953
-4.658343 -1.601779 3.542924
-4.230542 2.595933 4.311676
-5.875470 0.522961 4.564104
-6.257936 1.588808 5.038521
-6.518693 -0.523711 4.540185
-3.422039 -2.874445 -4.040669
-2.355491 -2.965084 -3.851447
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
S11

9
9
9
9
9
9
4
5
6
7
8
9
6
6
6
1
6
1
53
6
1
7
1
6
6
6
6
1
6
1
6
1
1
7
8
8
0
0
0
0
0
0
-1.637826 -1.823700 -3.490469
-1.714769 -4.195757 -3.970576
-0.275043 -1.977678 -3.283182
-2.144052 -0.867532 -3.374247
-0.347417 -4.302790 -3.733195
-2.285886 -5.076471 -4.254709
0.875585 -0.216493 -2.784947
0.404960 -3.176703 -3.397831
0.157548 -5.262528 -3.822206
2.448515 -1.462036 -2.127271
1.473640 -3.240116 -3.219197
3.653104 -0.889365 -1.990197
4.671022 -1.832714 -1.608513
4.038742 0.471385 -2.149732
5.958138 -1.416110 -1.366165
4.384113 -2.877186 -1.507915
5.333441 0.874932 -1.912798
3.299254 1.208057 -2.467057
6.280456 -0.059980 -1.493565
6.730816 -2.118871 -1.066674
5.636729 1.907513 -2.050293
7.615874 0.401192 -1.146885
7.785194 1.621055 -1.059366
8.474790 -0.454432 -0.942880
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
00
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
---------------------------------------------------------------------
S12

+
∙
[
Fe(F TPP)(NC H -p-NO )(PhI=NC H -p-NO )] (S = 3/2, )
2
0
6
4
2
6
4
2
Standard orientation:
--------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type
--------------------------------------------------------------------
-
X
Y
Z
-
1
2
3
4
5
6
7
8
9
6
6
7
6
6
6
6
6
6
0
0
0
0
0
0
0
0
0
3.437799 -1.533442 1.364461
2.059507 -1.563350 1.001777
1.588001 -0.285499 0.766578
2.664137 0.542062 0.983424
3.824094 -0.230582 1.329434
1.333863 -2.746235 0.837743
2.027352 -4.025878 1.127949
2.419345 -4.905247 0.118603
3.066593 -6.103577 0.394108
3.340390 -6.443788 1.716212
2.967507 -5.585000 2.746379
2.319460 -4.392797 2.443519
2.179484 -4.595171 -1.166060
3.427431 -6.918289 -0.594142
3.226123 -5.910673 4.006281
1.975825 -3.582437 3.446211
-0.334614 0.246894 0.502544
-0.802573 -1.689560 0.218113
1
0
1
2
3
4
5
6
7
8
6
0
1
1
1
1
1
1
1
1
6
6
0
0
0
0
0
0
9
9
9
9
26
7
0
0
S13

1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
6
6
6
6
6
6
6
6
6
6
6
9
9
9
9
6
6
7
6
6
6
6
6
7
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-2.031766 -2.209574 -0.108895
-1.979417 -3.642258 -0.156217
-0.718501 -4.001603 0.186670
0.007435 -2.788711 0.429982
-3.191497 -1.462987 -0.335950
-4.462109 -2.186809 -0.566206
-5.175485 -2.045163 -1.759376
-6.379093 -2.697182 -1.990470
-6.906616 -3.525487 -1.003781
-6.224237 -3.693254 0.197772
-5.019749 -3.029015 0.401744
-4.689922 -1.266940 -2.743051
-7.018170 -2.541619 -3.145366
-6.727883 -4.478988 1.140766
-4.392685 -3.212289 1.569939
2.663989 1.935247 0.858873
1.538590 2.675515 0.501730
0.296387 2.157019 0.210854
-0.500559 3.254240 -0.024987
0.256464 4.467585 0.093008
1.520037 4.108699 0.422640
-1.869377 3.217352 -0.283945
-2.611450 2.039280 -0.354129
-2.108846 0.756531 -0.252288
-3.212992 -0.070535 -0.366722
S14

4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
6
6
6
6
6
6
6
6
9
9
9
9
6
6
6
6
6
6
9
9
9
9
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-4.403113 0.705172 -0.545014
-4.029200 2.008209 -0.554087
3.941326 2.647109 1.094699
4.575912 3.362888 0.076437
5.828913 3.937974 0.239047
6.473379 3.835747 1.468048
5.852339 3.166730 2.519587
4.603601 2.586247 2.324305
3.985631 3.484278 -1.126994
4.042089 1.938813 3.348431
6.453070 3.084751 3.700734
6.413382 4.562565 -0.776369
-2.568503 4.506011 -0.508423
-3.512193 5.008039 0.389548
-4.158407 6.220110 0.175464
-3.857393 6.964532 -0.961988
-2.916949 6.493782 -1.874181
-2.289093 5.277166 -1.638746
-3.815691 4.312608 1.492477
-5.051170 6.671383 1.048859
-2.630855 7.203029 -2.960995
-1.387984 4.843716 -2.528622
-2.807692 -4.286090 -0.426915
-0.305649 -4.999969 0.266562
4.045863 -2.402717 1.584287
S15

6
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
1
1
1
1
1
9
9
9
9
7
6
6
6
6
1
6
1
6
1
1
7
8
8
7
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4.814807 0.170487 1.505731
2.366377 4.755159 0.618931
-0.140976 5.466080 -0.040399
-4.659985 2.879225 -0.680764
-5.402097 0.300066 -0.646908
3.954895 -7.584059 1.994820
7.666613 4.380065 1.637012
-4.466694 8.120958 -1.176299
-8.051440 -4.157243 -1.209737
2.515859 -1.425610 -2.069751
3.713789 -0.840089 -1.941560
4.748316 -1.781415 -1.599562
4.078151 0.531096 -2.076701
6.043328 -1.360844 -1.406628
4.473229 -2.829305 -1.506262
5.378767 0.939246 -1.885733
3.317813 1.270235 -2.331943
6.347723 -0.002182 -1.533631
6.833340 -2.061538 -1.151309
5.668500 1.978445 -2.002204
7.704548 0.460696 -1.247804
7.869823 1.677402 -1.150693
8.570988 -0.397181 -1.104475
-0.844669 0.426037 2.159512
-2.077665 0.452631 2.712942
S16

9
9
9
9
9
9
4
5
6
7
8
9
6
6
6
1
6
1
0
0
0
0
0
0
-2.813412 -0.740647 2.945591
-2.650555 1.697177 3.091701
-4.075482 -0.686672 3.504114
-2.368186 -1.694229 2.668826
-3.908379 1.746222 3.659793
-2.083469 2.608359 2.912499
-4.607949 0.555049 3.850243
-4.662287 -1.583569 3.677851
-4.370453 2.685661 3.949315
-5.956870 0.610256 4.424832
-6.377391 1.711874 4.769696
-6.573970 -0.449523 4.513313
0.919852 -0.206321 -2.708054
-0.207218 -1.975278 -3.233831
-1.578419 -1.837947 -3.390000
0.493378 -3.153756 -3.415929
-2.285761 -2.980795 -3.767458
-2.098185 -0.897164 -3.219668
-0.250319 -4.282990 -3.759823
1.568666 -3.205076 -3.280071
-1.626970 -4.193960 -3.946276
-3.359245 -2.904519 -3.918100
0.268029 -5.229549 -3.898689
-2.191417 -5.076405 -4.237920
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
00
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
6
0
1
1
7
8
8
53
6
6
6
6
1
6
1
6
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
---------------------------------------------------------------------
S17

Characterization of amination products
J. Med. Chem. 2004, 47, 5298–5310.
H NMR (300 MHz, CDCl ), δ 8.91 (brs, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.43 (dd, J = 8.4,
1
3
0
1
.6 Hz, 1H), 7.33 (td, J = 7.8, 1.2 Hz, 1H), 7.28 (d, J=0.6 Hz, 1H), 7.16 (td, J=7.8, 0.6 Hz,
H), 3.95 (s, 3H).
Org. Lett. 2008, 10, 4899–4901.
1
H NMR (300 MHz, CDCl ), δ 8.90 (brs, 1H), 7.35 (dd, J = 9.0, 3.9 Hz, 1H), 7.31-7.26
3
(m, 1H), 7.17 (s, 1H), 7.09 (td, J = 9.3, 1.5 Hz, 1H), 3.95 (s, 3H).
Org. Lett. 2008, 10, 4899–4901.
1
H NMR (300 MHz, CDCl ), δ 8.99 (brs, 1H), 7.66 (s, 1H), 7.35 (d, J = 8.4 Hz, 1H), 7.28
3
(dd, J = 8.4, 1.8 Hz, 1H), 7.15 (d, J = 0.9 Hz, 1H), 3.95 (s, 3H).
Synth. Commun. 2009, 39, 2506–2515.
1
H NMR (400 MHz, CDCl ), δ 9.03 (brs, 1H), 7.83 (d, J = 2.0 Hz, 1H), 7.40 (dd, J = 8.8,
3
2
1
.0 Hz, 1H), 7.30 (d, J = 9.2 Hz, 1H), 7.15 (d, J = 2.0 Hz, 1H), 4.42 (q, J = 7.2 Hz, 2H),
.42 (t, J = 7.2 Hz, 3H).
Chem. Asian J. 2009, 4, 1551–1561.
S18

1
H NMR (400 MHz, DMSO-d ), δ 8.27-8.25 (m, 2H), 7.74-7.70 (m, 2H), 7.68-7.61 (m,
6
3
H), 7.40-7.35 (m, 2H).
Org. Lett. 2008, 10, 3367–3370.
1
H NMR (400 MHz, DMSO-d ), δ 8.17-8.14 (m, 2H), 7.61-7.48 (m, 4H), 7.39 (d, J = 9.2
6
Hz, 1H), 7.09-7.04 (m, 1H).
Org. Lett. 2008, 10, 3367–3370.
1
H NMR (400 MHz, DMSO-d ), δ 12.63 (brs, 1H), 8.12 (d, J = 7.6 Hz, 2H), 7.52 (t, J =
6
7
.6 Hz, 2H), 7.47-7.25 (m, 3H), 2.32 (s, 6H).
Org. Biomol. Chem. 2007, 5, 103–113.
H NMR (400 MHz, CDCl ), δ 8.50 (d, J = 8.0 Hz, 1H), 8.32 (d, J = 8.0 Hz, 1H), 7.79-
1
3
7
.4 (m, 2H), 7.51-7.43 (m, 3H), 7.32 (d, J = 8.0 Hz, 1H), 4.43 (t, J = 6.4 Hz, 2H), 3.11 (t,
J = 6.4 Hz, 2H).
Chin. Pharm. J. 2000, 52, 167–177.
1
H NMR (300 MHz, CDCl ), δ 8.34 (d, J = 7.8 Hz, 1H), 7.79-7.72 (m, 2H), 7.56-7.48 (m,
3
6
H), 4.04 (q, J = 6.9 Hz, 2H), 1.22 (t, J = 6.9 Hz, 3H).
S19

Chin. Pharm. J. 2000, 52, 167–177.
1
H NMR (400 MHz, CDCl ), δ 8.34 (d, J = 8.0 Hz, 1H), 7.79-7.74 (m, 2H), 7.58-7.50 (m,
3
6
H), 3.50 (s, 3H).
J. Am. Chem. Soc. 2008, 130, 416–417.
H NMR (400 MHz, CDCl ), δ 8.28 (dd, J = 8.0, 1.2 Hz, 1H), 7.73 (td, J =7.6, 2.0 Hz,
1
3
1
H), 7.65 (d, J =7.2 Hz, 1H), 7.45 (td, J = 7.8, 1.2Hz, 1H), 4.21 (t, J = 7.2 Hz, 2H), 3.18
(t, J = 8.0 Hz, 2H), 2.33-2.26 (m, 2H).
Org. Biomol. Chem. 2007, 5, 103–113.
1
H NMR (400 MHz, CDCl ), δ 8.27 (dd, J = 7.6, 1.2 Hz, 1H), 7.72 (td, J = 7.6, 2.0 Hz,
3
1
H), 7.60 (d, J = 8.8 Hz, 1H), 7.43 (td, J = 7.6, 1,2 Hz, 1H), 4.09 (t, J = 6.0 Hz, 2H), 3.01
(t, J = 6.8 Hz, 2H), 2.04-1.94 (m, 4H).
1
H NMR (400 MHz, CDCl ), δ 8.25 (dd, J = 8.0, 1.2 Hz, 1H), 7.70 (td, J = 7.6, 1.2 Hz,
3
1
H), 7.26 (d, J = 8.0 Hz, 1H), 7.42 (td, J = 7.6, 1.2 Hz, 1H), 4.07 (t, J = 8.0 Hz, 2H), 2.81
(
t, J = 8.0 Hz, 2H), 1.89-1.81 (m, 2H), 1.76-1.68 (m, 2H), 1.48-1.42 (m, 6H), 1.40-1.33
+
(m, 4H), 0.96-0.88 (m, 6H). EIMS 300 (M ), HREIMS (C H N O) cacld. 300.2197,
1
9
28
2
found 300.2200.
S20

J. Am. Chem. Soc. 2009, 131, 15996–15997.
1
H NMR (400 MHz, CDCl ), δ 8.33 (dd, J = 7.2, 1.6 Hz, 1H), 8.06 (s, 1H), 7.77 (td, J =
3
7
.6, 1.6 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.51 (td, J = 7.6, 1.6 Hz, 1H), 3.61 (s, 3H).
Tetrahedron Lett. 2003, 44, 1883.
H NMR (400 MHz, CDCl ), δ 8.63 (d, J = 8.1 Hz, 1H), 8.44 (dd, J = 7.9, 0.7 Hz, 1H),
1
3
8
.03 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.85 (t, J = 8.1 Hz, 1H), 7.79 (t, J = 7.5
Hz, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H).
.
Tetrahedron 2004, 60, 3417–3420.
1
H NMR (400 MHz, CDCl ), δ 9.48 (s, 1H), 8.32 (d, J = 7.8 Hz, 1H), 7.70-7.62 (m, 3H),
3
7
.40 (t, J = 7.9 Hz, 1H), 7.37 (d, J = 8.2 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.18 (t, J = 7.7
Hz, 1H), 4.59 (t, J = 6.8 Hz, 2H), 3.23 (t, J = 6.8 Hz, 2H).
Tetrahedron 2006, 62, 4306–4316.
1
H NMR (400 MHz, CDCl ), δ 8.27 (d, J = 7.6 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.38-
3
7
.21 (m, 6H), 4.22 (t, J = 6.9 Hz, 2H), 3.19 (t, J = 6.9 Hz, 2H).
S21

Chem. Eur. J. 2010, 16, 10494–10501.
1
H NMR (400 MHz, DMSO-d )  8.16 (d, J = 9.1 Hz, 1H), 8.04 (d, J = 9.1 Hz, 2H), 7.4
6
(m, 4H), 7.25 (m, 2H), 7.15 (m, 2H), 6.95 (d, J = 9.1 Hz, 1H), 6.32 (d, J = 9.1 Hz, 1H).
Chem. Eur. J. 2010, 16, 10494–10501.
1
H NMR (400 MHz, CDCl )  8.07 (d, J = 8.0 Hz, 2H), 7.74 (d, J = 7.1 Hz, 2H), 7.54 (d,
3
J = 7.1 Hz, 2H), 7.45 (m, 2H), 7.30 (m, 2H), 6.68 (d, J = 8.0 Hz, 2H), 5.72 (s, 1H), 4.97
(br s, 1H).
Chem. Eur. J. 2010, 16, 10494–10501.
H NMR (300 MHz, CDCl )  8.10 (d, J = 9.1 Hz, 2H), 7.20 (m, 4H), 6.60 (d, J = 9.1 Hz,
1
3
2
H), 4.74 (m, 1H), 2.85 (m, 2H), 2.06 (m, 2H), 1.85 (m, 2H).
S22

Adv. Synth. Catal. 2013, 355, 181–190.
1
H NMR (400 MHz, CDCl )  8.12 (d, J = 8.8 Hz, 2H), 7.35-7.30 (m, 3H), 7.28-7.22 (m,
3
1
H), 6.65 (d, J = 8.8 Hz, 2H), 5.10 (q, J = 6.8Hz, 1H), 4.73 (d, J = 6.8 Hz, 1H), 3.11-3.03
(m, 1H), 2.99-2.91 (m, 1H), 2.68-2.60 (m, 1H), 2.01-1.92 (m, 1H).
1
H NMR (400 MHz, CDCl )  7.35 (d, J = 7.0 Hz, 1H), 7.27-7.20 (m, 3H), 5.30 (q, J =
3
8
1
1
3
.2 Hz, 1H), 4.01 (d, J = 8.2 Hz, 1H), 3.07-3.00 (m, 1H), 2.93-2.84 (m, 1H), 2.60-2.55 (m,
1
3
H), 1.95-1.87 (m, 1H). C NMR (150 MHz, CDCl )  146.14 (m), 144.56 (m), 143.55,
3
43.33, 138.52 (m), 136.92 (m), 128.44, 126.97, 125.04, 124.13, 60.72 (t, J = 3.9 Hz),
+
5.15, 29.98. EIMS 359 (M ), HREIMS (C H BrF N) cacld. 358.9927, found 358.9929.
1
5
10
4
J. Porphyrins Phthalocyanines 2010, 14, 732–740.
H NMR (400 MHz, CDCl )  7.34-7.25 (m, 4H), 7.17 (s, 1H), 7.03 (s, 2H), 5.05 (q, J =
1
3
6
.9 Hz, 1H), 4.35 (d, J = 6.9 Hz, 1H), 3.10-3.00 (m, 1H), 2.99-2.90 (m, 1H), 2.67-2.61 (m,
1
3
1
H), 1.97-1.90 (m,1H). C NMR (100 MHz, CDCl )  148.31, 143.62, 143.08, 132.59 (q,
3
J = 32.6 Hz), 128.50, 127.68, 126.98, 125.16, 124.07, 123.62 (q, J = 271.1 Hz), 112.12 (d,
+
J = 3.0 Hz), 110.20 (quint, J = 3.9 Hz), 58.42, 33.46, 30.25. EIMS 345 (M ), HREIMS
(
C H F N) cacld. 345.0947, found 345.0950.
17 13 6
S23

1
H NMR (400 MHz, CDCl )  7.37 (m, 5H), 7.15 (s, 1H), 6.95 (s, 2H), 5.94 (dd, J = 7.3,
.7 Hz, 1H), 4.42 (brs 1H), 3.64-3.60 (m, 1H), 3.52-3.50 (m, 1H), 2.09 (s, 3H). C NMR
3
1
3
4
(
100 MHz, CDCl )  170.58, 148.32, 137.54, 132.32 (q, J = 32.4 Hz), 128.86, 128.73,
3
1
=
26.58, 125.16, 124.07, 123.53 (q, J = 270.9 Hz), 112.03 (d, J = 3.1 Hz), 110.20 (quint, J
4.0 Hz), 74.55, 48.73, 21.00. EIMS 391 (M ), HREIMS (C H F NO ) cacld.
18 15 6 2
+
3
91.1002, found 391.1004.
1
H NMR (400 MHz, CDCl )  7.36 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 7.17 (s,
3
1
H), 6.96 (s, 2H), 5.91 (dd, J = 7.2, 4.8 Hz, 1H), 4.36 (brs 1H), 3.64-3.58 (m, 1H), 3.52-
1
3
3
1
.49 (m, 1H), 2.10 (s, 3H). C NMR (100 MHz, CDCl )  170.39, 148.10, 136.07,
3
34.65， 132.51 (q, J = 32.6 Hz), 129.09, 127.88, 123.48 (q, J = 271.1 Hz), 112.05 (d, J
+
=
3.0 Hz), 110.80 (t, J = 3.8 Hz), 73.87, 48.60, 21.00. EIMS 425 (M ), HREIMS
(
C H ClF NO ) cacld. 425.0612, found 425.0611.
18 14 6 2
Tetrahedron 2004, 60, 4989–4994.
H NMR (400 MHz, CDCl )  7.11 (s, 1H), 6.93 (s 2H), 5.92 (m, 1H), 5.70 (m, 1H), 4.10
1
3
1
3
(
brs, 1H), 4.03 (brs, 1H), 2.05 (brs, 2H), 1.92 (m, 1H), 1.74-1.62 (m, 3H). C NMR (100
MHz, CDCl )  147.78, 132.65 (q, J = 32.4 Hz), 131.47, 126.99, 123.63 (q, J = 271.0 Hz),
3
+
1
12.05 (d, J = 3.2 Hz), 109.84 (t, J = 3.8 Hz), 47.77, 28.45, 25.00, 19.42. EIMS 309 (M ),
HREIMS (C H F N) cacld. 309.0947, found 309.0949.
1
4
13 6
S24

1
H NMR (400 MHz, CDCl )  7.09 (s, 1H), 6.90 (s 2H), 5.28 (s, 1H), 4.18 (d, J = 7.6 Hz,
3
1
1
1
5
H), 4.13 (m, 1H), 2.32-2.24 (m, 2H), 2.09 (t, J = 5.4 Hz, 1H), 1.74 (s, 3H), 1.36 (s, 3H),
1
3
.22 (d, J = 9.0 Hz, 1H), 0.99 (s, 3H). C NMR (100 MHz, CDCl )  149.43, 147.91,
3
32.29 (q, J = 32.2 Hz), 123.64 (q, J = 271.1 Hz), 116.00, 111.98, 109.68 (t, J = 3.9 Hz),
+
2.71, 47.71, 44.11, 43.92, 27.87, 26.48, 22.80, 20.54. EIMS 363 (M ), HREIMS
(
C H F N) cacld. 363.1417, found 363.1414.
18 19 6
1
H NMR (400 MHz, CDCl )  7.07 (s, 1H), 6.92 (s 2H), 5.74-5.64 (m, 1H), 5.20 (d, J =
3
1
1
1
3
5.8 Hz, 1H), 5.17 (d, J = 9.8 Hz, 1H), 4.10 (brs, 1H), 3.82 (brs, 1H), 1.67-1.59 (m, 2H),
13
.44-1.23 (brs, 12H), 0.88 (t, J = 6.5 Hz, 3H). C NMR (100 MHz, CDCl )  148.13,
3
38.46, 132.59 (q, J = 32.2 Hz), 123.54 (q, J = 271.1 Hz), 115.98, 112.38, 109.96 (t, J =
.8 Hz), 55.95, 35.71, 31.89, 29.74, 29.53, 29.46, 29.31, 25.83, 22.70, 14.14. EIMS 395
+
(M ), HREIMS (C H F N) cacld. 395.2043, found 395.2045.
2
0
27 6
1
H NMR (400 MHz, CDCl )  7.09 (s, 1H), 6.93 (s 2H), 5.76-5.64 (m, 1H), 5.53-5.30 (m,
3
1
0
H), 4.19 (brs, 0.7H), 4.10 (brs, 0.3H), 3.80 (brs, 0.6H), 3.75 (brs, 1.4H), 2.17-2.10 (m,
.6H), 2.07-2.02 (m, 1.4H), 1.26 (brs, 12H), 0.87 (t, J = 6.5 Hz, 3H). EIMS 395 (M ),
+
HREIMS (C H F N) cacld. 395.2043, found 395.2045.
2
0
27 6
S25

H
N
NO2
Chem. Eur. J. 2010, 16, 10494–10501.
1
H NMR (400 MHz, CDCl )  8.07 (d, J = 9.2 Hz, 2H), 6.45 (d, J = 9.2 Hz, 2H), 4.45 (br
3
s, 1H), 3.59 (m, 1H), 1.92 (m, 2H), 1.75 (m, 2H), 1.66-1.40 (m, 10H).
1
H NMR (400 MHz, CDCl )  7.08 (s, 1H), 6.85 (s 2H), 4.04 (d, J = 6.5 Hz, 1H), 3.54 (m,
H), 1.92-1.85 (m, 2H), 1.76-1.71 (m, 2H), 1.66-1.55 (brs, 10H). C NMR (100 MHz,
3
1
3
1
CDCl )  147.73, 132.41 (q, J = 32.3 Hz), 123.66 (q, J = 270.9 Hz), 112.05, 109.42 (t, J
3
+
=
3.9 Hz), 52.55, 33.65, 27.06, 25.78, 23.82. EIMS 339 (M ), HREIMS (C H F N)
1
6
19 6
cacld. 339.1417, found 339.1418.
1
H NMR (300 MHz, CDCl )  7.08 (s, 1H), 6.88 (s 2H), 3.88 (brs, 1H), 3.53-3.30 (m,
3
+
1
H), 1.64-1.20 (m, 10H), 0.96-0.86 (m, 6H). EIMS 339 (M ), HREIMS (C H F N)
16
19 6
+
cacld. 339.1417, found 339.1418. EIMS 341 (M ), HREIMS (C H F N) cacld.
1
6
21 6
3
41.1573, found 341.1575.
26

27

28

29