Post on 02-Dec-2018
S1
Supporting Information
Metal-Free Reduction of Aromatic Nitro Compounds to Aromatic
Amines with B2pin2 in Isopropanol
Hongtao Lu,† Zhiyue Geng,
† Jingya Li,
‡ Dapeng Zou,
*,† Yusheng Wu,
*,‡,§ and Yangjie
Wu*,†
†The College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052,
People’s Republic of China
‡ Tetranov Biopharm, LLC. and Collaborative Innovation Center of New Drug Research and Safety
Evaluation, Zhengzhou, 450052, People’s Republic of China
§Tetranov International, Inc. 100 Jersey Avenue, Suite A340, New Brunswick, New Jersey 08901,
United States
Email: zdp@zzu.edu.cn;
wyj@zzu.edu.cn;
yusheng.wu@tetranovglobal.com
Table of Contents
1. General information…………………………………………………...…..S2
2. Optimization of the reaction conditions (Table S1-S5)………………………S2
3. General procedure………..…………………………..………………………S4
4. Preliminary mechanistic studies…………….…………………………S4
4.1 Control experiments…………………………………………………….S5
4.2 Dosage of B2pin2 effect on the reduction…...……………………………S5
4.3 1 1B NMR exper iment…………………………………… .………S5
5. Analytical data and copies of NMR spectra…………………..……...……....S6
6. References……………………………………………….…………………..S35
S2
1. General information
All reactions were performed in dried glass reaction tube equipped with a magnetic stir bar under
air atmosphere. Flash column chromatography was performed using silica gel (60-Å pore size,
32-63 µm, standard grade). Analytical thin-layer chromatography was performed using glass
plates pre-coated with 0.25 mm 230-400 mesh silica gel impregnated with a fluorescent indicator
(254 nm). Thin layer chromatography plates were visualized by exposure to ultraviolet light. The
bottled solvents were used in the reactions untreated. The transformation progress was indicated
by GC-MS using Thermo Fisher Scientific DSQ II. NMR spectra were obtained on Bruker
AVANCE III systems using CDCl3 as solvent, TMS as internal standard substance, at 400 MHz for 1H NMR, 100 MHz for
13C NMR, and 128 MHz for
11B NMR.
11B NMR spectra were referenced
by an external BF3.Et2O sample.
2. Optimization of the reaction conditions (Table S1-S5)
Table S1 Base effect on the reduction of aromatic nitro compounds to amines with B2pin2a
NO2 NH2base (2.0 eq)
MeOH, 80 °C, 8 h BrBr
B2pin2
1a 2 3a
entry base yield (%)b
1 AcOK trace
2 K2CO3 trace
3 Na2CO3 trace
4 Cs2CO3 85
5 KOtBu 89
6 NaOtBu 75
7 LiOtBu 74
8 MeONa 80
9 TEA n.r.c
10 DIPEA n.r.c
aReaction conditions: 1a (1.0 mmol), 2 (3.0 mmol), base (2.0 mmol), MeOH (4.0 mL), 80 °C, 8 h.
bHPLC yield.
cn.r. = no reaction.
Table S2 Solvent effect on the reduction of aromatic nitro compounds to amines with B2pin2a
entry solvent yield (%)b
NO2 NH2KOtBu (2.0 eq)
solvent, 80 °C, 8 hBrBr
B2pin2
1a 2 3a
S3
1 EtOH 89
2 iPrOH 91
3 tBuOH 84
4 dioxane 12
5 THF 9
6 toluene 13
7 H2O trace
aReaction conditions: 1a (1.0 mmol), 2 (3.0 mmol), base (2.0 mmol), solvent (4.0 mL), 80 °C, 8 h.
bHPLC yield.
Table S3 Ratio of base and B2pin2 effect on the reduction of aromatic nitro compounds to aminesa
NO2 NH2
BrBr
B2pin2
1a 2 3a
KOtBu
iPrOH, 100 °C, 8 h
entry tBuOK(x eq) B2pin2(y eq) yield (%)b
1 2.0 3.5 94
2 1.5 3.1 94
3 1.2 3.1 95
4 1.0 3.1 90
5 0.5 3.1 85
aReaction conditions: 1a (1.0 mmol), 2 (x mmol), base (y mmol), iPrOH (4.0 mL), 100 °C, 8 h.
bHPLC yield.
Table S4 Temperature effect on the reduction of aromatic nitro compounds to aromatic amines
with B2pin2a
NO2 NH2KOtBu, iPrOH
temp, timeBrBr
B2pin2
1a 2 3a
entry temp (oC) yield (%)
b
1c 30
trace
2c 50
65
3c 80
88
4d 100
95
5d 110
96(87)e
aReaction conditions: 1a (1.0 mmol), 2 (3.1 mmol), base (1.2 mmol), iPrOH (4.0 mL).
bHPLC yield.
c24 h.
d2 h.
eIsolated yield in parentheses.
S4
Table S5 Boron sources effect on the reduction of aromatic nitro compounds to aminesa
KOtBu, iPrOH
temp, 8 h
NO2 NH2
BrBr
Boron sources
1a 2 3a
OB
O
H
D E
HOB
OH
OH
A
OO
B
OB
O
O
B
O
C
NaBH4 BH3.THF
F
entry temp (oC) boron sources yield (%)
b
1 100 A n.r.
2 100 B n.r.
3 100 C n.r.
4c 60
D 42
5d 40
E 35
6d 100
F trace
aReaction conditions: 1a (1.0 mmol), 2 (3.1 mmol), base (1.2 mmol), iPrOH (4.0 mL), 8 h.
bHPLC yield.
cMeOH as solvent.
dTHF as solvent.
3. General procedure
A dried glass reaction tube equipped with a magnetic stir bar was charged with aromatic nitro
compounds (1.0 mmol, 1.0 equiv), B2pin2 (3.1 mmol, 3.1 equiv) and KOtBu (1.2 mmol, 1.2 equiv),
iPrOH (4.0 mL, without any purification) was added and the mixture was then stirred in
the preheated oil base at 110 °C for 2 h. The reaction progress was monitored by TLC. The yields
of standard reaction were obtained by HPLC. After cooling to room temperature, the crude
production was diluted with ethyl acetate and then washed with saturated NaCl solution. The
organic layers dried over anhydrous Na2SO4, concentrated in vacuo, and purified by flash column
chromatograph to give the pure products. The products were characterized by 1H NMR,
13C NMR,
GC-MS and LC-MS.
4. Preliminary mechanistic studies
4.1 Controll experiment
S5
NO2NH2
iPrOH110 °C, 8 h
BrBr
1a 3a
KOtBu (1.1 eq)
NO2NH2
BrBr
1a 3a
B2pin2 (3.1 eq)
iPrOH110 °C, 8 h
a)
b)
trace
no reaction
Both B2pin2 and KOtBu showed almost no reaction when used alone under optimized conditions.
4.2 Dosage of B2pin2 effect on the reduction of aromatic nitro compounds to amines a
iPrOH110 °C, 2 h
NO2 NH2
BrBrB2pin2
1a 2 3a
KOtBu (1.1 eq)
entry B2pin2 (eq) yield (%)b
1 3.1 96
2 2.5 90
3c 2.0
85
4c 1.0
60
5c 0.5
50
aReaction conditions: 1a (1.0 mmol), KOtBu (1.2 mmol), iPrOH (4.0 mL), 2 h.
bHPLC yield.
c8 h.
These experimental results show that more than 3.0 equivent of B2pin2 are necessary for the
complete transformation of starting material 1-bromo-4-nitrobenzene 1a.
4.3 11
B NMR experiment
11B NMR spectrum of the reaction mixture was obtained prior to an aqueous workup of the reaction
(Figure S1, c), and 2-isopropoxy -4,4,5,5-tetramethyl-1,3,2-dioxaborolane have the same chemical
shift at 11
B NMR spectrum (21 ppm). Besides, bis(pinacolato)diboron (B2pin2) was consumed
completely in this condition.1
S6
Figure S1, a
Figure S1, b
Figure S1, c
It is important to point out that further mechanisms could be hypothesized, but we present here the
simplest ones as basic hypothesis. The reduction of nitro group is believed to involve several
intermediates including nitroso, hydroxylamine, azoxy, and diazo. However, all attempts to detect
these intermediates under our conditions by GC-MS or LC-MS were unsuccessful. Only the final
product could be observed. Most likely the intermediates are converted into the final amines very
rapidly without building sufficient concentration.2
5. Analytical data and copies of NMR spectra
Br
H2N 3a
4-Bromoaniline (3a).3
Brown solid (149 mg, yield 87%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.23 (d, J = 8.7 Hz, 2 H), 6.56 (d, J = 8.7 Hz,
2 H), 3.65 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 145.4, 132.0, 116.7, 110.2. GC-MS
(EI, m/z): [M]+
170.7 (100%), [M+2]+
172.7 (97%).
S7
NH2
Br3b
2-Bromoaniline (3b).4
Brown solid (142 mg, yield 83%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.40 (dd, J = 8.0, 1.2 Hz, 1 H), 7.10 (dt, J =
7.4, 1.4 Hz, 1 H), 6.76 (dd, J = 8.0, 1.4 Hz, 1 H), 6.61 (dt, J = 7.5, 1.4 Hz, 1 H), 4.07 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 144.1, 132.6, 128.3, 119.4, 115.7, 109.3. GC-MS (EI, m/z):
[M]+
170.7 (100%), [M+2]+
172.7 (97%).
F
H2N 3c
4-Fluoroaniline (3c).5
Yellow liquid (66 mg, yield 60%), flash chromatography eluting with petroleum ether/ethyl acetate
(8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 6.87-6.83 (m, 2 H), 6.63-6.60 (m, 2 H), 3.53 (br s, 2
H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 156.4 (d, J = 234.2 Hz), 142.4 (d, J = 2.1 Hz), 116.1
(d, J = 29.5 Hz), 115.7 (d, J = 117.1 Hz). GC-MS (EI, m/z): [M]+
110.8.
H2N
Cl
3d
4-Chloroaniline (3d).3
Brown solid (109 mg, yield 86%), flash chromatography eluting with petroleum ether/ethyl acetate
(8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.09 (d, J = 8.7 Hz, 2 H), 6.60 (d, J = 8.7 Hz, 2 H),
3.64 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 145.0, 129.1, 123.2, 116.2. LC-MS (ESI,
m/z): [M+H]+ 128.2
(100%), [M+2+H]
+ 130.2
(32%).
NH2
I
3e
3-Iodoaniline (3e).4
Yellow liquid (194 mg, yield 89%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.08-7.04 (m, 2 H), 6.85 (t, J = 7.9 Hz, 1 H),
6.63-6.60 (m, 1 H), 3.64 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 147.7, 130.8, 127.5,
123.7, 114.3, 94.9. LC-MS (ESI, m/z): [M+H]+ 220.1.
Br
NH2
Cl
3f
2-Bromo-5-chloroaniline (3f).6
Yellow liquid (184 mg, yield 90%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.03 (d, J = 8.4 Hz, 1 H), 6.75 (d, J = 2.4 Hz,
1 H), 6.59 (dd, J = 8.4, 2.4 Hz, 1 H), 4.14 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ =
145.0, 133.9, 133.3, 119.3, 115.2, 107.0. LC-MS (ESI, m/z): [M+H]+ 206.1 (66%), [M+2+H]
+
S8
208.0 (100%), [M+4+H]+ 210.0 (32%).
Br
NH2
Cl
3g
3-Bromo-4-chloroaniline (3g).
Brown solid (180 mg, yield 88%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.17 (d, J = 8.8 Hz, 1 H), 6.94 (d, J = 2.8 Hz,
1 H), 6.65 (dd, J = 8.4, 2.4 Hz , 1 H), 3.70 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ =
146.0, 130.5, 123.1, 122.6, 119.5, 115.2. LC-MS (ESI, m/z): [M+H]+
206.1 (66%), [M+2+H]+
208.0 (100%), [M+4+H]+ 210.0 (32%).
Br
NH2 3h
2-Bromo-3-methylaniline (3h).7
Yellow liquid (168 mg, yield 91%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 6.99 (t, J = 7.8 Hz, 1 H), 6.64-6.60 (m, 2 H),
4.10 (br s, 2 H), 2.37 (s, 3 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 144.3, 138.8, 127.4, 120.3,
113.1, 112.2, 23.6. LC-MS (ESI, m/z): [M+H]+ 186.1 (100%), [M+2+H]
+ 188.1 (97%).
NH2
OBr
3i
3-Bromo-5-methoxyaniline (3i).8
Yellow liquid (181 mg, yield 90%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 6.47-6.44 (m, 2 H), 6.13 (t, J =2.1 Hz, 1 H),
3.74 (s, 3 H), 3.70 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 161.3, 148.6, 123.3, 110.9,
107.4, 99.9, 55.4. LC-MS (ESI, m/z): [M+H]+
(100%), 204.1 [M+2+H]+
(97%).
OBn
NH23k
4-(Benzyloxy) aniline (3k).9
Brown solid (173 mg, yield 87%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.42-7.28 (m, 5 H), 6.81 (d, J =8.7 Hz, 2 H),
6.63 (d, J =8.7 Hz, 2 H), 4.99 (s, 2 H), 3.42 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ =
152.0, 140.2, 137.5, 128.5, 127.8, 127.5, 116.4, 116.1, 70.8. GC-MS (EI, m/z): [M]+198.8.
S9
OBz
NH23l
4-Aminophenyl benzoate (3l).10
Brown solid (106 mg, yield 50%), flash chromatography eluting with petroleum ether/ethyl
acetate (8:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 8.19-8.17 (m, 2 H), 7.62 (t, J = 7.4 Hz, 1 H),
7.49 (t, J = 7.8 Hz, 2 H), 7.00 (d, J = 8.8 Hz, 2 H), 6.71 (d, J = 8.8 Hz, 2 H), 3.66 (br s, 2 H). 13
C
NMR (100 MHz, CDCl3, ppm): δ = 165.7, 144.3, 143.1, 133.4, 130.1, 129.9, 128.5, 122.3, 115.7.
GC-MS (EI, m/z): [M]+ 212.8.
HN
O OH
O
3m
4-Acetamidobenzoic acid (3m).11
3m was isolated as 4-acetamidobenzoic acid. White solid (159 mg, yield 89%). 1H NMR (400
MHz, DMSO-d6, ppm): δ = 12.67 (br s, 1H), 10.24 (s, 1H), 7.88 (d, J = 8.4 Hz, 2H), 7.69 (d, J =
8.4 Hz, 2H), 2.09 (s, 3H). 13
C NMR (100 MHz, DMSO-d6, ppm): δ = 168.8, 166.9, 143.3, 130.3,
124.9, 118.1, 24.1. LC-MS (ESI, m/z): [M+H]+ 180.6.
NH2
O O
3n
Methyl-4-aminobenzoate (3n).9
3n was isolated as a mixture of isopropyl 4-aminobenzoate (1:0.7). Brown solid (128 mg,
yield 85%), flash chromatography eluting with petroleum ether/ethyl acetate (6:1). 1H NMR (400
MHz, CDCl3, ppm): δ = 7.84 (d, J = 8.6 Hz, 2 H), 6.64 (d, J = 8.6 Hz, 2 H), 4.03 (br s, 2 H), 3.85
(s, 3 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 167.2, 150.9, 131.5, 119.7, 113.7, 51.6. GC-MS
(EI, m/z): [M]+ 151.1.
NH2
O N
O
3o
4-(4-Aminobenzoyl)morpholine (3o).9
Brown solid (164 mg, yield 80%), flash chromatography eluting with petroleum ether/ethyl
S10
acetate (6:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.26 (d, J = 8.5 Hz, 2 H), 6.64 (d, J = 8.5 Hz,
2 H), 3.94 (br s, 2 H), 3.68 (br s, 4 H), 3.64 (br s, 4 H). 13
C NMR (100 MHz, CDCl3, ppm): δ =
170.9, 148.4, 129.4, 124.5, 114.2, 67.0. LC-MS (ESI, m/z): [M+H]+ 207.6.
NH2
CN
3p
3-Aminobenzonitrile (3p).9
Brown solid (100 mg, yield 85%), flash chromatography eluting with petroleum ether/ethyl
acetate (6:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.22 (t, J = 7.8 Hz, 1 H), 7.02-7.01 (m, 1 H),
6.90-6.85 (m, 2 H), 3.88 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 147.0, 130.1, 122.0,
119.2, 119.1 117.4, 113.0. GC-MS (EI, m/z): [M]+
118.1.
NH2 3q
4-Ethynylaniline (3q).12
Brown solid (70 mg, yield 60%), flash chromatography eluting with petroleum ether/ethyl acetate
(6:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.3 (d, J = 8.6 Hz, 2 H), 6.59 (d, J = 8.6 Hz, 2 H),
3.81 (br s, 2 H), 2.95 (s, 1 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 147.0, 133.5, 114.6, 111.4,
84.4, 74.9. LC-MS (ESI, m/z): [M+H]+ 118.1.
NH23s
Aniline (3s).3
Brown liquid (74 mg, yield 80%), flash chromatography eluting with petroleum ether/ethyl acetate
(6:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.15 (t, J = 7.4 Hz, 2 H), 6.75 (t, J = 7.4 Hz, 1 H),
6.67 (d, J = 7.5 Hz, 2 H), 3.53 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 146.4, 129.3,
118.6, 115.1. GC-MS (EI, m/z): [M]+ 93.1.
N NH2
Br
3t
5-Bromopyridin-2-amine (3t).13
Brown solid (155 mg, yield 90%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:2). 1H NMR (400 MHz, CDCl3, ppm): δ = 8.10 (d, J = 2.4 Hz, 1 H), 7.39 (dd, J = 8.4,
2.4 Hz, 1 H), 6.42 (d, J = 8.8 Hz, 1 H), 4.47 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ =
157.0, 148.8, 140.1, 110.0, 108.4. GC-MS (EI, m/z): [M]+
172.7 (100%), [M+2]+
174.7 (97%).
N Cl
H2N
3u
6-Chloro-5-methylpyridin-3-amine (3u).14
S11
Brown solid (126 mg, yield 89%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:2). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.70 (d, J = 2.8 Hz, 1 H), 6.88 (d, J = 2.8 Hz,
1 H), 3.63 (br s, 2 H), 2.29 (s, 3 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 141.8, 140.7, 133.9,
132.3, 125.6, 19.6. LC-MS (ESI, m/z): [M+H]+ 143.2 (100%), [M+2+H]
+ 145.2 (32%).
N Cl
H2N
Cl 3v
2,6-Dichloropyridin-3-amine (3v).14
Brown solid (119 mg, yield 73%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:2). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.08-7.01 (m, 2 H), 4.11 (brs, 2 H).
13C NMR
(100 MHz, CDCl3, ppm): δ = 138.7, 137.6, 134.9, 125.0, 123.6. LC-MS (ESI, m/z): [M+H]+ 163.1
(100%), [M+2+H]+ 165.1
(64%).
N O
H2N
Cl 3w
2-Chloro-6-methoxypyridin-3-amine (3w).14
Brown solid (119 mg, yield 75%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:2). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.07 (d, J = 8.4 Hz, 1 H), 6.56 (d, J = 8.4 Hz,
1 H), 3.86 (s, 3 H), 3.68 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 156.4, 133.2, 132.3,
128.0, 110.1, 53.9. LC-MS (ESI, m/z): [M+H]+
159.2 (100%), [M+2+H]+
161.2 (32%).
N
H2N
3x
Quinolin-6-amine (3x).4
Brown solid (130 mg, yield 90%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:1). 1H NMR (400 MHz, CDCl3, ppm): δ = 8.63 (dd, J = 4.2, 1.6 Hz, 1H), 7.93 (d, J =
9.0 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.26 (dd, J = 8.1, 4.2 Hz, 1H), 7.16 (dd, J = 8.8, 2.4 Hz, 1H),
6.89 (d, J = 2.6 Hz, 1 H), 3.90 (br s, 2 H). 13
C NMR (100 MHz, CDCl3, ppm): δ = 146.6, 144.7,
143.2, 133.9, 130.3, 129.8, 121.7, 121.4, 107.4. LC-MS (ESI, m/z): [M+H]+ 145.2.
H2N
NH
N
3y
1H-indazol-5-amine (3y).15
Brown solid (117 mg, yield 88%), flash chromatography eluting with petroleum ether/ethyl
acetate (1:1). 1H NMR (400 MHz, DMSO-d6, ppm): δ = 12.56 (br s, 1 H) 7.72 (s, 1 H), 7.24 (d, J
= 8.6 Hz, 1 H), 6.78 (dd, J = 8.6, 1.8 Hz, 1 H), 6.75 (s, 1 H), 4.75 (br s, 2 H). 13
C NMR (100 MHz,
DMSO, ppm): δ = 142.1, 131.3, 123.8, 117.9, 110.1, 100.3. LC-MS (ESI, m/z): [M+H]+ 134.2.
S12
Figure 1 1H NMR of compound 3a
Figure 2 13
C NMR of compound 3a
S13
Figure 3 1H NMR of compound 3b
Figure 4 13
C NMR of compound 3b
S14
Figure 5 1H NMR of compound 3c
Figure 6 13
C NMR of compound 3c
S15
Figure 7 1H NMR of compound 3d
Figure 8 13
C NMR of compound 3d
S16
Figure 9 1H NMR of compound 3e
Figure 10 13
C NMR of compound 3e
S17
Figure 11 1H NMR of compound 3f
Figure 12 13
C NMR of compound 3f
S18
Figure 13 1H NMR of compound 3g
Figure 14 13
C NMR of compound 3g
S19
Figure 15 1H NMR of compound 3h
Figure 16 13
C NMR of compound 3h
S20
Figure 17 1H NMR of compound 3i
Figure 18 13
C NMR of compound 3i
S21
Figure 19 1H NMR of compound 3k
Figure 20 13
C NMR of compound 3k
S22
Figure 21 1H NMR of compound 3l
Figure 22 13
C NMR of compound 3l
S23
Figure 23 1H NMR of compound 3m
Figure 24 13
C NMR of compound 3m
S24
Figure 25 1H NMR of compound 3n
Figure 26 13
C NMR of compound 3n
S25
Figure 27 1H NMR of compound 3o
Figure 28 13
C NMR of compound 3o
S26
Figure 29 1H NMR of compound 3p
Figure 30 13
C NMR of compound 3p
S27
Figure 31 1H NMR of compound 3q
Figure 32 13
C NMR of compound 3q
S28
Figure 33 1H NMR of compound 3s
Figure 34 13
C NMR of compound 3s
S29
Figure 35 1H NMR of compound 3t
Figure 36 13
C NMR of compound 3t
S30
Figure 37 1H NMR of compound 3u
Figure 38 13
C NMR of compound 3u
S31
Figure 39 1H NMR of compound 3v
Figure 40 13
C NMR of compound 3v
S32
Figure 41 1H NMR of compound 3w
Figure 42 13
C NMR of compound 3w
S33
Figure 43 1H NMR of compound 3x
Figure 44 13
C NMR of compound 3x
S34
Figure 45 1H NMR of compound 3y
Figure 46 13
C NMR of compound 3y
S35
6. References
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A. J.; Clark, T. B. Org. Lett. 2014, 16, 6056-6059.
2. De Noronha, R. G.; Romão, C. C.; Fernandes, A. C. J. Org. Chem. 2009, 74, 6960-6964.
3. Feng, Y.-S.; Ma, J.-J.; Kang, Y.-M.; Xu, H.-J. Tetrahedron, 2014, 70, 6100-6105.
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