Synthesis of phenanthridines through iodine-supported intramolecular C-H amination and oxidation under visible light

Article abstract of DOI:10.1021/acs.joc.0c01390

Herein, we report a metal-free and step-economic synthesis of phenanthridines from 2-biarylmethanamines under mild conditions. The reaction involves iodine-supported intramolecular C-H amination and oxidation of 5,6-dihydrophenanthridine under air and benign visible light. The mechanism study reveals that visible light plays a key role in both these steps.

Full text of DOI:10.1021/acs.joc.0c01390

Subscriber access provided by CORNELL UNIVERSITY LIBRARY
Article
Synthesis of Phenanthridines through Iodine-Supported
Intramolecular C-H Amination and Oxidation under Visible Light
Yan Gao, Yi Jing, Lixin Li, Jie Zhang, Xuenian Chen, and Yan-Na Ma
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01390 • Publication Date (Web): 02 Sep 2020
Downloaded from pubs.acs.org on September 2, 2020
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 15
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
S y n th esi s of
P h en a n th ri di n es th rou g h
I odi n e- S u p p orted I n tra mol ec u l a r C - H
A mi n a ti on a n d O x i da ti on u n der V i s-
i b l e L i g h t
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Yan Gao,† Yi Jing,† Lixin Li,‡ Jie Zhang,† Xuenian Chen* and Yan-Na Ma*
† §
†
† School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced
Energy Materials, Henan Normal University, Xinxiang, Henan 453007, China.
‡ College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, Henan 464000,
China
§ College of Chemistry and Molecular Engineering, Zhengzhou
University, Zhengzhou, Henan 450001, China.
ABSTRACT: Herein, we report a metal-free and step-economic synthesis of phenanthridines from 2-biaryl-
methanamines under mild conditions. The reaction involves in an iodine-supported intramolecular C-H amina-
tion and oxidation of 5,6-dihydrophenanthridine under air and benign visible light. Mechanism study reveals
that visible light plays a key role in both of these two steps.
INTRODUCTION
(Scheme 1b, c),6,7 photolysis or oxidant-induced cy-
clization of oxime or imine via iminyl radical
(Scheme 1d).8 Although these methods were widely
studied, the substrate scope was relatively limited
due to the elaborated synthetic methods of starting
materials and similarly, only 6-substituted phenan-
thridine can be obtained. In 2017, Song and Xu’ s
group developed an electrochemical synthesis of
phenanthridine through anodic condensation of
biaryl aldehydes and NH3 under mild conditions
(Scheme 1e).9 In the same year, Alabugin’ s group
achieved the synthesis of 6-arylphenanthridines
through intramolecular C(sp3)-H amination using
tBuOK and molecular oxygen (Scheme 1f).10 But success
of this process requires an activated C(sp3)-H (BDE
< 85 kcal/mol). Apart from the above methods,
intermolecular annulation reactions were also
reported.11 For example, Pd-catalyzed cascade C-C
and C-N bond formation in a single step via Suzuki
Phenanthridine skeleton is an important N-het-
eroaryl core structural unit, which is present in
many molecules of natural alkaloids and biologi-
cally active pharmaceuticals.1 Represent compounds
include ethidium, which is an important DNA inter-
calator and stain,2 and alkaloids such as nitidine,
chelerythrine and sanguinarine.3 The most common
procedure for the preparation of phenanthridine
based on the cyclization of 2-amino biphenyl de-
rivatives by dehydrative ring-closure with phospho-
rus oxychloride (Scheme 1a).4 But this method can be
only used successfully into the synthesis of 6-sub-
stituted phenanthridines and is failed in the prep-
aration of phenanthridine itself. Recently, elegant
works have been developed by employing radical-me-
diated chemical or photochemical reactions, such as
tandem radical addition followed cyclization of 2-
isocyanobiphenyls and 2-(1-azidovinyl)biphenyls
coupling
bromobenzenealdehydes
and
condensation
between
and
ortho-
ortho-
ACS Paragon Plus Environment

The Journal of Organic Chemistry
aminobenzeneboronic acids;12 base-promoted aerobic
Page 2 of 15
product phenanthridine 2 was obtained in 75% yield.
1
2
3
4
5
6
7
8
oxidation/homolytic aromatic substitution cascade
reactions.13
Based on this result, different additives including
NaI, KI, NaBr, NH4I were examined but only moderate
yields were provided (Table 1, entries 2-5). Inves-
tigation of other oxidants indicated that
Intramolecular C-H amination was an important and
direct method for the synthesis of N-heterocycles.14
Recently, our group have paid attention to the
transition-metal-free intramolecular C-H amination
related tandem reactions and synthesized a series
of N-hetereocycles.15 So we wondered whether the
phenanthridines can be obtained with this method.
[ bis(trifluoroacetoxy)iodo] benzene
PhI(OTFA)2
could also promote this transformation to produce
phenanthridine in 65% yield (Table 1, entry 8). Next,
different solvents were explored and the best result
was obtained when CH3NO2 or 1,1,1,3,3,3-hexafluoro-
2-propanol (HFIP) was used (Table 1, entries 9-14).
Considering economic issue, CH3NO2 was selected as
the final solvent. What needs to be pointed out is
that: in the absence of iodine or light, the yields
decreased dramatically (Table 1, entries 15-16).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Through
transformation
our
endeavor,
with
we
achieved
this
2-
N-protected
biarylmethanamines as starting materials via
iodine-supported intramolecular C-H amination and
oxidant under visible light (Scheme 1g).16 Iodine
has been widely used as a catalyst in the
intramolecular C-H amination to synthesize N-
heterocycles as the broad substrate scope
accompanied with the fact that its use is not
hampered by the occurrence of residual metal
contamination.17 Among which, Muñiz’ s group has
made a great contribution.18 Compared with previous
methods for the synthesis of phenanthridines, this
procedure contains the following advantages: metal-
free, benign light induced reaction, step-economic
and conducted under air and room temperature.
With the optimized reaction conditions in hand,
we next explored the effects of N-substituents on
the efficiency of this reaction. N-Sulfonyl-con-
taining aryl, methyl and trifluoromethyl substrates
reacted well to provide the desired product in mod-
erate to good yields (Scheme 2, 1a-1i). N-Boc sub-
stituted substrate 1j could also be applied into
this reaction and gave the product in 33% yield.
However, N-acyl-protected substrates such as N-
([ 1,1'-biphenyl] -2-ylmethyl)benzamide 1k and N-
([ 1,1'-biphenyl] -2-ylmethyl)acetamide 1l were in-
effective and no product was detected. The N-phos-
phoryl substituted substrates were also explored
and the phenanthridine 2 was obtained in moderate
to good yields (Scheme 2, 1m-1n). While when N-
free [ 1,1'-biphenyl] -2-ylmethanamine 1o was used,
the methanamine group was oxidized to cyano group.
Scheme 1. Well-known methods for the synthesis of
phenanthridines
a,b
Table 1. Optimization of the reaction conditions
En-
try
Addi-
tives
Oxidant
Solvent
Yield(%)b
1
2
I2
NaI
KI
NaBr
NH4I
I2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
mCPBA
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF
75
44
3
35
4
38
5
62
6
10
7
I2
K2S2O8
n.r.
65
8
I2
PhI(OTFA)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
RESULTS AND DISCUSSION
9
I2
n.r.
60
10
11
12
13
14
I2
DCE
We started our investigation with N-([ 1,1'-bi-
phenyl] -2-ylmethyl)-4-methylbenzenesulfonamide 1a
as substrate, I2 as additive, PhI(OAc)2 as oxidant
in CH3CN under 10 w blue light at room temperature
(Table 1, entry 1). To our delight, the desired
I2
toluene
DMF
20
I2
n.r.
94
I2
CH3NO2
HFIP
I2
93
ACS Paragon Plus Environment

Page 3 of 15
1
The Journal of Organic Chemistry
15
16c
/
PhI(OAc)2
PhI(OAc)2
CH3NO2
CH3NO2
36
I2
trace
2
3
4
5
a
Reaction conditions: 1a (0.2 mmol), cat (20 mol%),
oxidant (0.4 mmol), solvent (2.0 mL), under air, rt,
10 w blue LED (400-410nm), 3 h. Isolated yields.
under dark.
b
c
6
7
8
Scheme 2. Scope of N-substituents a,b
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
a
Reaction conditions: 1 (0.3 mmol), I2 (20 mol%),
PhI(OAc)2 (0.6 mmol), CH3NO2 (2.5 mL), under air, rt,
10 w blue LED (400-410nm), 3 h. b Isolated yields.
To investigate the practicality of this transfor-
mation, a scaled-up reaction was carried out to pro-
vide product 2 in 87% yield. Next, different biaryl
derivatives were examined, which showed a good tol-
erance for a series of substituents (Scheme 3). For
example, 4’ -substituted arenes with different
electronic parameters were all suitable in this tan-
dem reaction (Scheme 3, 2-10). It is noted that if
the substituent was a strong eletronic-donating
group OMe, a mixture of 3-methoxyphenanthridine 8
and 2-iodo-3-methoxyphenanthridine 9 were obtained.
Under 5 mol% I2, product 8 was obtained in 70% yield.
While if the amount of I2 was increased 2.0 equiv-
alent, the iodinated compound 9 was separated in 53 %
yield. Only 25% yield was obtained when 2’ -methyl
substituted substrate was used which illustrates
that large steric hindrance group on 2’ position
has a negative effect on this reaction (Scheme 3,
11). 3’ -F substituted substrate gave a regioiso-
meric mixture of 12 and 13 (regioisomeric ratio 6:1).
While if the substituent was OMe, the pure product
14 with an excellent regioselectivity can be ob-
tained in 49% yield. This result may be attributed
to the larger steric hindrance of methoxy group than
fluorine atom. Polysubstituted arenes also under-
went this tandem reaction to give the corresponding
products in moderate to good yields (Scheme 3, 16-
19). Substrates with a hetereocycle such as pyridyl,
furyl, thienyl and indolyl were also explored, but
no products were detected. Next, different substit-
uents at different position on the other aryl were
examined and all the desired products were provided
in good yields (Scheme 3, 20-28). 6-Arylphenanthri-
dines 29-32 can be also obtained with this method in
moderate to good yields.
Scheme 3. Scope of biaryl derivativesa,b
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 15
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
a Reaction conditions: substrates (0.3 mmol), I2 (20 mol%), PhI(OAc)2 (0.6 mmol), CH3NO2 (2.5 mL), under air, rt,
10 w blue LED (400-410nm), 3 h. b Isolated yields. c 5 mol% I2 was used. d 2.0 equivalent I2 was used.
Encouraged by the above results, substrate 33 with
two reactive sites was subjected to this reaction
system and the corresponding product 3,3'-biphenan-
thridine 34 was obtained in 72% yield, which is a
potential bidentate nitrogen ligand in transition-
metal-catalyzed reactions (Scheme 4).
Scheme 4. Synthesis of 3,3'-biphenanthridine
We also tried to synthesize 6-alkylphenanthri-
dine, but only cyclic product was provided under
standard conditions. If the cyclic product 36 was
isolated and subjected into the standard conditions
ACS Paragon Plus Environment

Page 5 of 15
The Journal of Organic Chemistry
through a radical mechanism (Scheme 7F). Addition-
again, the corresponding product 6-methylphenan-
1
2
3
thridine 37 could be obtained in good yield. This
result should be caused by the steric hindrance and
eletronic-donating effect of methyl.
ally, 4-methylbenzenesulfonic acid was detected by
HRMS (see Figure S2 in the Supporting Information)
after the reaction was completed.
4
5
Scheme 5. Synthesis of 6-methylphenanthridine
Scheme 7. Control experiments
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
To study the reaction mechanism, some control ex-
periments were conducted (Scheme 6). When 3.0
equivalent amounts of free radical scavenger
(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) or
2,6-di-tert-butyl-4-methylphenol (BHT) was added
into the reaction system of 1a, no product was de-
tected. Additionally, (2-iodoethene-1,1-diyl)diben-
zene 38 was detected by HRMS (see Figure S1 in the
Supporting Information) if 1,1-diphenylethylene was
added into the reaction system, which indicated that
iodine radical maybe involved during the reaction.
Based on the above results and previous re-
ports,19,20 a plausible mechanism is proposed in
scheme 8 with 1a as the standard substrate. Ini-
tially, the reaction between PhI(OAc)2 and molecular
iodine generates the high reactive catalyst IOAc,
which promotes the formation of N-I intermediate A.
Photolytically assists homolysis of the N-I bond to
generate iodine radical and N-centered radical B.
As 36% yield of product 2 was obtained in the absence
of I2 (Table 1, entry 15). So, intermediate F should
be generated, which can also be transformed to B.15a
We tried to capture radical B with radical quench-
ers TEMPO, BHT and 1,1-diphenylethylene, but
failed.19c This electrophilic nitrogen radical B is
trapped by arene to produce a delocalized cyclohex-
adienyl radical C. Then radical intermediate C is
oxidized by PhI(OAc)2 to the cationic intermediate
D and regenerates IOAc catalyst. Re-aromatization
of D by final proton loss forms the C-N coupling
product 39. Hydrolysis of 39 produces 5,6-dihydro-
phenanthridine 40. Then single-electron transfer
occurs between O2 and 5,6-dihydrophenanthridine under
blue light to form intermediate E and superoxide
radical anion.20 Finally, intermediate E is oxidized
to phenanthridine 2.
Scheme 6. Control experiments
Tosyl-5,6-dihydrophenanthridine 39 was detected
after the reaction was stirred for 1 hour. So, we
think 39 should be a reaction intermediate. To con-
firm this speculation, 39 was subjected to the
standard conditions and the desired product phenan-
thridine was obtained in 94% yield, which indicated
that 39 was initially formed (Scheme 7A). To get
insight into the mechanism from 39 to phenanthridine,
some control experiments were conducted, which re-
vealed that catalyst iodine and oxidant PhI(OAc)2
were all not necessary for the transformation from
N-tosyl-5,6-dihydrophenanthridine 39 to phenanthri-
dine 2 (Scheme 7B,C). But almost no product was
obtained in the absence of light or oxygen (Scheme
7D,E). When free radical scavenger (2,2,6,6-tetra-
methylpiperidin-1-yl)oxyl (TEMPO) or 2,6-di-tert-
butyl-4-methylphenol (BHT) was added into the reac-
tion system, the reaction was inhibited completely,
which indicated that this transformation went
Scheme 8. Study of mechanism
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 15
(oil bath) for 24 hours. After the reaction was com-
1
2
3
4
5
6
pleted, water was added and the organic layer was sep-
arated. The aq. layer was extracted with dichloro-
methane. The combined organic layers were dried over
Na2SO4. The crude reaction mixture was purified by flash
chromatography on silica gel plug to give the coupling
product.
7
8
9
Tosyl chloride was slowly added to the reaction
mixture of coupling product 2-phenylbenzylamine (1.0
eq) and Et3N (2.0 eq) in DCM (25 mL) at 0 oC. Then the
reaction system was warmed to room temperature and
stirred for 2 hours. After consumption of starting ma-
terial, 2M HCl aq. (30 mL) was added and the organic
layer was separated. The aq. layer was extracted with
dichloromethane (30 mL x 2). The combined organic lay-
ers were dried over Na2SO4, filtered, and concentrated
in vacuo. The crude reaction mixture was purified by
flash chromatography on silica gel to give the pure
product.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
General procedure for the tandem reaction. The mix-
ture of N-Ts-2-phenylbenzylamine (0.3 mmol, 1.0 equiv),
I2 (20 mol%), PhI(OAc)2 (0.6 mmol, 2.0 equiv) in CH3NO2
(2.5 mL) was stirred under 10 w blue light at room
temperature for 3 hours. The resulting solution was
concentrated under vacuo. The residue was purified by
column chromatography on silica gel to give the desired
pure product.
CONCLUSIONS
In summary, we have developed a metal-free direct synthesis of
phenanthridines
from
N-protected-2-biarylmethanamine
Gram-scale experimental for the synthesis of 2. To
a stirred solution of 1a (5 mmol, 1.0 equivalent) in
CH3NO2 (25 mL) was added I2 (254 mg, 20 mol%), PhI(OAc)2
(3.22 g, 10 mmol, 2.0 equivalent). Then the reaction
mixture was stirred under 10 w blue light at room tem-
perature for 5 hours. The resulting solution was con-
centrated under vacuo. The residue was purified by
column chromatography on silica gel to give the desired
pure product 2 in 87% yield (0.78g).
through one-pot iodine supported intramolecular C-H amination,
followed oxidation of the cyclic intermediate by molecular ox-
ygen under blue light. Through this method, a series of phenan-
thridines containing different functional groups were obtained
in good yields. Meanwhile, this process opens a new and quick
access to the synthesis of phenanthridine and its derivatives.
E X P E R I ME NT A L S E C T I O N
General. 1H, 13C, 19F NMR spectra were recorded on a Bruker
advance Ⅲ400 spectrometer (400 MHz for 1H, 100 MHz for
General procedure for the synthesis of 3,3'-biphenan-
thridine 30. The mixture of substrate 29 (0.2 mmol,
1.0 equiv), I2 (40 mol%), PhI(OAc)2 (0.8 mmol, 4.0 equiv)
in CH3NO2 (3.0 mL) was stirred under 10 w blue light at
room temperature for 6 hours. The resulting solution
was concentrated under vacuo. The residue was purified
by column chromatography to give the desired product
30 in 72% yield (51.3 mg).
13C, and 376 MHz for F) and Ⅲ600 spectrometer (600
19
MHz for 1H, 151 MHz for 13C) in CDCl3, DMSO-d6. Chemical
shifts (δ) were measured in ppm relative to TMS δ =
1
13
0 for H and to chloroform δ = 77.0 for C as the
internal standard, to CFCl3 δ = 0 for 19F, as external
standard. Data are reported as follows: Chemical shift,
multiplicity (s = singlet, d = doublet, t = triplet, q
= quartet, m = multiplet), Coupling constants, J, are
reported in hertz. The starting materials and solvents
were purchased from Aldrich, Acros Organics, J&K Chem-
icals, Energy Chemical, Aladdin, Macklin or TCI and
used without further purification. Thin-layer chroma-
tography (TLC) was performed using 60 mesh silica gel
plates visualized with short-wavelength UV light (254
nm).
Characterization Data of substates.
N-([1,1'-biphenyl]-2-ylmethyl)-4-methylbenzenesulfonamide (1a):
eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.55 g, 92%; 1H NMR
(600 MHz, CDCl3) δ: 7.55 (d, J = 8.2 Hz, 2H), 7.38-7.35 (m, 1H),
7.33 (dd, J = 6.1, 3.6 Hz, 3H), 7.30 (ddd, J = 10.0, 5.8, 3.7 Hz, 2H),
7.23-7.15 (m, 5H), 4.47 (t, J = 5.9 Hz, 1H), 4.10 (d, J = 6.1 Hz,
2H), 2.41 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.2,
141.7, 140.1, 136.6, 133.4, 130.2, 129.5, 129.4, 128.8, 128.4, 127.9,
127.8, 127.3, 127.0, 45.1, 21.4; HRMS (ESI-TOF) m/z: [M + H]+
calcd for C20H20NSO2 338.1209; found 338.1201.
Preparation of substrates. An oven-dried one-neck
flask was charged with 2-bromobenzylamine (5 mmol, 1.0
equiv), PhB(OH)2 (7.5 mmol, 1.5 equiv), S-Phos (4.8
mol%), Pd2dba3 (2 mol%), and K3PO4 (15 mmol, 3.0 equiv)
in glovebox, then 25 mL of DME/H2O (4:1) were injected
into the flask, and the reaction was stirred at 80 °C
N-([1,1'-biphenyl]-2-ylmethyl)benzenesulfonamide (1b): eluent:
1
PE/EtOAc = 6:1; yellow solid; yield: 1.45 g, 90%; H NMR (600
ACS Paragon Plus Environment

Page 7 of 15
The Journal of Organic Chemistry
MHz, CDCl3) δ: 7.66 (d, J = 8.2 Hz, 2H), 7.51 (t, J = 7.3 Hz, 1H),
13C{1H} NMR (151 MHz, CDCl3) δ: 142.0, 139.8, 132.5, 130.5,
1
2
3
4
5
6
7
8
7.40 (t, J = 7.7 Hz, 2H), 7.35 (d, J = 7.0 Hz, 1H), 7.33-7.30 (m,
3H), 7.30-7.25 (m, 2H), 7.18-7.12 (m, 3H), 4.62 (d, J = 43.2 Hz,
1H), 4.12 (s, 2H); 13C{1H} NMR (151MHz, CDCl3) δ: 141.7,
140.1, 139.6, 133.3, 132.4, 130.2, 129.4, 128.9, 128.7, 128.4, 128.0,
127.8, 127.4, 126.9,45.1; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C19H18NSO2 324.1053; found 324.1050.
129.0, 128.8,128.7,128.6, 128.1 , 127.8 , 119.5,(q, J = 321.6 Hz)
118.41, 46.1;19F{1H} NMR (565 MHz, CDCl3): -77.22; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C14H13F3NSO2 338.0433;
found 338.0427.
tert-butyl ([1,1'-biphenyl]-2-ylmethyl)carbamate
(1j): eluent:
1
PE/EtOAc = 7:1; white solid; yield: 835 mg, 59%; H NMR (600
MHz, CDCl3) δ: 7.44 (d, J = 7.3 Hz, 1H), 7.40 (t, J = 7.4 Hz, 3H),
7.34 (dd, J = 11.9, 4.3 Hz, 3H), 7.33-7.27 (m, 4H), 7.23 (dd, J =
7.5, 1.1 Hz, 1H), 4.65 (s, 1H), 4.27 (d, J = 5.3 Hz, 2H), 1.41 (d, J
= 15.1 Hz, 9H); 13C{1H} NMR (151 MHz, CDCl3) δ: 155.7, 142.3,
141.5, 140.7, 139.6, 129.1, 129.0, 128.6, 128.3, 128.1, 127.7, 127.2,
127.1, 45.8, 42.4, 28.3; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C18H22NO2 284.1645; found 284.1638.
N-([1,1'-biphenyl]-2-ylmethyl)-4-(trifluoromethyl)benzenesulfona-
mide (1d): eluent: PE/EtOAc= 6:1; white solid; yield: 1.68 g, 86%;
1H NMR (600 MHz, CDCl3) δ: 7.72 (d, J = 8.2 Hz, 2H), 7.63 (d, J
= 8.3 Hz, 2H), 7.34-7.24 (m, 6H), 7.15 (dd, J = 7.3, 1.2 Hz, 1H),
7.11 (dd, J = 7.4, 1.9 Hz, 2H), 4.67 (t, J = 5.8 Hz, 1H), 4.15 (d, J
= 5.9 Hz, 2H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.1 , 141.8,
139.9 , 134.1 (q, J = 33.2 Hz), 132.7, 130.3 , 129.6, 128.6, 128.5,
128.2 , 127.8 , 127.5, 127.4, 126.0 (q, J = 4.5 Hz), 123.2 (q, J =
273.3 Hz), 45.3; 19F{1H} NMR (565 MHz, CDCl3): -63.12; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C20H17F3NSO2 392.0927;
found 392.0924.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-([1,1'-biphenyl]-2-ylmethyl)benzamide (1k): eluent: PE/EtOAc=
7:1; yellow solid; yield: 1.03 g, 72%; 1H NMR (600 MHz, CDCl3)
δ: 7.62 (d, J = 7.5 Hz, 2H), 7.49-7.46 (m, 1H), 7.43 (dd, J = 14.7,
7.5 Hz, 3H), 7.38-7.33 (m, 7H), 7.29-7.27 (m, 1H), 6.26 (s, 1H),
4.61 (d, J = 5.6 Hz, 2H); 13C{1H} NMR (151 MHz, CDCl3) δ:
167.0, 141.7, 140.7, 135.4, 134.3, 131.4, 130.2, 128.9, 128.8, 128.5,
128.4, 127.8, 127.5, 127.4, 126.8, 45.8; HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C20H18NO 288.1383; found 288.1376.
N-([1,1'-biphenyl]-2-ylmethyl)-4-nitrobenzenesulfonamide (1e):
eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.64 g, 89%; 1H NMR
(400 MHz, CDCl3) δ: 8.20 (d, J = 8.7 Hz, 2H), 7.75 (d, J = 8.7 Hz,
2H), 7.36-7.28 (m, 6H), 7.18-7.14 (m, 1H), 7.11 (dd, J = 6.2, 2.8
Hz, 2H), 4.50 (t, J = 5.6 Hz, 1H), 4.22 (d, J = 5.9 Hz, 2H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 149.8, 145.5, 141.8, 139.9, 132.6,
130.5, 129.6, 128.6, 128.5, 128.1, 127.9, 127.6, 124.1, 45.4; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C19H17N2SO4 369.0904; found
369.0903.
N-([1,1'-biphenyl]-2-ylmethyl)acetamide (1l): eluent: PE/EtOAc =
1
7:1; yellow solid; yield：765 mg，68%; H NMR (600 MHz,
CDCl3) δ: 7.43-7.38 (m, 3H), 7.37-7.34 (m, 1H), 7.34-7.30 (m, 2H),
7.30-7.27 (m, 2H), 7.26-7.23 (m, 1H), 5.73 (s, 1H), 4.37 (d, J = 5.6
Hz, 2H), 1.87 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 169.7,
141.6, 140.6, 135.4, 130.1, 128.9, 128.7, 128.3, 127.7, 127.4, 127.2,
41.5, 23.0; HRMS (ESI-TOF) m/z: [M + H]+ calcd for C15H16NO
226.1226; found 226.1225.
N-([1,1'-biphenyl]-2-ylmethyl)-4-chlorobenzenesulfonamide (1f):
eluent: PE/EtOAc = 6:1; white solid; yield: 1.64 g, 92%; 1H NMR
(600 MHz, CDCl3) δ: 7.53 (d, J = 8.6 Hz, 2H), 7.34-7.26 (m, 8H),
7.16 (dd, J = 7.2, 1.3 Hz, 1H), 7.12 (dd, J = 7.5, 1.6 Hz, 2H), 4.73
(t, J = 5.8 Hz, 1H), 4.09 (d, J = 6.0 Hz, 2H); 13C{1H} NMR (151
MHz, CDCl3) δ: 141.7, 140.0, 138.8, 138.0, 133.0, 130.2, 129.4,
129.1, 128.7, 128.4, 128.3, 128.0, 127.8, 127.4, 45.1; HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C19H17ClNSO2 358.0663; found
358.0656.
N-([1,1'-biphenyl]-2-ylmethyl)-P,P-diphenylphosphini-
camide(1m): eluent: PE/EtOAc = 7:1; yellow solid; yield:1.72 g,
1
90%; H NMR (600 MHz, CDCl3) δ: 7.75 (dd, J = 11.8, 7.7 Hz,
4H), 7.56 (d, J = 7.6 Hz, 1H), 7.43 (t, J = 7.4 Hz, 2H), 7.39-7.32
(m, 8H), 7.30 (t, J = 7.3 Hz, 1H), 7.21 (dd, J = 10.9, 4.2 Hz, 3H),
4.09 (s, 2H), 3.03 (d, J = 17.1 Hz, 1H); 13C{1H} NMR (151 MHz,
CDCl3) δ: 141.5, 140.6, 136.7 (d, J = 9.1 Hz), 132.4, 131.9 (d, J =
10.6 Hz),131.7 (d, J = 1.5 Hz), 131.6, 130.1, 128.9, 128.8, 128.4,
128.3 (d, J = 9.1 Hz), 127.7, 127.2, 127.1, 42.1; 31P{1H} NMR (243
MHz, CDCl3): 23.60; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C25H23NOP 384.1512; found 384.1507.
N-([1,1'-biphenyl]-2-ylmethyl)-4-bromobenzenesulfonamide (1g):
1
eluent: PE/EtOAc = 6:1; white solid; yield: 1.8 g, 90%; H NMR
(600 MHz, CDCl3) δ: 7.52-7.48 (m, 2H), 7.46 (d, J = 8.6 Hz, 2H),
7.36-7.26 (m, 6H), 7.18-7.15 (m, 1H), 7.14-7.09 (m, 2H), 4.59 (t, J
= 5.8 Hz, 1H), 4.11 (t, J = 8.3 Hz, 2H); 13C{1H} NMR (151 MHz,
CDCl3) δ: 141.7, 140.0, 138.6, 135.6, 132.1, 130.3, 129.5, 128.7,
128.5, 128.1, 127.9, 127.8, 127.4, 127.4, 45.1; HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C19H17BrNSO2 402.0158; found 402.0160.
N-([1,1'-biphenyl]-2-ylmethyl)-P,P-bis(2-oxooxazolidin-3-
yl)phosphinic amide
(1n): eluent: PE/EtOAc= 7:1; white solid;
1
yield: 1.58 g, 79%; H NMR (600 MHz, CDCl3) δ: 7.54-7.51 (m,
1H), 7.43 (t, J = 7.4 Hz, 2H), 7.38 (t, J = 4.9 Hz, 1H), 7.37-7.33
(m, 2H), 7.33-7.31 (m, 2H), 7.27-7.23 (m, 1H), 4.37 (td, J = 8.8,
6.6 Hz, 2H), 4.31-4.23 (m, 4H), 4.19 (dd, J = 16.1, 7.1 Hz, 1H),
3.93 (qd, J = 8.8, 1.1 Hz, 2H), 3.76 (td, J = 9.1, 6.5 Hz, 2H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 156.3 (d, J = 9.7 Hz), 141.6 , 140.4,
135.9 (d, J = 6.6 Hz), 130.4 , 129.0 , 128.5, 128.4, 127.7, 127.6 ,
127.3, 63.8 (d, J = 8.7 Hz), 44.2 (d, J = 3.6 Hz), 42.0; 31P{1H}
NMR (243 MHz, CDCl3): 0.07 ; HRMS (ESI-TOF) m/z: [M + H]+
calcd for C19H21N3O5P 402.1213; found 402.1210.
N-([1,1'-biphenyl]-2-ylmethyl)methanesulfonamide (1h): eluent:
1
PE/EtOAc = 7:1; white solid; yield: 809 mg, 62%; H NMR (600
MHz, CDCl3) δ: 7.48 (s, 1H), 7.41 (d, J = 6.8 Hz, 2H), 7.38-7.27
(m, 6H), 7.24 (s, 1H), 4.75 (s, 1H), 4.23 (d, J = 2.6 Hz, 2H), 2.60
(s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 141.7, 140.2, 133.7,
130.3, 129.1, 128.8, 128.5, 127.9, 127.8, 127.4, 44.9, 40.0; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C14H16NSO2 262.0896; found
262.0894.
N-([1,1'-biphenyl]-2-ylmethyl)-1,1,1-trifluoromethanesulfonamide
1
(1i): eluent: PE/EtOAc = 7:1; yellow solid; yield: 1.36 g, 81%; H
4-methyl-N-((4'-methyl-[1,1'-biphenyl]-2-yl) methyl)benzenesul-
fonamide (3’): eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.60 g,
91%; 1H NMR (600 MHz, CDCl3) δ: 7.55 (d, J = 8.0 Hz, 2H), 7.32
NMR (600 MHz, CDCl3) δ:7.45 (ddd, J = 9.2, 5.4, 1.5 Hz, 4H),
7.42-7.37 (m, 4H), 7.30 – 7.25 (m, 4H), 4.89 (s, 1H), 4.40 (s, 3H);
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 15
(d, J = 7.2 Hz, 1H), 7.29-7.23 (m, 2H), 7.19 (d, J = 8.0 Hz, 2H),
158.8, 143.2, 141.4, 136.5, 133.5, 132.4, 130.3, 129.8, 129.5, 129.4,
1
2
3
4
5
6
7
8
7.16 (d, J = 7.3 Hz, 1H), 7.12 (d, J = 7.7 Hz, 2H), 7.04 (d, J = 7.8
Hz, 2H), 4.61-4.43 (m, 1H), 4.09 (d, J = 6.0 Hz, 2H), 2.39 (d, J =
15.8 Hz, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.1, 141.7,
137.1, 137.0, 136.6, 133.4, 130.3, 129.4, 129.1, 128.6, 127.9, 127.6,
127.0, 45.2, 21.5, 21.1; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H22NSO2 352.1366; found 352.1354.
127.9, 127.5, 127.0, 113.8, 55.2, 45.2, 21.4; HRMS (ESI-TOF)
m/z: [M + Na]+ calcd for C21H21NSO3Na 390.1134; found
390.1126.
N-([1,1':4',1''-terphenyl]-2-ylmethyl)-4-methylbenzenesulfonamide
1
(10’): eluent: PE/EtOAc = 6:1; white solid; yield: 1.84 g, 89%; H
NMR (600 MHz, CDCl3) δ: 7.62 (s, 2H), 7.59-7.44 (m, 6H), 7.35
(d, J = 40.4 Hz, 5H), 7.19 (d, J = 43.8 Hz, 5H), 4.47 (s, 1H), 4.14
(s, 2H), 2.29 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.3,
141.4, 140.4, 140.1, 139.0, 136.5, 133.4, 130.3, 129.7, 129.5, 129.2,
128.9, 128.1, 127.9, 127.5, 127.1, 127.0, 45.2, 21.3; HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C26H24NSO2 414.1522; found
414.1511.
N-((4'-isopropyl-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesul-
fonamide (4’): eluent: PE/EtOAc = 6:1; white solid; yield: 1.52 g,
80%; 1H NMR (600 MHz, CDCl3) δ: 7.60-7.56 (m, 2H), 7.32 (d, J
= 7.2 Hz, 1H), 7.26 (dd, J = 13.5, 5.9 Hz, 2H), 7.21 (d, J = 8.1 Hz,
2H), 7.17 (d, J = 7.6 Hz, 3H), 7.10-7.06 (m, 2H), 4.55 (s, 1H), 4.10
(d, J = 6.1 Hz, 2H), 2.93 (dt, J = 13.8, 6.9 Hz, 1H), 2.40 (s, 3H),
1.28 (t, J = 10.0 Hz, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ:
147.9, 143.2, 141.7, 137.5, 136.7, 133.5, 130.3, 129.5, 129.4, 128.7,
127.9, 127.6, 127.1, 126.5, 45.2, 33.8, 23.9, 21.5; HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C23H26NSO2 380.1679; found
380.1673.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
4-methyl-N-((2'-methyl-[1,1'-biphenyl]-2-yl)methyl)benzenesul-
fonamide (11’): eluent: PE/EtOAc= 6:1; white solid; yield: 1.44 g,
82%; 1H NMR (600 MHz, CDCl3) δ: 8.15 (d, J = 2.4 Hz, 1 H), 8.04
(dd, J = 5.0 Hz, J = 8.2 Hz, 1 H), 7.80 (dd, J = 7.6 Hz, J = 13.2 Hz,
1 H), 7.72-7.64 (m, 3 H), 7.50-7.45 (m, 2 H), 7.40-7.35 (m, 2 H),
7.30-7.15 (m, 6 H), 6.87 (d, J = 8.8 Hz, 1 H), 5.17 (dd, J = 6.4 Hz,
J = 16.8 Hz, 1 H), 4.67 (dd, J = 7.2 Hz, J = 16.8 Hz, 1 H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 143.2, 141.0, 139.5, 136.5, 135.5,
133.9, 130.1, 129.8, 129.1, 129.0, 127.8, 127.7, 127.7, 126.9, 125.7,
45.0, 21.5, 19.8; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H22NSO2 352.1366; found 352.1356.
N-((4'-fluoro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesulfon-
amide (5’): eluent: PE/EtOAc= 6:1; yellow solid; yield:1.60 g, 90%;
1H NMR (600 MHz, CDCl3) δ: 7.56 (d, J = 8.1 Hz, 2H), 7.38- 7.34
(m, 1H), 7.30-7.24 (m, 2H), 7.20 (d, J = 8.1 Hz, 2H), 7.15- 7.09 (m,
3H), 6.95 (t, J = 8.6 Hz, 2H), 4.85 (d, J = 31.9 Hz, 1H), 4.00 (s,
2H), 2.41 (s, 4H); 13C{1H} NMR (151 MHz, CDCl3) δ: 162.0 (d, J
= 246.1 Hz), 143.3 , 140.7, 136.3 , 136.0 , 133.4 , 130.5 , 130.4(d,
J = 7.6 Hz), 130.2, 129.5 (d, J = 3.0 Hz), 127.9, 126.9, 115.2, 115.0,
44.8, 21.4; 19F{1H} NMR (376 MHz, CDCl3): -114.87; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C20H19FNSO2 356.1115; found
356.1107.
N-((3'-fluoro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesulfon-
amide (12’): eluent: PE/EtOAc= 6:1; white solid; yield: 1.53 g, 86%;
1H NMR (400 MHz, CDCl3) δ: 7.57 (d, J = 8.2 Hz, 2H), 7.41- 7.35
(m, 1H), 7.35-7.28 (m, 3H), 7.27 (d, J = 6.8 Hz, 2H), 7.22 (d, J =
8.1 Hz, 2H), 7.19-7.14 (m, 1H), 7.01 (t, J = 7.5 Hz, 1H), 6.95 (d, J
= 7.6 Hz, 1H), 6.84 (d, J = 9.5 Hz, 1H), 4.50-4.35 (m, 1H), 4.09
(dd, J = 19.5, 5.9 Hz, 2H), 2.43 (d, J = 7.7 Hz, 4H); 19F{1H} NMR
(376 MHz, CDCl3) δ: -112.48; 13C{1H} NMR (151 MHz, CDCl3)
δ: 162.5 (d, J = 247.6 Hz), 143.4, 142.3 (d, J = 7.4 Hz), 140.5 ,
133.3, 130.1, 129.9 (d, J = 8.6 Hz), 129.7 , 129.6 (d, J = 8.8 Hz),
128.3, 128.1, 127.0 , 124.6 (d, J = 2.3 Hz), 116.0, 115.8 , 114.3 (d,
J = 21Hz), 45.0, 21.5; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C20H19FNSO2 356.1115; found 356.1110.
N-((4'-chloro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesulfon-
amide (6’): eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.41 g,76%;
1H NMR (600 MHz, CDCl3) δ: 7.58-7.52 (m, 2H), 7.39-7.35 (m,
1H), 7.28 (dd, J = 5.5, 3.6 Hz, 2H), 7.22 (dd, J = 7.9, 3.6 Hz, 4H),
7.13 (dd, J = 8.1, 4.5 Hz, 1H), 7.07 (d, J = 8.2 Hz, 2H), 4.79 (s,
1H), 4.00 (s, 2H), 2.42 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3)
δ: 143.4, 140.5, 138.4, 136.2, 133.3, 133.2, 130.1, 130.0, 129.7,
129.6, 129.5, 128.4, 128.1, 128.1, 128.0, 127.0, 44.8, 21.5; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C20H19ClNSO2 372.0820;
found 372.0814.
N-((3'-methoxy-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesul-
fonamide (14’): eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.45 g,
81%; 1H NMR (400 MHz, CDCl3) δ: 7.54 (d, J = 8.0 Hz, 2H), 7.33
(dd, J = 9.7, 6.3 Hz, 1H), 7.31-7.22 (m, 3H), 7.18 (dd, J = 11.6, 4.9
Hz, 3H), 6.87 (dd, J = 8.3, 2.2 Hz, 1H), 6.76-6.68 (m, 2H), 4.59-
4.40 (m, 1H), 4.09 (d, J = 6.1 Hz, 2H), 3.77 (s, 3H), 2.40 (s, 3H);
13C{1H} NMR (151 MHz, CDCl3) δ: 159.5, 143.2, 141.6, 141.5,
136.5, 133.4, 130.1, 129.5, 129.5, 128.0, 127.9, 127.0, 121.1, 114.2,
113.2, 55.2, 45.2, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ calcd
for C21H21NSO3Na 390.1134; found 390.1130.
4-methyl-N-((4'-(trifluoromethyl)-[1,1'-biphenyl]-2-yl)methyl)ben-
zenesulfonamide (7’): eluent: PE/EtOAc = 6:1; white solid; yield:
1.80 g, 84%; 1H NMR (400 MHz, CDCl3) δ: 7.56 (dd, J = 16.6, 8.1
Hz, 4H), 7.42 (dd, J = 8.9, 3.3 Hz, 1H), 7.40-7.32 (m, 2H), 7.30-
7.25 (m, 3H), 7.23 (d, J = 8.0 Hz, 2H), 7.19 (dt, J = 3.6, 2.9 Hz,
1H), 4.38 (t, J = 5.7 Hz, 1H), 4.03 (d, J = 5.9 Hz, 2H), 2.42 (s, 3H);
19F{1H} NMR (376 MHz, CDCl3) δ: -62.48; 13C{1H} NMR (151
MHz, CDCl3) δ: 143.8 , 143.6 , 140.4 , 136.3, 133.2 , 130.0, 129.8 ,
129.6 ,129.4(d, J = 33.2 Hz), 129.3, 128.5, 128.1, 127.0 , 124.1 (q,
J = 271.8 Hz), 44.7 , 21.3; HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C21H18F3NSO2Na 428.0903; found 428.0894.
N-((3',4'-difluoro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzene-
sulfonamide (16’): eluent: PE/EtOAc= 6:1; white solid; yield: 1.57
1
g, 84%; H NMR (400 MHz, CDCl3) δ: 7.57 (d, J = 8.2 Hz, 2H),
N-((4'-methoxy-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesul-
7.40- 7.36 (m, 1H), 7.36-7.29 (m, 2H), 7.28-7.21 (m, 3H), 7.17-
7.12 (m, 1H), 7.07 (dd, J = 18.5, 8.3 Hz, 1H), 6.98-6.91 (m, 1H),
6.91- 6.85 (m, 1H), 4.43 (t, J = 5.6 Hz, 1H), 4.02 (d, J = 5.9 Hz,
2H), 2.44 (s, 3H); 19F{1H} NMR (376 MHz, CDCl3): -137.03 (d,
J = 22.56 Hz), -139.35 (d, J = 22.56 Hz); 13C{1H} NMR (151
MHz, CDCl3) δ: 150.8-150.4 (m), 149.1-148.8 (m), 143.6, 139.7,
137.1-136.7 (m), 136.1, 133.2, 130.1 , 129.7, 129.5, 128.4, 128.1,
fonamide (8’): eluent: PE/EtOAc = 6:1; white solid; yield: 1.75
1
g ,90%; H NMR (600 MHz, CDCl3) δ: 7.55 (d, J = 8.2 Hz, 2H),
7.32 (dd, J = 7.3, 1.4 Hz, 1H), 7.29-7.22 (m, 2H), 7.19 (d, J = 8.1
Hz, 2H), 7.15 (dd, J = 7.2, 1.5 Hz, 1H), 7.09-7.05 (m, 2H), 6.85 –
6.81 (m, 2H), 4.58 (t, J = 5.9 Hz, 1H), 4.08 (d, J = 6.0 Hz, 2H),
3.83 (s, 3H), 2.40 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ:
ACS Paragon Plus Environment

Page 9 of 15
The Journal of Organic Chemistry
127.0 , 125.2 - 124.9 (m), 44.7, 21.4; HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C20H18F2NSO2 374.1021; found 374.1013.
44.5, 21.35; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C21H18F3NSO2Na 428.0903; found 428.0894.
1
2
3
4
5
6
7
8
9
N-((2',3'-dimethyl-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzene-
N-([1,1':4',1''-terphenyl]-2'-ylmethyl)-4-methylbenzenesulfona-
mide (23’): eluent: PE/EtOAc= 8:1; white solid; yield: 1.20 g, 61%;
1H NMR (400 MHz, CDCl3) δ: 7.60-7.50 (m, 5H), 7.50-7.42 (m,
3H), 7.40-7.33 (m, 4H), 7.27-7.24 (m, 2H), 7.23-7.16 (m, 4H), 4.45
(t, J = 6.0 Hz, 1H), 4.20 (d, J = 6.1 Hz, 2H), 2.37 (s, 3H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 143.3, 140.6, 140.6, 140.1, 139.8,
136.8, 133.9, 130.8, 129.6, 128.8, 128.5, 128.1, 127.6, 127.5, 127.0,
127.0, 126.5, 45.3, 21.5; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C26H24NSO2 414.1522; found 414.1510.
sulfonamide (18’): eluent: PE/EtOAc= 6:1; yellow solid; yield: 1.13
1
g, 62%; H NMR (400 MHz, CDCl3) δ:7.49 (d, J = 7.6 Hz, 2H),
7.40 – 7.23 (m, 4H), 7.23-7.00 (m, 5H), 6.82 (d, J = 6.9 Hz, 1H),
4.26 (s, 1H), 3.85 (ddd, J = 17.9, 13.2, 5.9 Hz, 2H), 2.41 (s, 3H),
2.25 (s, 3H), 1.83 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ:
143.1, 141.8, 139.6, 137.3, 136.4, 134.0, 133.9, 130.0, 129.5, 129.2,
129.0, 127.9, 127.6, 126.9, 126.9, 125.4, 45.3, 21.5, 20.5, 16.5;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C22H24NSO2 366.1522;
found 366.1518.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
4-methyl-N-((6-methyl-[1,1'-biphenyl]-2-yl)methyl)benzenesulfon-
amide (24’): eluent: PE/EtOAc = 7:1; yellow solid; yield: 1.43 g,
82%; 1H NMR (600 MHz, CDCl3) δ: 7.49 (d, J = 8.1 Hz, 2H), 7.36-
7.29 (m, 3H), 7.18 (dd, J = 10.3, 5.0 Hz, 5H), 7.03-6.99 (m, 2H),
4.36 (d, J = 21.6 Hz, 1H), 3.83 (d, J = 5.6 Hz, 2H), 2.40 (s, 3H),
1.97 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.1 , 141.3 ,
139.0 , 136.7, 136.5, 134.0, 129.5 , 129.5, 128.7, 128.7, 127.6,
127.2 , 127.0 , 126.6, 45.6 , 21.5, 20.6; HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C21H22NSO2 352.1366; found 352.1359.
4-methyl-N-((3',4',5'-trifluoro-[1,1'-biphenyl]-2-yl)methyl)ben-
zenesulfonamide (19’): eluent: PE/EtOAc = 6:1; white solid; yield:
1
1.15 g, 59%; H NMR (400 MHz, CDCl3) δ: 7.58 (d, J = 8.0 Hz,
2H), 7.39 (d, J = 6.8 Hz, 1H), 7.36-7.28 (m, 2H), 7.24 (d, J = 8.1
Hz, 2H), 7.11 (d, J = 6.6 Hz, 1H), 6.77 (t, J = 7.1 Hz, 2H), 4.74 (t,
J = 5.2 Hz, 1H), 4.00 (d, J = 5.8 Hz, 2H), 2.43 (s, 3H); 19F{1H}
NMR (376 MHz, CDCl3) δ: -133.83 (d, J = 20.5 Hz), -161.85 (s),
-161.93 (d, J = 20.5 Hz); 13C{1H} NMR (151 MHz, CDCl3) δ:
151.5 , 149.8 (d, J = 9.8 Hz), 143.7 , 139.9 , 138.9 , 138.3 , 136.0 ,
133.1 , 129.9 (d, J = 4.5 Hz), 129.5 , 128.7 , 128.2 , 126.9 , 113.2
(dd, J = 16.5, 4.4 Hz), 44.6 , 21.4; HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C16H17F3NSO2 392.0927; found 392.0924.
4-methyl-N-((5-methyl-[1,1'-biphenyl]-2-yl)methyl)benzenesulfon-
amide (25’): eluent: PE/EtOAc = 7:1; yellow solid; yield: 1.42 g,
81%; 1H NMR (600 MHz, CDCl3) δ: 7.54 (d, J = 8.1 Hz, 2H), 7.34-
7.29 (m, 3H), 7.21 (dd, J = 11.5, 8.0 Hz, 3H), 7.15 (dt, J = 7.4, 3.8
Hz, 2H), 7.10 (d, J = 7.8 Hz, 1H), 7.00 (s, 1H), 4.37 (s, 1H), 4.04
(s, 2H), 2.41 (s, 3H), 2.33 (s, 3H); 13C{1H} NMR (151 MHz,
CDCl3) δ: 143.2, 141.6, 140.3, 137.8, 136.6, 131.0, 130.4, 129.5,
128.7, 128.5, 128.4, 127.2, 127.0, 44.9, 21.5, 21.0; HRMS (ESI-
TOF) m/z: [M + Na]+ calcd for C21H21NSO2Na 374.1182; found
374.1185.
4-methyl-N-((4-methyl-[1,1'-biphenyl]-2-yl)methyl)benzenesulfon-
amide (20’): eluent: PE/EtOAc= 6:1; white solid; yield: 1.51 g, 86%;
1H NMR (600 MHz, CDCl3) δ: 7.58-7.53 (m, 2H), 7.32 - 7.28 (m,
3H), 7.19 (d, J = 8.1 Hz, 2H), 7.14 (dd, J = 5.3, 2.2 Hz, 2H), 7.09
(d, J = 8.5 Hz, 2H), 7.06 (d, J = 7.6 Hz, 1H), 4.51 (s, 1H), 4.05 (s,
2H), 2.40 (s, 4H), 2.30 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3)
δ: 143.1, 140.1, 138.8, 137.5, 136.6, 133.1, 130.1, 130.1, 129.5,
128.9, 128.6, 128.3, 127.1, 127.0, 45.1, 21.4, 20.9; HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C21H22NSO2 352.1366; found
352.1362.
4-methyl-N-((3-methyl-[1,1'-biphenyl]-2-yl)methyl)benzenesulfon-
amide (26’): eluent: PE/EtOAc= 7:1; white solid; yield: 1.49 g, 85%;
1H NMR (600 MHz, CDCl3) δ: 7.50 (d, J = 8.2 Hz, 2H), 7.28-7.25
(m, 1H), 7.25-7.20 (m, 3H), 7.17 (dd, J = 15.7, 7.3 Hz, 3H), 7.10
(d, J = 7.1 Hz, 2H), 7.02 (d, J = 7.3 Hz, 1H), 4.26 (t, J = 5.4 Hz,
1H), 3.97 (d, J = 5.5 Hz, 2H), 2.41 (s, 3H), 2.38 (s, 3H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 143.2, 143.1, 140.7, 138.2, 135.9,
131.0, 130.0, 129.5, 128.7, 128.1, 128.0, 128.0, 127.0, 126.9, 42.2,
21.5, 19.4; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H22NSO2 352.1366; found 352.1359.
N-((4-fluoro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesulfon-
amide (21’): eluent: PE/EtOAc = 6:1; yellow solid; yield: 1.66 g,
88%; 1H NMR (600 MHz, CDCl3) δ: 7.57 (d, J = 8.1 Hz, 2H), 7.37-
7.31 (m, 3H), 7.21 (d, J = 8.0 Hz, 2H), 7.17-7.10 (m, 3H), 7.06 (dd,
J = 9.5, 2.4 Hz, 1H), 6.97 (td, J = 8.3, 2.5 Hz, 1H), 4.64 (t, J = 6.0
Hz, 1H), 4.06 (d, J = 6.3 Hz, 2H), 2.41 (s, 3H); 19F{1H} NMR (565
MHz, CDCl3) δ: -114.31; 13C{1H} NMR (151 MHz, CDCl3) δ:
162.1(d, J = 246.1 Hz), 143.5, 139.2, 137.5 (d, J = 3.0 Hz), 136.6,
135.9, (d, J = 7.6 Hz), 131.7, (d, J = 7.6 Hz), 129.6, 128.9, 128.5,
127.5, 127.0, 115.8 (d, J = 22.7 Hz), 114.7 (d, J = 21.1Hz),44.8,
N-((6-fluoro-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesulfon-
amide (27’): eluent: PE/EtOAc= 7:1; white solid; yield: 1.40 g, 79%;
1H NMR (600 MHz, CDCl3) δ: 7.52 (d, J = 8.2 Hz, 2H), 7.34 (dd,
J = 6.4, 3.8 Hz, 3H), 7.23 (td, J = 7.9, 5.6 Hz, 1H), 7.18 (dd, J =
7.8, 4.0 Hz, 3H), 7.12 (dd, J = 6.4, 2.8 Hz, 2H), 7.02 (t, J = 8.6 Hz,
1H), 4.76 (t, J = 6.2 Hz, 1H), 3.96 (d, J = 6.2 Hz, 2H), 2.38 (d, J =
3.8 Hz, 4H); 19F{1H} NMR (565 MHz, CDCl3) δ: -114.38; 13C{1H}
NMR (151 MHz, CDCl3) δ: 160.4, 158.8, 143.3, 136.7-136.4 (m),
129.5 (d, J = 3.6 Hz), 129.1-128.9 (m), 128.5, 127.9, 126.9 (d, J =
7.9 Hz), 44.5 (d, J = 3.1 Hz), 21.4; HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C20H19FNSO2 356.1115; found 356.1109.
21.5; HRMS (ESI-TOF) m/z: [M
+
Na]+ calcd for
C20H18FNSO2Na 378.0934; found 378.0929.
4-methyl-N-((4-(trifluoromethyl)-[1,1'-biphenyl]-2-yl)methyl)ben-
zenesulfonamide (22’): eluent: PE/EtOAc= 6:1; yellow solid; yield:
1
1.28 g, 70%; H NMR (600 MHz, CDCl3) δ: 7.57-7.52 (m, 3H),
7.50 (d, J = 8.0 Hz, 1H), 7.39-7.34 (m, 3H), 7.26 (d, J = 7.9 Hz,
1H), 7.18 (dd, J = 7.9, 5.3 Hz, 4H), 5.00 (t, J = 6.2 Hz, 1H), 4.13
(d, J = 6.3 Hz, 2H), 2.37 (s, 3H); 19F{1H} NMR (565 MHz, CDCl3)
δ: -62.46; 13C{1H} NMR (151 MHz, CDCl3) δ: 145.1 , 143.5,
138.8(d, J = 398.6 Hz), 138.7, 136.5, 134.7, 130.6, 130.0 (d, J =
7.8 Hz), 128.6 (d, J = 83.1 Hz), 128.6 (d, J = 8.6 Hz), 128.3, 128.0,
125.9 (d, J = 3.6 Hz), 123.8(d, J = 271.8 Hz), 124.4 (d, J = 3.4 Hz),
N-((5-methoxy-[1,1'-biphenyl]-2-yl)methyl)-4-methylbenzenesul-
fonamide (28’): eluent: PE/EtOAc= 7:1; yellow solid; yield: 1.51 g,
82%; 1H NMR (600 MHz, CDCl3) δ: 7.54 (d, J = 8.2 Hz, 2H), 7.34-
7.30 (m, 3H), 7.27-7.23 (m, 1H), 7.20 (d, J = 8.1 Hz, 2H), 7.16 (dd,
J = 7.2, 2.0 Hz, 2H), 6.82 (dd, J = 8.5, 2.7 Hz, 1H), 6.72 (d, J = 2.7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 15
Hz, 1H), 4.36 (s, 1H), 4.01 (s, 2H), 3.79 (s, 3H), 2.41 (s, 3H);
N-(1-([1,1'-biphenyl]-2-yl)ethyl)-4-methylbenzenesulfonamide
13C{1H} NMR (151 MHz, CDCl3) δ: 159.0, 143.2, 140.1, 136.6,
131.0, 129.5, 128.6, 128.4, 127.4, 127.0, 125.6, 115.5, 113.3, 55.3,
44.7, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C21H21NSO3Na 390.1134; found 390.1125.
(35): eluent: PE/EtOAc= 6:1; white solid; yield: 983 mg, 56%; 1H
NMR (400 MHz, CDCl3) δ: 7.47 (d, J = 7.7 Hz, 2H), 7.34 (s, 4H),
7.22 (dd, J = 11.7, 6.4 Hz, 2H), 7.10 (d, J = 7.8 Hz, 5H), 5.14 (d, J
= 5.1 Hz, 1H), 4.60-4.50 (m, 1H), 2.37 (s, 3H), 1.29 (d, J = 6.5 Hz,
3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 142.8, 140.4, 140.2,
140.1, 137.2, 129.8, 129.3, 129.1, 128.1, 127.9, 127.0, 126.8, 125.8,
49.7, 24.5, 21.4; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H22NSO2 352.1366; found 352.1354.
1
2
3
4
5
6
7
8
N-([1,1'-biphenyl]-2-yl(phenyl)methyl)-4-methylbenzenesulfona-
mide (29’): eluent: PE/EtOAc= 8:1; yellow solid; yield: 1.65 g, 80%;
1H NMR (600 MHz, CDCl3) δ: 7.44 (d, J = 8.2 Hz, 2H), 7.42 - 7.39
(m, 1H), 7.33-7.23 (m, 6H), 7.16-7.12 (m, 4H), 7.10 (d, J = 7.9 Hz,
2H), 6.98 (d, J = 6.3 Hz, 2H), 6.89-6.82 (m, 2H), 5.65 (d, J = 6.4
Hz, 1H), 4.98 (d, J = 6.3 Hz, 1H), 2.37 (s, 3H).; 13C{1H} NMR (151
MHz, CDCl3) δ: 143.1, 141.3, 141.0, 140.3, 137.7, 137.1, 130.2,
129.3, 129.2, 128.4, 128.1, 127.7, 127.5, 127.4, 127.3, 127.2, 127.2,
57.9, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C26H23NSO2Na 436.1342; found 436.1340.
9
Characterization Data of the products.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Phenanthridine (2): eluent: PE/EtOAc = 8:1; yellow solid; yield:
1
50.5 mg, 94%; H NMR (600 MHz, CDCl3) δ: 9.27 (s, 1H), 8.57
(dd, J = 16.3, 8.2 Hz, 2H), 8.19 (d, J = 8.1 Hz, 1H), 8.02 (t, J = 6.5
Hz, 1H), 7.86-7.81 (m, 1H), 7.76-7.72 (m, 1H), 7.70-7.64 (m, 2H);
13C{1H} NMR (151 MHz, CDCl3) δ: 153.5, 144.4, 132.5, 130.9,
130.1, 128.7, 128.6, 127.4, 127.0, 126.3, 124.0, 122.2, 121.8.21c
N-([1,1'-biphenyl]-2-yl(p-tolyl)methyl)-4-methylbenzenesulfona-
mide (30’): eluent: PE/EtOAc= 8:1; white solid; yield: 1.75 g, 82%;
1H NMR (600 MHz, CDCl3) δ: 7.46-7.40 (m, 3H), 7.33-7.27 (m,
3H), 7.27-7.25 (m, 3H), 7.15-7.12 (m, 1H), 7.10 (d, J = 8.0 Hz, 2H),
7.00 (d, J = 6.7 Hz, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.75 (d, J = 8.1
Hz, 2H), 5.60 (d, J = 6.2 Hz, 1H), 4.89 (d, J = 6.2 Hz, 1H), 2.38 (s,
3H), 2.26 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 143.0, 140.3,
137.9, 137.3, 130.2, 129.3, 129.2, 129.1, 128.1, 127.7, 127.5, 127.4,
127.2, 127.1, 57.7, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ calcd
for C27H25NSO2Na 450.1498; found 450.1496.
3-methylphenanthridine (3): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 56.2 mg, 97%; 1H NMR (400 MHz, CDCl3) δ: 9.16 (s, 1H),
8.45 (d, J = 8.3 Hz, 1H), 8.35 (d, J = 8.3 Hz, 1H), 7.95-7.87 (m,
2H), 7.78-7.70 (m, 1H), 7.62-7.52 (m, 1H), 7.41 (dd, J = 8.3, 1.4
Hz, 1H), 2.51 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 153.4,
144.3, 138.9, 132.6, 131.0, 129.4, 128.8, 128.7, 127.0, 126.0, 121.9,
121.7, 121.6, 21.5.21f
3-isopropylphenanthridine (4): eluent: PE/EtOAc = 8:1; yellow
solid; yield: 38.5 mg, 58%; 1H NMR (400 MHz, CDCl3) δ: 9.26 (s,
1H), 8.56 (d, J = 8.0 Hz, 1H), 8.49 (d, J = 8.4 Hz, 1 H), 8.05 (d, J
= 1.6 Hz, 1 H), 8.02 (d, J = 8.0 Hz, 1H), 7.85-7.81 (m, 1H), 7.68-
7.64 (m, 1H), 7.58 (dd, J = 2.0 Hz, 8.4 Hz, 1H), 3.22-3.12 (m, 1H),
1.40 (d, J = 6.8 Hz, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ: 153.4,
149.8, 144.6, 132.6, 130.9, 128.7, 127.0, 126.8, 126.5, 126.1, 122.1,
121.7, 34.1, 23.9; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C16H16N 222.1277; found 222.1270.
N-([1,1'-biphenyl]-2-yl(4-methoxyphenyl)methyl)-4-methylben-
zenesulfonamide (31’): eluent: PE/EtOAc= 8:1; yellow solid; yield:
1.88 g, 85%; 1H NMR (600 MHz, CDCl3) δ: 7.43 (dd, J = 11.2, 4.8
Hz, 3H), 7.34-7.24 (m, 6H), 7.13 (dd, J = 7.2, 1.7 Hz, 1H), 7.10 (d,
J = 8.0 Hz, 2H), 6.99 (d, J = 6.5 Hz, 2H), 6.77 (d, J = 8.7 Hz, 2H),
6.69 -6.65 (m, 2H), 5.58 (d, J = 6.2 Hz, 1H), 4.93 (d, J = 6.2 Hz,
1H), 3.73 (s, 3H), 2.38 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3)
δ: 158.9, 143.0, 141.2, 140.3, 137.9, 137.1, 133.2, 130.2, 129.3,
129.1, 128.7, 128.0, 127.7, 127.3, 127.2, 127.1, 113.8, 57.5, 55.2,
21.5; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C27H25NSO3Na
466.1447; found 466.1444.
3-fluorophenanthridine (5): eluent: PE/EtOAc = 8:1; yellow solid;
yield: 47.3 mg, 80%; 1H NMR (600 MHz, CDCl3) δ: 9.29 (s, 1H),
8.56-8.52 (m, 2H), 8.04 (d, J = 7.8 Hz, 1H), 7.88-7.85 (m, 1H), 7.84
(dd, J = 9.9 Hz, 2.7 Hz, 1H), 7.72-7.69 (m, 1H), 7.45-7.42 (m, 1H);
19F{1H} NMR (565 MHz, CDCl3) δ: -111.97; 13C{1H} NMR (151
MHz, CDCl3) δ: 162.6 (d, J = 247.9 Hz), 154.8, 145.8 (d, J = 12.1
Hz), 132.3, 131.4, 128.9, 127.3, 125.956.0, 124.1 (d, J = 9.8 Hz),
121.6, 120.8, 116.1 (d, J = 24.2 Hz), 114.7 (d, J = 20.7 Hz).21e
N-([1,1'-biphenyl]-2-yl(4-chlorophenyl)methyl)-4-methylbenzene-
sulfonamide (32’): eluent: PE/EtOAc= 8:1; white solid; yield: 1.70
1
g, 76%; H NMR (400 MHz, CDCl3) δ: 7.44-7.41 (m, 2H), 7.38-
7.35 (m, 1H), 7.33-7.30 (m, 1H), 7.30-7.23 (m, 5H), 7.14-7.10 (m,
2H), 7.10-7.05 (m, 4H), 6.96 (d, J = 6.8 Hz, 2H), 6.80 (d, J = 8.5
Hz, 2H), 5.63 (d, J = 7.0 Hz, 1H), 5.45 (d, J = 7.0 Hz, 1H), 2.37 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 143.2, 141.1, 140.0,
139.6, 137.3, 137.0, 133.2, 130.3, 129.3, 129.0, 128.8, 128.4, 128.2,
127.9, 127.5, 127.3, 127.1, 127.1, 57.3, 21.5.; HRMS (ESI-TOF)
m/z: [M + Na]+ calcd for C26H22ClNSO2Na 470.0952; found
470.0948.
3-chlorophenanthridine (6): PE/EtOAc(eluent) 8 : 1; yellow solid;
yield: 42.3 mg, 66%; 1H NMR (400 MHz, CDCl3) δ: 9.27 (s, 1H),
8.50 (dd, J = 24.6, 8.5 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 8.04 (d, J
= 7.9 Hz, 1H), 7.87 (ddd, J = 8.3, 7.2, 1.3 Hz, 1H), 7.75-7.69 (m,
1H), 7.62 (dd, J = 8.8, 2.2 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ: 154.7, 145.1, 134.3, 132.1, 131.4, 129.3, 128.9, 127.8,
127.6, 126.3, 123.6, 122.6, 121.8.21d
N,N'-([1,1':4',1'':4'',1'''-quaterphenyl]-2,2'''-diylbis(meth-
ylene))bis(4-methylbenzenesulfonamide (33): eluent: PE/EtOAc =
10:1; white solid; yield: 1.65 g, 49%; 1H NMR (400 MHz, CDCl3)
δ: 7.59 (t, J = 8.6 Hz, 8H), 7.39 (dd, J = 7.0, 1.9 Hz, 2H), 7.37-7.32
(m, 4H), 7.32 -7.27 (m, 6H), 7.19 (d, J = 8.1 Hz, 4H), 4.42 (t, J =
5.9 Hz, 2H), 4.17 (d, J = 6.0 Hz, 4H), 2.31 (s, 6H); 13C{1H} NMR
(151 MHz, CDCl3) δ: 143.4, 141.3, 139.4, 136.6, 133.4, 130.3,
129.6, 129.4, 128.1 (d, J = 13.8 Hz), 127.0 (d, J = 14.7 Hz), 45.2,
21.4; HRMS (ESI-TOF) m/z: [M + H]+ calcd for C40H37N2S2O4
673.2189; found 673.2185.
3-(trifluoromethyl)phenanthridine (7): eluent: PE/EtOAc= 8:1; yel-
1
low solid; yield: 38.5 mg, 52%; H NMR (400 MHz, CDCl3) δ:
9.32 (s, 1H), 8.60 (dd, J = 15.4, 8.4 Hz, 2H), 8.45 (s, 1H), 8.06 (d,
J = 7.8 Hz, 1H), 7.94-7.87 (m, 1H), 7.84 (dd, J = 8.6, 1.6 Hz, 1H),
7.81-7.73 (m, 1H); 19F{1H} NMR (376 MHz, CDCl3) δ: -62.22;
13C{1H} NMR (100 MHz, CDCl3) δ: 154.8, 143.7, 131.6, 131.5,
130.4 (q, J = 32.7 Hz), 128.9, 128.6, 127.6 (q, J = 4.2 Hz), 126.8,
ACS Paragon Plus Environment

Page 11 of 15
The Journal of Organic Chemistry
126.4, 124.0 (q, J = 270.7 Hz), 123.2, 122.9 (q, J = 3.4 Hz),
(376 MHz, CDCl3) δ:-134.59 (d, J = 21.8 Hz) (16), -135.55 (d, J =
122.2.21a
21.8 Hz) (16), -137.10 (d, J = 19.6 Hz) (17), -149.63 (d, J = 19.6
Hz) (17); 13C{1H} NMR (151 MHz, CDCl3) δ: 153.9 (d, J = 5.3
Hz), 150.9 (dd, J = 251.7 Hz, 14.6 Hz), 150.1 (d, J = 250.5 Hz,
14.6 Hz), 141.4 (d, J = 9.8 Hz), 131.6 (d, J = 2.6 Hz), 131.4, 128.9,
127.9, 125.9, 121.8, 121.2 (dd, J = 6.6 Hz, 2.0 Hz), 117.0 (d, J =
16.6 Hz), 109.2 (d, J = 18.7 Hz).22e
1
2
3
4
5
6
7
8
3-methoxyphenanthridine (8): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 43.9 mg, 70%; 1H NMR (600 MHz, CDCl3) δ: 9.26 (s, 1H),
8.49 (dd, J = 17.7, 8.7 Hz, 2H), 8.02 (d, J = 7.9 Hz, 1H), 7.87-7.79
(m, 1H), 7.67-7.59 (m, 2H), 7.33 (dd, J = 9.0, 2.7 Hz, 1H), 4.00 (s,
3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 160.08, 153.96, 146.08,
132.78, 131.08, 128.80, 126.40, 125.56, 123.38, 121.36, 118.13,
118.10, 109.95, 55.55.21b
1,2-dimethylphenanthridine (18): eluent: PE/EtOAc = 8:1; yellow
solid; yield: 17.4 mg, 28%; 1H NMR (600 MHz, CDCl3) δ: 9.18 (s,
1H), 8.78 (d, J = 8.4 Hz, 1H), 8.06 (dd, J = 1.2 Hz, 7.2 Hz, 1H),
7.97 (d, J = 7.8 Hz, 1H), 7.83-7.80 (m, 1H), 7.70 (t, J = 7.5 Hz,
1H), 7.57 (d, J = 8.4 Hz, 1H), 2.96 (s, 3H), 2.59 (s, 3H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 152.7, 144.4, 136.7, 133.3, 133.1,
130.7, 129.7, 128.8, 127.8, 127.7, 127.1, 126.6, 124.2, 21.8, 21.2;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C15H14N 208.1121;
found 208.1120.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2-iodo-3-methoxyphenanthridine (9): eluent: PE/EtOAc= 8:1; yel-
1
low solid; yield: 53.1 mg, 53%; H NMR (600 MHz, CDCl3) δ:
9.16 (s, 1H), 8.90 (s, 1H), 8.37 (d, J = 8.3 Hz, 1H), 7.94 (d, J = 7.9
Hz, 1H), 7.77 (dd, J = 11.3, 4.0 Hz, 1H), 7.58 (t, J = 7.4 Hz, 1H),
7.44 (s, 1H), 3.98 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ:
157.9, 154.3, 145.8, 133.4, 131.5, 131.4, 128.9, 127.0, 125.5, 121.3,
119.7, 109.2, 87.9, 56.6; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C14H11ION 335.9880; found 335.9879.
2,3,4-trifluorophenanthridine (19): eluent: PE/EtOAc = 8:1; white
solid; yield: 57.3 mg, 82%; 1H NMR (400 MHz, CDCl3) δ: 9.31 (s,
1H), 8.42 (d, J = 8.2 Hz, 1H), 8.09 (t, J = 10.3 Hz, 2H), 7.93 (t, J
= 7.6 Hz, 1H), 7.80 (t, J = 7.4 Hz, 1H); 19F{1H} NMR (376 MHz,
CDCl3) δ: -132.70 (dd, J = 6.8 Hz, 21.1 Hz), -144.19 (dd, J = 6.4
Hz, 18.8 Hz), -157.72 (dd, J = 19.6 Hz, 21.4 Hz); 13C{1H} NMR
(151 MHz, CDCl3) δ: 154.1 , 150.4 (dd, J = 250.7, 8.6 Hz) , 147.0
(dd, J = 267.3, 14.0 Hz) , 140.0 (dd, J = 250.7, 30.8 Hz), 131.9,
131.1, 129.2, 128.6, 126.4, 122.0, 120.7 (d, J = 8.0 Hz), 103.6 (dd,
J = 18.8, 4.6 Hz), 29.7; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C13H7F3N 234.0525; found 234.0525.
3-phenylphenanthridine (10): eluent: PE/EtOAc= 8:1; yellow solid;
1
yield: 38.3 mg, 50%; H NMR (400 MHz, CDCl3) δ:9.23 (s, 1H),
8.54 (dd, J = 8.4, 3.1 Hz, 2H), 8.35 (d, J = 1.9 Hz, 1H), 7.97 (d, J
= 7.7 Hz, 1H), 7.87 (dd, J = 8.5, 1.9 Hz, 1H), 7.79 (ddd, J = 8.3,
7.2, 1.3 Hz, 1H), 7.73 (dd, J = 5.2, 3.3 Hz, 2H), 7.67-7.59 (m, 1H),
7.44 (dd, J = 10.4, 4.8 Hz, 2H), 7.37-7.29 (m, 1H); 13C{1H} NMR
(151 MHz, CDCl3) δ: 154.7, 145.1, 134.3, 132.1, 131.4, 129.3,
128.9, 127.8, 127.6, 126.3, 123.6, 122.6, 121.8.21f
1-methylphenanthridine (11): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 15.5 mg, 25%; 1H NMR (600 MHz, CDCl3) δ: 9.26 (s, 1H),
8.90 (d, J = 8.6 Hz, 1H), 8.13-8.07 (m, 2H), 7.89-7.84 (m, 1H), 7.73
(dd, J = 13.7, 6.3 Hz, 1H), 7.64 (t, J = 7.7 Hz, 1H), 7.53 (d, J = 7.2
Hz, 1H), 3.14 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 153.6,
146.1, 135.5, 133.8, 131.2, 130.3, 129.1, 129.1, 127.8, 127.5, 126.7,
126.4, 123.8, 26.7.21g
8-methylphenanthridine (20): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 43.4 mg, 75%; 1H NMR (400 MHz, CDCl3) δ: 9.21 (s, 1H),
8.51 (d, J = 8.0 Hz, 1H), 8.46 (d, J = 8.4 Hz, 1H), 8.17 (d, J = 8.0
Hz, 1H), 7.79 (s, 1H), 7.73-7.63 (m, 3H), 2.58 (s, 3H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 153.2, 143.9, 137.5, 132.8, 130.4,
129.8, 128.2, 128.1, 127.0, 126.4, 124.1, 122.0, 121.7, 21.4.9
2-fluorophenanthridine (12) and 4-fluorophenanthridine (13):
12:13=6:1; eluent: PE/EtOAc = 8:1; yellow solid; yield: 50.8 mg,
86%; 1H NMR (400 MHz, CDCl3) δ: 9.19 (s, 1H), 8.40 (d, J = 8.4
Hz, 1H), 8.14 (dd, J = 5.6 Hz, 8.8 Hz, 1H), 8.09 (dd, J = 2.8 Hz,
10.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.84-7.80 (m, 1H), 7.72-
7.68 (m, 1H), 7.44 (dt, J = 2.8 Hz, 8.8 Hz, 1H); 19F{1H} NMR (376
MHz, CDCl3) δ: -112.46 (12), -124.45 (13); 13C{1H} NMR (151
MHz, CDCl3) δ: 161.2 (d, J = 247.6 Hz), 152.5, 140.8, 132.0 (d, J
= 9.2 Hz), 131.1, 128.7, 128.1, 126.1, 125.4 (d, J = 9.3 Hz), 121.9,
117.5 (d, J = 24.3 Hz), 107.0 (d, J = 23.4 Hz).14b
8-fluorophenanthridine (21): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 50.8 mg, 86%; 1H NMR (400 MHz, CDCl3) δ: 9.22 (s, 1H),
8.59 (dd, J = 5.2 Hz, 9.2 Hz, 1H), 8.51 (d, J = 8.0 Hz, 1H), 8.19 (d,
J = 8.0 Hz,1H), 7.76-7.73 (m, 1H), 7.71-7.65 (m, 2H), 7.59 (dt, J
= 2.5 Hz, 8.8 Hz, 1H); 19F{1H} NMR (376 MHz, CDCl3) δ:-112.34;
13C{1H} NMR (151 MHz, CDCl3) δ: 161.5 (d, J = 249.6 Hz), 152.4
(d, J = 4.1 Hz), 144.1, 130.3, 129.2, 128.5, 127.5, 127.4, 124.5 (d,
J = 8.2 Hz), 123.7, 121.9, 120.2 (d, J = 23.6 Hz), 112.7 (d, J = 20.8
Hz).22c
8-(trifluoromethyl)phenanthridine (22): eluent: PE/EtOAc = 8:1;
yellow solid; yield: 54.1 mg, 73%; 1H NMR (400 MHz, CDCl3) δ:
9.33 (s, 1H), 8.70 (d, J = 8.4 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.33
(s, 1H), 8.23 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 8.8 Hz, 1H), 7.83 (t,
J = 7.6 Hz, 1H), 7.76-7.72 (m, 1H); 19F{1H} NMR (565 MHz,
CDCl3) δ: -62.28; 13C{1H} NMR (151 MHz, CDCl3) δ: 153.1,
145.1, 134.6, 130.4, 129.9, 129.4 (q, J = 33.2 Hz), 127.7, 126.8 (q,
J = 3.0 Hz), 126.2 (q, J = 4.1 Hz), 125.5, 123.9 (q, J = 272.8 Hz),
123.1, 123.0, 122.5.22f
2-methoxyphenanthridine (14) and 4-methoxyphenanthridine (15) :
14:15>20:1; eluent: PE/EtOAc= 8:1; yellow solid; yield: 30.7 mg,
49%; 1H NMR (400 MHz, CDCl3) δ: 9.16 (s, 1H), 8.48 (d, J = 8.0
Hz, 1H), 8.16 (d, J = 8.0 Hz, 1H), 7.94 (d, J = 8.8 Hz, 1H), 7.89 (s,
1H), 7.73 (t, J = 7.2 Hz, 1H), 7.66-7.63 (m, 1 H), 7.31-7.28 (m, 1H),
4.03 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 158.5, 150.5,
138.7, 132.1, 130.9, 130.8, 128.8, 127.6, 126.2, 125.2, 121.8, 118.7,
103.0, 55.6.22e
2,3-difluorophenanthridine (16) and 3,4-difluorophenanthridine
(17): 16:17=6:1; eluent: PE/EtOAc = 8:1; yellow solid; yield: 53.5
mg, 83%; 1H NMR (400 MHz, CDCl3) δ: 9.23 (s, 1H), 8.38 (d, J =
8.4 Hz, 1H), 8.23 (dd, J = 8.3 Hz, 11.5 Hz, 1H), 8.04 (d, J = 8.0
Hz, 1H), 7.95-7.85 (m, 2H), 7.73 (t, J = 7.4 Hz, 1H); 19F{1H} NMR
8-phenylphenanthridine (23): eluent: PE/EtOAc = 10:1; yellow
solid; yield: 38.3 mg, 50%; 1H NMR (400 MHz, CDCl3) δ:9.36 (s,
1H), 8.64 (d, J = 8.4 Hz, 1H), 8.57 (d, J = 8.0 Hz), 8.23-8.21 (m,
2H), 8.11 (dd, J = 1.4 Hz, 8.4 Hz, 1H), 7.77-7.67 (m, 4H), 7.54-
7.50 (m, 2H), 7.45-7.41 (m, 1H); 13C{1H} NMR (151 MHz,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 15
CDCl3) δ: 153.6, 144.0, 140.4, 139.8, 131.6, 130.4, 129.8, 129.1,
128.8, 128.0, 127.3, 126.7, 124.0, 122.5, 122.3; HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C19H14N 256.1121; found 256.1120.
138.6, 136.9, 133.5, 130.5, 130.3, 129.7, 129.1, 129.0, 128.8, 127.1,
126.8, 125.3, 123.7, 122.2, 121.9, 21.3.17g
1
2
3
4
5
6
7
8
9
6-(4-methoxyphenyl)phenanthridine (31): eluent: PE/CH2Cl2 = 1:2;
yellow solid; yield: 50.4 mg, 59%; 1H NMR (400 MHz, CDCl3) δ:
8.70 (d, J = 8.3 Hz, 1H), 8.61 (d, J = 7.8 Hz, 1H), 8.24 (dd, J = 8.1,
0.7 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H), 7.87-7.83 (m, 1H), 7.77-7.73
(m, 1H), 7.73-7.65 (m, 3H), 7.65-7.60 (m, 1H), 7.12-7.08 (m, 2H),
3.92 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 160.9, 160.1,
143.8, 133.5, 133.5, 132.3, 131.2, 130.4, 130.2, 128.9, 128.8, 127.1,
127.0, 126.72, 125.3, 123.6, 122.2, 121.9,55.4.17g
10-methylphenanthridine (24): eluent: PE/EtOAc = 8:1; yellow
solid; yield: 35.9 mg, 62%; 1H NMR (400 MHz, CDCl3) δ: 9.25 (s,
1H), 8.85 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 7.6 Hz, 1H), 7.93 (d, J
= 7.6 Hz, 1H), 7.77-7.74 (m, 1H), 7.69-7.67 (m, 2H), 7.63-7.60 (m,
1H), 3.12 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 154.4, 145.4,
135.3, 135.2, 131.9, 130.2, 128.0, 127.9, 127.9, 127.0, 126.5, 126.4,
125.7, 26.5.21g
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9-methylphenanthridine (25): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 48.1 mg, 83%; 1H NMR (400 MHz, CDCl3) δ: 9.23 (s, 1H),
8.55 (d, J = 8.0 Hz, 1H), 8.37 (s, 1H), 8.18 (d, J = 8.0 Hz, 1H), 7.93
(d, J = 8.0 Hz, 1H), 7.73 (t, J = 7.6 Hz, 1H), 7.66 (t, J = 7.6 Hz,
1H), 7.52 (d, J = 8.0 Hz, 1H), 2.64 (s, 3H); 13C{1H} NMR (151
MHz, CDCl3) δ: 153.1, 144.1, 141.8, 132.7, 129.7, 129.3, 128.7,
128.6, 126.9, 124.4, 124.0, 122.2, 121.5, 22.4.21g
6-(4-chlorophenyl)phenanthridine (32): eluent: PE/CH2Cl2 = 4:1;
yellow solid; yield: 57.2 mg, 66%; 1H NMR (600 MHz, CDCl3) δ:
8.72 (d, J = 8.3 Hz, 1H), 8.63 (d, J = 8.1 Hz, 1H), 8.24 (d, J = 8.1
Hz, 1H), 8.07 (d, J = 8.2 Hz, 1H), 7.88 (t, J = 7.6 Hz, 1H), 7.80-
7.75 (m, 1H), 7.73-7.68 (m, 3H), 7.64 (t, J = 7.6 Hz, 1H), 7.57-7.53
(m, 2H); 13C{1H} NMR (151 MHz, CDCl3) δ: 160.0, 143.6, 138.1,
134.93, 133.5, 131.2, 130.8, 130.3, 129.0, 128.7, 128.5, 127.3,
127.2, 125.0, 123.8, 122.3, 122.0.17g
7-methylphenanthridine (26): eluent: PE/EtOAc= 8:1; yellow solid;
yield: 32.4 mg, 56%; 1H NMR (400 MHz, CDCl3) δ: 9.57 (s, 1H),
8.59 (d, J = 8.3 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 8.21 (d, J = 7.6
Hz, 1H), 7.77-7.67 (m, 3H), 7.50 (d, J = 6.8 Hz, 1H), 2.88 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ: 150.1, 143.7, 136.7, 132.9,
130.9, 129.7, 128.9, 128.6, 127.2, 124.8, 124.3, 122.4, 120.0,
18.9.22a
3,3'-biphenanthridine (34): eluent: PE/CH2Cl2 = 6:1; yellow solid;
1
yield: 51.3 mg, 72%; H NMR (600 MHz, DMSO-d6) δ: 9.46 (s,
2H), 8.96 (s, 4H), 8.61 (s, 2H), 8.31 (s, 4H), 7.93 (d, J = 91.9 Hz,
4H); 13C{1H} NMR (151 MHz, DMSO-d6) δ: 154.2, 139.6, 131.9,
130.1, 129.1, 128.2, 127.3, 126.3, 126.1, 124.1, 123.3, 123.2, 122.5;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C26H17N2 357.1386;
found 357.1386.
10-fluorophenanthridine (27): eluent: PE/EtOAc= 8:1; yellow solid;
1
6-methyl-5-tosyl-5,6-dihydrophenanthridine
(36):
eluent:
yield: 44.9 mg, 76%; H NMR (600 MHz, CDCl3) δ: 9.28 (d, J =
1
2.4 Hz, 1H), 8.97 (d, J = 8.4 Hz, 1H), 8.22 (d, J = 7.8 Hz, 1H), 7.88
(d, J = 7.8 Hz, 1H), 7.79 (t, J = 7.2 Hz, 1H), 7.73-7.71 (m, 1H),
7.69-7.66 (m, 1 H), 7.59-7.56 (m, 1H); 19F{1H} NMR (565 MHz,
CDCl3) δ:-110.65; 13C{1H} NMR (151 MHz, CDCl3) δ: 160.3 (d, J
= 255.5 Hz), 144.7, 120.0, 128.9, 128.7, 127.8 (d, J = 8.9 Hz),
127.7, 127.1, 127.0, 124.8 (d, J = 3.6 Hz), 121.7, 121.7, 117.5 (d, J
= 23.7 Hz); HRMS (ESI-TOF) m/z: [M + H]+ calcd for C13H9FN
198.0714; found 198.0714.
PE/EtOAc = 15:1; yellow solid; yield: 33.5 mg, 32%; H NMR
(600 MHz, CDCl3) δ: 7.80 (d, J = 7.9 Hz, 1H), 7.58 (d, J = 7.6 Hz,
1H), 7.39 (t, J = 7.2 Hz, 1H), 7.33 (t, J = 7.4 Hz, 1H), 7.27-7.21
(m, 1H), 7.12 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.3 Hz, 1H), 7.02 (d,
J = 7.3 Hz, 1H), 6.92 (d, J = 8.2 Hz, 2H), 6.68 (d, J = 8.1 Hz, 2H),
5.42 (q, J = 7.0 Hz, 1H), 2.14 (d, J = 8.1 Hz, 3H), 1.26 (d, J = 7.0
Hz, 4H); 13C{1H} NMR (151 MHz, CDCl3) δ: 142.7, 136.7, 134.1,
133.1, 129.9, 129.6, 129.1, 128.4, 128.3, 127.8, 127.3, 127.2, 127.0,
125.8, 123.4, 123.1, 54.9, 21.7, 21.2; HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C21H20NSO2 350.1209; found 350.1202.
9-methoxyphenanthridine (28): eluent: PE/EtOAc = 6:1; yellow
solid; yield: 32.0 mg,51%; 1H NMR (400 MHz, CDCl3) δ: 9.16 (s,
1H), 9.48 (d, J = 8.0 Hz, 1H), 9.16 (d, J = 8.0 Hz, 1H), 7.94 (d, J
= 8.0 Hz, 1H), 7.89 (s, 1H), 7.73 (t, J = 8.0 Hz, 1H), 7.66-7.63 (m,
1 H), 7.29 (dd, J = 1.8 Hz, 8.4 Hz, 1H), 4.03 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ: 162.1, 152.5, 144.0, 134.7, 130.8, 129.6,
128.9, 126.7, 123.9, 122.3, 121.3, 118.1, 102.6, 55.7.22d
6-methylphenanthridine (37): eluent: PE/EtOAc= 7:1; yellow solid;
1
yield: 46.3 mg, 80%; H NMR (600 MHz, CDCl3) δ: 8.64 (d, J =
8.3 Hz, 1H), 8.55 (d, J = 8.1 Hz, 1H), 8.24 (d, J = 8.2 Hz, 1H), 8.12
(d, J = 8.1 Hz, 1H), 7.86 (t, J = 7.6 Hz, 1H), 7.71 (td, J = 7.6, 3.9
Hz, 2H), 7.63 (t, J = 7.5 Hz, 1H), 3.06 (s, 3H); 13C{1H} NMR (151
MHz, CDCl3) δ: 158.9, 132.7, 131.4, 129.1, 128.8, 127.4, 126.7,
126.5, 125.8, 123.8, 122.4, 122.0, 29.7, 22.7.8a
6-phenylphenanthridine (29): eluent: PE/CH2Cl2 = 4 : 1; yellow solid;
yield: 61.2 mg, 80%; 1H NMR (600 MHz, CDCl3) δ: 8.71 (d, J =
8.3 Hz, 1H), 8.63 (d, J = 8.1 Hz, 1H), 8.26 (d, J = 8.1 Hz, 1H), 8.11
(d, J = 8.2 Hz, 1H), 7.90 - 7.84 (m, 1H), 7.78-7.73 (m, 3H), 7.72-
7.67 (m, 1H), 7.62 (t, J = 7.6 Hz, 1H), 7.59-7.51 (m, 3H); 13C{1H}
NMR (151 MHz, CDCl3) δ: 161.3, 143.7, 139.7, 133.5, 130.6,
130.3, 129.7, 128.9, 128.8, 128.7, 128.4, 127.1, 126.9, 125.2, 123.7,
122.2, 121.9.17g
A S S O C I A T E D C O NT E NT
S u p p orti n g I n f orma ti on
The Supporting Information is available free of charge
on the ACS Publications website.
Experimental details, characterization data, and
copies of 1 H 19F, 31P and 13C NMR spectra (PDF)
6-(p-tolyl)phenanthridine (30): eluent: PE/CH2Cl2 = 1:2; white solid;
yield: 56.5 mg, 70%; 1H NMR (600 MHz, CDCl3) δ: 8.70 (d, J =
8.3 Hz, 1H), 8.62 (d, J = 8.1 Hz, 1H), 8.25 (d, J = 8.1 Hz, 1H), 8.14
(d, J = 8.2 Hz, 1H), 7.86 (ddd, J = 8.2, 7.0, 1.2 Hz, 1H), 7.78-7.73
(m, 1H), 7.72-7.66 (m, 1H), 7.66-7.59 (m, 3H), 7.37 (d, J = 7.8 Hz,
2H), 2.48 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ: 161.3, 143.8,
A U T H O R I NF O R MA T I O N
C orresp on di n g A u th or
* Email: mayanna@htu.edu.cn
* Email: xnchen@htu.edu.cn
ACS Paragon Plus Environment

Page 13 of 15
Notes
The Journal of Organic Chemistry
(7)(a) Sun, X.; Yu, S. Visible-Light-Promoted Iminyl
1
Radical Formation from Vinyl Azides: Synthesis of 6-
(Fluoro)alkylated Phenanthridines. Chem. Commun. 2016, 52,
10898-10901. (b) Mackay, E. G.; Studer, A. Electron-Cat-
alyzed Fluoroalkylation of Vinyl Azides. Chem. Eur. J.
2016, 22, 13455-13458. (c) Li, Y.; Zhu, Y.; Yang, S.-D.
Visible-Light-Induced Tandem Phosphorylation Cyclization
of Vinyl Azides under Mild Conditions. Org. Chem. Front.
2018, 5, 822-826.
The authors declare no competing financial interest.
2
3
A C K NO WL E D G ME NT
4
5
6
We are grateful for the financial support from the
National Natural Science Foundation of China (No.
21801065, U180425, 21771057).
7
8
R E F E R E NC E S
(8)(a) Deb, I.; Yoshikai, N. Phenanthridine Synthesis
through Iron-Catalyzed Intramolecular N-Arylation of O-
Acetyl Oxime. Org. Lett. 2013, 15, 4254-4257. (b) Chen,
Y.-F.; Hsieh, J.-C. Synthesis of Polysubstituted Phenan-
thridines via Ligand-Free Copper-Catalyzed Annulation.
Org. Lett. 2014, 16, 4642-4645. (c) Hofstra, J. L.; Grass-
baugh, B. R.; Tran, Q. M.; Armada, N. R.; Lijser, H. J.
P. Catalytic Oxidative Cyclization of 2’ -Arylbenzalde-
hyde Oxime Ethers under Photoinduced Electron Transfer
Conditions. J. Org. Chem. 2015, 80, 256-265. (d) Jiang,
H.; An, X.; Tong, K.; Zheng, T.; Zhang, Y.; Yu, S. Visible-
Light-Promoted Iminyl-Radical Formation from Acyl Oximes:
A Unified Approach to Pyridines, Quinolines, and Phenan-
thridines. Angew. Chem. Int. Ed. 2015, 54, 4055-4059. (e)
An, X.-D.; Yu, S. Visible-Light-Promoted and One-Pot Syn-
thesis of Phenanthridines and Quinolines from Aldehydes
and O-Acyl Hydroxylamine. Org. Lett. 2015, 17, 2692-2695.
(9)(a) Zhao, H.-B.; Liu, Z.-J.; Song, J.; Xu, H.-C.
Reagent-Free C-H/N-H Cross-Coupling: Regioselective Syn-
thesis of N-Heteroaromatics from Biaryl Aldehydes and NH3.
Angew. Chem., Int. Ed. 2017, 56, 12732-12735. (b) Zhao,
H.-B.; Xu, P.; Song, J.; Xu, H.-C. Cathode Material De-
termines Product Selectivity for Electrochemical C-H Func-
tionalization of Biaryl Ketoximes. Angew. Chem., Int. Ed.
2018, 57, 15153-15156. (c) Xiong, P.; Xu, H.-C.; Chemistry
with Electrochemically Generated N-Centered Radicals. Acc.
Chem. Res. 2019, 52, 3339-3350.
(10) (a) Evoniuk, C. J.; Gomes, G. P.; Hill, S. P.;
Fujita, S.; Hanson, K.; Alabugin, I. V. Coupling N-H
Deprotonation, C-H Activation, and Oxidation: Metal-Free
C(sp3)-H Aminations with Unprotected Anilines. J. Am. Chem.
Soc. 2017, 139, 16210-16221. (b) Elliott, Q.; Gomes, G.
P.; Evoniuk, C. J.; Alabugin, I. V. Testing the Limits of
Radical-Anionic CH-Amination: a 10-Million-Fold Decrease
in Basicity Opens a New Path to Hydroxyisoin-
dolines via a Mixed C-N/C-O-Forming Cascade. Chem. Sci.
2020, 11, 6539-6555.
(11)(a) Han, W.; Zhou, X.; Yang, S.; Xiang, G.; Cui,
B.; Chen, Y. Palladium-Catalyzed Nucleophilic Substitu-
tion/C-H Activation/ Aromatization Cascade Reaction: One
Approach to Construct 6-Unsubstituted Phenanthridines. J.
Org. Chem. 2015, 80, 11580-11587; (b) Jaiswal, Y.; Kumar,
Y.; Pal, J.; Subramanian, R.; Kumar, A. Rapid synthesis
of polysubstituted phenanthridines from simple ali-
phatic/aromatic nitriles and iodo arenes via Pd( II) cat-
alyzed domino C- C/C- C/C- N bond formation. Chem. Commun.
2018, 54, 7207-7210.
(1)(a) Abdel-Halim, O. B.; Morikawa, T.; Ando, S.;
Matsuda, H.; Yoshikawa, M. New Crinine-Type Alkaloids with
Inhibitory Effect on Induction of Inducible Nitric Oxide
Synthase from Crinum yemense. J. Nat. Prod. 2004, 67,
1119-1124. (b) Keller, P. A. Product class: phenanthridine,
Sci. Synth. 2005, 15, 1065. (c) Tumir, L.-M.; Radić
Stojković , M.; Piantanida, I. Come-back of phenanthridine
and phenanthridinium derivatives in the 21st century
Beilstein J. Org. Chem. 2014, 10, 2930-2954.
(2)Stevens, N.; O’ Connor, N.; Vishwasrao, H.; Samaroo,
D.; Kandel, E. R.; Akins, D. L.; Drain, C. M.; Turro, N.
J. Two Color RNA Intercalating Probe for Cell Imaging
Applications. J. Am. Chem. Soc. 2008, 130, 7182-7183.
(3)(a) Treus, M.; Estevez, J. C.; Castedo, L.; Esteves,
R. J. A New Route to 3-(2-Vinylphenyl)-2-methyl-2H-iso-
quinolin-1-ones and Benzo[ c] phenanthridines: Total Syn-
thesis of Fagaronine. Tetrahedron Lett. 2002, 43, 5323-
5325. (b) Clement, B.; Weide, M.; Wolschendorf, U.; Kock,
I. A Two-Step Synthesis of Cytostatically Active
Benzo[ c] phenanthridine Derivatives. Angew. Chem. Int.
Ed. 2005, 44, 635-638.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(4)Morgan, G. T.; Walls, L. P. Researches in the phe-
nanthridine series. Part I. A new synthesis of phenan-
thridine homologues and derivatives. J. Chem. Soc. 1931,
2447-2456.
(5)(a) Sripada, L.; Teske, J. A.;
Deiters, A. Phe-
nanthridine synthesis via [ 2+ 2+ 2] cyclotrimerization
reactions. Org. Biomol. Chem. 2008, 6, 263-265. (b) Pear-
son, R.; Zhang, S.; He, G.; Edwards, N.; Chen, G. Synthesis
of Phenanthridines via Palladium-Catalyzed Picolinamide-
Directed Sequential C-H Functionalization, Beilstein J.
Org. Chem. 2013, 9, 891-899. (c) Tang, C.; Yuan, Y.; Jiao,
N. Metal-Free Nitrogenation of 2-Acetylbiphenyls: Expedi-
tious Synthesis of Phenanthridines. Org. Lett. 2015, 17,
2206− 2209. (d) Natarajan, P.; Chuskit and Priya, D.
Metal-Free, Visible-Light-Promoted Oxidative Radical Cy-
clization of N-Biarylglycine Esters: One-Pot Construction
of Phenanthridine-6-carboxylates in Water. Green Chem.
2019, 21, 4406-4411.
(6)(a) Wang, Q.; Dong, X.; Xiao, T.; Zhou, L.
PhI(OAc)2-Mediated Synthesis of 6-(Trifluoromethyl)phe-
nanthridines by Oxidative Cyclization of 2-Isocyanobi-
phenyls with CF3SiMe3 under Metal-Free Conditions. Org.
Lett. 2013, 15, 4846-4849. (b) Zhang, B.; Mü ck-Lichten-
feld, C.; Daniliuc, C. G.; Studer, A. 6-Trifluoromethyl-
Phenanthridines through Radical Trifluoromethylation of
Isonitriles. Angew. Chem. Int. Ed. 2013, 52, 10792-10795.
(c) Yang, B.; Tian, Q.; Yang, S.-D. Silver-Promoted P-
radical Cyclization Reaction with the Addition to Isoni-
trile. Chin. J. Org. Chem. 2014, 34, 717-721. (d) Zhang,
B.; Studer, A. Recent Advances in the Synthesis of Nitro-
gen Heterocycles via Radical Cascade Reactions Using
Isonitriles as Radical Acceptors. Chem. Soc. Rev. 2015,
44, 3505-3521. (e) Wang, C.-H.; Li, Y.-H.; Yang, S.-D.
Autoxidation Photoredox Catalysis for the Synthesis of 2-
Phosphinoylindoles. Org. Lett. 2018, 20, 2382-2385.
(12)(a) Dhara, S.; Ghosh, M.; Ray, J. K. Synthesis of
Phenanthridines and Analogues via Suzuki Coupling and Con-
densation. Synlett 2013, 24, 2263-2265. (b) Borah, A.;
Gogoi, P. Cascade C-C and C-N Bond Formation: A Straight-
forward Synthesis of Phenanthridines and Fused Quinolines.
Eur. J. Org. Chem. 2016, 2200-2206. (c) Bao, Y.; Wang,
Z.; Chen, C.; Zhu, B.; Wang, Y.; Zhao, J.; Gong, J.; Han,
M.; Liu, C. Palladium-Catalyzed Tandem Cyclization of
Fluorinated Imidoyl Chlorides with 2-Bromophenylboronic
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 15
Acid: Synthesis of 6-Fluoroalkyl-Phenanthridines. Tetra-
hedron 2019, 75, 1450-1456.
(13)Maiti, D.; Halder, A.; Sarkar, S. D. Base-Promoted
Aerobic Oxidation/Homolytic Aromatic Substitution Cascade
toward the Synthesis of Phenanthridines. Adv. Synth. Catal.
2019, 361, 4941-4948.
(14)(a) Borpatra, P. J.; Deka, B.; Deb, M. L.; Baruah,
P. K. Recent Advances in Intramolecular C-O/C-N/C-S bond
formation via C-H Functionalization. Org. Chem. Front.
2019, 6, 3445-3489. (b) Chowdhury, D.; Dana, S.; Mandal,
A.; Baidya, M. A Ruthenium-Catalyzed Free Amine Directed
(5+ 1) Annulation of Anilines with Olefins: Diverse Syn-
thesis of Phenanthridine Derivatives. Chem. Commun. 2019,
55, 11908-11911.
Selective Piperidine Synthesis Exploiting Iodine-Cata-
lyzed Csp3-H Amination under Visible Light. ACS Catal. 2017,
7, 4122-4125. (c) Becker, P.; Duhamel, T.; Martí nez, C.;
Muñiz, K. Designing Homogeneous Bromine Redox Catalysis
for Selective Aliphatic C-H Bond Functionalization. Angew.
Chem. Int. Ed. 2018, 57, 5166-5170. (d) Duhamel, T.; Stein,
C. J.; Martí nez, C.; Reiher, M.; Muñiz, K. Engineering
Molecular Iodine Catalysis for Alkyl-Nitrogen Bond For-
mation. ACS Catal. 2018, 8, 3918-3925. (e) Bosnidou, A.
E.; Muñiz, K. Intermolecular Radical C(sp3)-H Amination
under Iodine Catalysis. Angew. Chem. Int. Ed. 2019, 58,
7485-7489. (f) Duhamel, T.; Martí nez, M. D.; Sideri, I.
K.; Muñiz, K. 1,3-Diamine Formation from an Interrupted
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Hofmann-Lö ffler Reaction: Iodine Catalyst Turnover
(15)(a) Ma, Y.-N.; Guo, C.-Y.; Zhao, Q.; Zhang, J.;
Chen, X. Synthesis of Dibenzothiazines from Sulfides by
One-Pot N,O-Transfer and Intramolecular C-H Amination.
Green Chem. 2018, 20, 2953-2958. (b) Ma, Y.-N.; Bian, Y.;
Liu, X.; Zhang, J.; Chen, X. One-Pot Synthesis of Iodo-
Dibenzothiazines from 2-Biaryl Sulfides. J. Org. Chem.
2019, 84, 450-457. (c) Li, L.; Li, Y.; Zhao, Z.; Luo, H.;
Ma, Y.-N. Facial Syntheses of Bromobenzothiazines via Cat-
alyst-Free Tandem C-H Amination/Bromination in Water. Org.
Lett. 2019, 21, 5995-5999. (d) Ma, Y.-N.; Gao, Y.; Jing,
Y.; Kang, J.; Zhang, J.; Chen, X. Syntheses of Bromo-N-
heterocycles through Dibromohydantoin-Promoted Tandem C-
H Amination/Bromination. J. Org. Chem. 2020, 85, 2918-
2926.
through Ritter-Type Amination. ACS Catal. 2019, 9, 7741-
7745.
(19)(a) Martinez, C.; Bosnidou, A. E.; Allmendinger,
S.; Muniz, K. Towards Uniform Iodine Catalysis: Intramo-
lecular C-H Amination of Arenes under Visible Light. Chem.
Eur. J. 2016, 22, 9929-9932. (b) Xiong, T.; Zhang, Q. New
amination strategies based on nitrogen-centered radical
chemistry. Chem. Soc. Rev. 2016, 45, 3069-3087. (c) Ma,
Y.-N.; Zhang, X.; Yang, S.-D. Tandem Oxidative C-H Amina-
tion and Iodization to Synthesize DifunctionalAtropoiso-
meric P-Stereogenic Phosphinamides. Chem. Eur. J. 2017,
23, 3007-3011. (d) Ma, Y.-N.; Cheng, M.-X.; Yang, S.-D.
Diastereoselective Radical Oxidative C-H Aminations to-
ward Chiral Atropoisomeric (P, N) Ligand Precursors. Org.
Lett. 2017, 19, 600-603.
(20)(a) Hayyan, M.; Hashim, M. A.; AlNashef, I. M. Su-
peroxide Ion: Generation and Chemical Implications. Chem.
Rev. 2016, 116, 3029-3085. (b) Chen, S.; Wan, Q.; Badu-
Tawiah, A. K. Picomole-Scale Real-Time Photoreaction
Screening: Discovery of the Visible-Light-Promoted Dehy-
drogenation of Tetrahydroquinolines under Ambient Condi-
tions. Angew. Chem. Int. Ed. 2016, 55, 9345-9349. (c)
Huang, Y.-Q.; Song, H.-J.; Liu, Y.-X.; Wang, Q.-M. Dehy-
drogenation of N-Heterocycles by Superoxide Ion Generated
through Single-Electron Transfer. Chem. Eur. J. 2018, 24,
2065-2069.
(21)(a) Li, D. J.; Zhao, B. P.; LaVoie, E. J. Ni-
troarylstannanes as Synthons for the Preparation of Phe-
nanthridine and Benzo[ i] phenanthridine Derivatives. J.
Org. Chem. 2000, 65, 2802-2805. (b) Mcburney, R. T.;
Slawin, A. M. Z.; Smart. L. A.; Yu, Y.; Walton, J. C. UV
Promoted Phenanthridine Syntheses from Oxime Carbonate
Derived Iminyl Radicals. Chem. Commun. 2011, 47, 7974-
7976. (c) Linsenmeier, A. M.; Williams, C. M.; Brä se,
S. Synthesis of Phenanthridine Derivatives via Photolysis.
J. Org. Chem. 2011, 76, 9127-9132. (d) Read, M. L.; Gunder-
sen, L.-L. Synthesis of Phenanthridine Derivatives by Mi-
crowave-Mediated Cyclization of o-Furyl(allylamino)arenes.
J. Org. Chem. 2013, 78, 1311-1316. (e) Li, Z.; Fan, F.;
Yang, J.; Liu, Z.-Q. A Free Radical Cascade Cyclization
of Isocyanides with Simple Alkanes and Alcohols. Org. Lett.
2014, 16, 3396-3399. (f) Liu. X.; Qing, Z.; Cheng, P.;
Zheng, X.; Zeng, J.; Xie, H. Metal-Free Photoredox Cata-
lyzed Cyclization of O-(2,4-Dinitrophenyl)oximes to Phe-
nanthridines. Molecules 2016, 21, 1690-1700. (g) Yang, S.-
Y.; Han, W.-Y.; Zhang, D.-L.; Zhou, X.-J.; Bai,
M.; Cui, B.-D.; Wan, N.-W.; Yuan, W.-C.; Chen, Y.-
Z. Synthesis of Phenanthridines through Palladium-Cata-
lyzed Cascade Reaction of 2-Halo-N-M-arylamines with Ben-
zyl Halides/Sulfonates. Eur. J. Org. Chem. 2017, 2017,
996-1003.
(16)Wang, L.; Zhang, Y.; Li, F.; Hao, X.; Zhang, H.-
Y.; Zhao, J. Direct C-H Trifluoromethylation of Quinoxa-
lin-2(1H)-ones under Transition-Metal-Free Conditions.
Adv. Synth. Catal. 2018, 360, 3969-3977.
(17)(a) Freire, R.; Marrero, J. J.; Rodriguez, M. S.;
Suárez, E. Synthesis of Medium-Sized Lactones-Iodosoben-
zene Diacetate an Efficient Reagent for beta-Fragmentation
of Alkoxy Radicals. Tetrahedron Lett. 1986, 27, 383-386.
(b) Togo, H.; Hoshina, Y.; Muraki, T.; Nakayama, H.; Yoko-
yama, M. Study on Radical Amidation onto Aromatic Rings
with (Diacyloxyiodo)arenes. J. Org. Chem. 1998, 63, 5193-
5200. (c) Boto, A.; Hernández, R.; Velázquez, S. M.;
Suá rez, E.; Prangé, T. Stereospecific Synthesis of 1,2-
Dioxolanes by Alkoxy Radical β-Fragmentation of Steroidal
Cyclic Peroxyhemiacetals. J. Org. Chem. 1998, 63, 4697-
4705. (d) Betancor, C.; Freire, R.; Pé rez-Martí n, I.;
Prangé , T.; Suá rez, E. Hydrogen atom transfer methodol-
ogy for the synthesis of C-22, C-23, and C-25 stereoiso-
mers of cephalostatin north 1 side chain from spirostan
sapogenins. Tetrahedron 2005, 61, 2803-2814. (e) Moroda,
A.; Furuyama, S.; Togo, H. Facile Preparation of 3,4-
Dihydro-2,1-benzothiazine 2,2-Dioxides and Related Reac-
tion with 1,3-Diiodo-5,5-dimethylhydantoin under Photo-
chemical Conditions. Synlett 2009, 8, 1336-1340. (f)
Batchu, H.; Bhattacharyya, S.; Batra, S. Iodine-Mediated
Intramolecular Electrophilic Aromatic Cyclization in Al-
lylamines: A General Route to Synthesis of Quinolines,
Pyrazolo[ 4,3-b] pyridines, and Thieno[ 3,2-b] pyridines.
Org. Lett. 2012, 14, 6330− 6333. (g) Kishi, A.; Moriyama,
K.; Togo, H. Preparation of Phenanthridines from o-Cyano-
biaryls via Addition of Organic Lithiums to Nitriles and
Imino Radical Cyclization with Iodine. J. Org. Chem. 2018,
83, 11080-11088. (h) Kobayashi, E.; Kishi, A.; Togo, H.
6-Arylphenanthridines from Aryl o-Biaryl Ketones with
1,1,1,3,3,3-Hexamethyldisilazane and Molecular Iodine.
Eur. J. Org. Chem. 2019, 7335-7347.
(18)(a) Muñ iz, K. Aminations with Hypervalent Iodine.
Top. Curr. Chem. 2015, 373, 105. (b) Zhang, H.; Muñiz, K.
ACS Paragon Plus Environment

Page 15 of 15
1
The Journal of Organic Chemistry
(22) (a) Ca, N. D.; Motti, E.; Mega, A.; Catellani, M.
Thongsornkleeb, C.; Ruchirawat, S. A New Synthetic Ap-
proach to 6-Unsubstituted Phenanthridine and Phenanthri-
dine-Like Compounds under Mild and Metal-Free Conditions.
Org. Biomol. Chem. 2014, 12, 5077-5081. (e) Ghosh, M.;
Ahmed, A; Singha, R.; Ray, J. K. Domino Suzuki Coupling
and Condensation Reaction: an Efficient Strategy towards
Synthesis of Phenanthridines. Tetrahedron. 2015, 56, 353-
355. (f) Annamalai, P.; Hsu, K. C.; Raju, S.; Hsiao, H.
C.; Chou, C. W.; Lin, G. Y.; Hsieh, C. M.; Chen, P. L.;
Liu, Y. H. and Chuang, S. C. Palladium(II)-Catalyzed Mono-
and Bis-alkenylation of N-Acetyl-2-aminobiaryls through
Regioselective C-H Bond Activation. J. Org. Chem. 2018,
83, 3840-3856.
One-Pot Palladium-Catalyzed Synthesis of Selectively Sub-
stituted Phenanthridines by Sequential Aryl-Aryl and Heck
Couplings, Aza-Michael and Retro‐Mannich Reactions. Adv.
2
3
4
5
6
7
8
9
Synth. Catal. 2010, 352, 1451-1454. (b) Blanchot, M.; Can-
dito, D. A.; Larnaud, F.; Lautens, M. Formal Synthesis of
Nitidine and NK109 via Palladium-Catalyzed Domino Direct
Arylation/N-Arylation of Aryl Triflates. Org. Lett. 2011,
13, 1486-1489. (c) Liu, Y. Y.; Song, R. J.; Wu, C. Y.;
Gong L. B.; Hu, M.; Wang, Z. Q.; Xie, Y. X.; Li, J. H.
Palladium-Catalyzed Oxidative C-C Bond Cleavage Cycliza-
tion of Biaryl-2-amines with Alkenes Involving C-H Ole-
fination and Carboamination. Adv. Synth. Catal. 2012, 354,
347-353. (d) Tummatorn, J.; Krajangsri, S.; Norseeda, K.;
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment