Ag-promoted azido-carbocyclization of activated alkenes via C - H bond cleavage

Article abstract of DOI:10.1002/asia.201300960

A sliver of silver: An efficient silver-promoted azido-carbocyclization of activated alkenes via a radical pathway has been developed. Azido oxindoles, which hold great potential for subsequent transformation of the azido unit, are efficiently constructed by this protocol. Radical addition and C - H functionalization processes are involved in this transformation with the formation of C - N and C - C bonds. Silver is observed to promote the single-electron oxidation process. Copyright

Full text of DOI:10.1002/asia.201300960

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013
À
Ag-Promoted Azido-Carbocyclization of Activated Alkenes via C H Bond
Cleavage
[
a]
[a]
[a]
[a, b]
Yizhi Yuan, Tao Shen, Kui Wang, and Ning Jiao*
asia_201300960_sm_miscellaneous_information.pdf

Table of Contents
General Remarks.
S1
S2
Screening with Different Reaction Conditions.
Substrate Scope and Mechanistic Experiments
Experimental Procedure and Characterization Data for
Products
S3-S4
S5-S11
1
13
H NMR and C NMR Spectra of Products
S12-S62

General Remarks.
1
All manipulations were conducted with a standard Schlenk technique. H-NMR
spectra were recorded on a Bruker AVANCE III-400 spectrometers. Chemical shifts
(
in ppm) were referenced to tetramethylsilane (δ = 0 ppm) in CDCl
standard or in DMSO. 13C-NMR spectra were obtained by using the same NMR
spectrometers and were calibrated with CDCl (δ = 77.00 ppm) or DMSO (39.5).
3
as an internal
3
High Resolution Mass spectra were recorded using a Fourier Transform Ion Cyclotron
Resonance Mass Spectrometer (APEX IV, Bruker). Unless otherwise noted, materials
obtained from commercial suppliers were used without further purification.
S1

Table S1. Screening with Different Reaction Conditions for Azido Oxindole
Formation.[a]
oxidant
Cat. (10 mol%)
N3
O
+
TMSN3
o
MeCN, 80 C
N
O
N
24 h, Ar
1
a
2a
yield of 2a (%)b
recovery of 1a (%)b
entry
Cat. (10 mol%)
AgNO3
oxidant (equiv.)
1c
2c
3c
4c
5c
6c
7c
8c
9c
Ce(SO ) (2.0)
60
42
45
39
49
53
16
28
47
43
62
32
40
37
41
32
21
47
28
28
30
4 2
AgOAc
AgOCN
Ce(SO4)2 (2.0)
Ce(SO4)2 (2.0)
Ag CO3
Ce(SO ) (2.0)
4 2
2
CoCl2
Ce(SO ) (2.0)
4 2
Cu(OAc)2
Ce(SO4)2 (2.0)
Ce(SO4)2 (2.0)
FeBr3
FeCl2
Ce(SO ) (2.0)
4 2
Mn(OAc)3 2H2O
CuI
Ce(SO4)2 (2.0)
Ce(SO4)2 (2.0)
Ce(SO4)2 (2.0)
Ce(SO ) (2.5)
1
0c
1d
2
AgNO3
1
1
1
1
1
1
1
29
0
100 (96)e
37
AgNO3
4
2
3
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
AgNO3
none
CAN (2.5)
PIDA (2.5)
trace
6
4
66
5
NaIO (2.5)
13
73
60
N.D.
79
26
21
76
67
4
6
K S O (2.5)
33
2
2
8
7
DDQ (2.5)
N.D.
18
TBHP (2.5)
N.D.
9f
Ce(SO ) (2.5)
28
1
2
2
4 2
0
1
Ce(SO4)2 (2.5)
none
58
4
AgNO3
AgNO3
2
2
2g
3h
none
7
AgNO3
AgNO3
Ce(SO ) (2.5)
80
82
19
0
4 2
2 i
4
Ce(SO ) (2.5)
4 2
[
3
a] Reaction conditions: 1a (0.30 mmol), TMSN (2.0 equiv.), Cat. (10 mol%), oxidant (equiv.) and MeCN (3.5
o
mL), stirred at 80 C under argon atmosphere for 24 h. N.D. = not determined, TMS = trimethylsilyl, CAN = ceric
ammonium nitrate, PIDA = phenyliodine diacetate, DDQ = 2,3-dichloro-5,6-dicyanobenzoquinone, TBHP =
1
tert-butyl hydrogen peroxide (anhydrous, about 5.5 M in decane). [b] Determined by H NMR. [c] The reaction
was stirred for 12 h. [d] The reaction was stirred for 36 h. [e] The number in parenthesis is isolated yield. [f] The
reaction was carried out under O
2
. [g] 1.5 equiv. of AgNO
was used.
3 3 3
was employed. [h] NaN instead of TMSN was used.
[
i] Togni's azide reagent instead of TMSN
3
S2

Table S2. Silver Promoted Polysubstituted Azido Oxindole Formation.a
R3
N3
R3
AgNO (10 mol%)
3
R1
TMSN , Ce(SO )
3
4 2
R1
O
o
N
O
MeCN, 80 C
4 h, Ar
N
R2
2
R2
2
1
N3
N3
N3
N3
Br
O
O
O
N
N
N
N
Et
Bn
2c: 71%b
Boc
H
2
b: 90%
2d: 0%
2e: 0%
1
2
2
2
2
f: R = Me
75%
N3
1
t-
N3
1
g:R = Bu
69%
90%
91%
88%
2m: R = F 85%
R1
R1
1
1
h:R = NO
2n: R = Cl 93%
2
O
1
O
1
i: R = CF
2o: R = Br 88%
3
N
N
1
1
2
j: R = CN
2p: R = I
88%
1
2
k:R = CO2Me 75%
1
2
l: R = CF3O 86%
N3
N3
N3
F
N3
+
O
O
O
O
N
N
N
N
F
Br
2
q + 2q': 87% (1 : 1.4)b
2r: 54%
2s: 74%
AcO
N3
Ph
Bn
N3
N3
F
N3
O
O
O
O
N
N
2w: 81%
N3
N
N
F
2
t: 80%b
2u: 70%
2v: 86%
N3
N3
O
O
O
N
N
N
2x: 63%
2y: 62%
2a: 87%c
[a] Reaction conditions: see entry 12, Table S1. Isolated yields. [b] The reaction was stirred for 36 h. [c] The reaction was
performed in gram scale.
S3

Table S3. Some Substrates that Cannot Give Corresponding Products under Optimal
Condition.
Mechanistic Experiments:
TEMPO = 2,2,6,6-Tetramethylpiperidinooxy
BHT = 2,6-di-tert-butyl-4-methylphenol
S4

Experimental Section:
Typical Procedure for the Synthesis of Substrates:
[
S1]
Method A: Substrate 1 was prepared according to literatures.
[S2]
Method B: Substrate 1 was prepared according to literature.
[
S2, S3]
Method C: Substrates 1u and 1v were prepared according to literatures.
[
S1]
Method D: Substrate 1w was prepared according to literature.
General Procedure for the Synthesis of Azido Oxindoles:
1
3 4 2
(0.30 mmol), AgNO (0.030 mmol, 5.1 mg) and Ce(SO ) (0.75 mmol, 249.2 mg) were added to
a Schlenk tube with a magnetic bar and charged with argon for 3 times. 3.5 mL MeCN was added
o
followed by the addition of TMSN
3
(0.60 mmol, 69.1 mg). The mixture was heated to 80 C for 24
hours (or 36 hours for 1c, 1q, 1t). The reaction mixture was diluted with EtOAc (5 mL) and
filtered. The filtrate was concentrated in vacuo giving the resulting material, which was purified
by column chromatography to give product 2.
S5

Analytical Data for Compounds 2, 3, 5 & 7:
3
-(Azidomethyl)-1,3-dimethylindolin-2-one (2a):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.32 (td, J = 7.6, 1.2 Hz, 1 H), 7.28
(
d, J = 7.6, 1 H), 7.10 (td, J = 7.6, 0.8 Hz, 1 H), 6.88 (d, J = 7.6 Hz, 1 H),
3
1
.66-3.60 (m, 2 H), 3.23 (s, 3 H), 1.37 (s, 3 H); 13C NMR: (100 MHz, CDCl
3
) δ
78.1, 143.4, 131.3, 128.6, 122.9, 122.7, 108.3, 57.1, 48.7, 26.3, 20.4; IR: (KBr)
-
1
ν
max 2929, 2103, 1714, 1614, 1472, 754 cm ; HRMS m/z (ESI) calcd. for
+
C
11
H
13
N
4
O (M + H) 217.1084, found 217.1085.
3
-(Azidomethyl)-1-ethyl-3-methylindolin-2-one (2b):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.33-7.27 (m, 2 H), 7.09 (t, J = 7.4
Hz, 1 H), 6.90 (d, J = 8.0 Hz, 1 H), 3.86-3.71 (m, 2 H), 3.62 (s, 2 H), 1.36 (s, 3
H), 1.28 (t, J = 7.2 Hz, 3 H); 13C NMR: (100 MHz, CDCl
) δ 177.7, 142.5,
31.6, 128.6, 123.1, 122.5, 108.4, 57.3, 48.6, 34.7, 20.3, 12.5; IR: (KBr) νmax
3
1
2
-
1
977, 2103, 1709, 1613, 1490, 1453 cm ; HRMS m/z (ESI) calcd. for
+
C
12
H
15
N
4
O (M + H) 231.1240, found 231.1233.
3
-(Azidomethyl)-1-benzyl-3-methylindolin-2-one (2c):
1
Colorless oil. H NMR : (400 MHz, CDCl
3
) δ 7.31-7.24 (m, 6 H), 7.19 (t, J =
7
1
.6 Hz, 1 H), 7.06 (t, J = 7.4 Hz, 1 H), 6.73 (d, J = 8.0 Hz, 1 H), 5.02 (d, J =
1
3
5.6 Hz, 1 H), 4.86 (d, J = 15.6 Hz, 1 H), 3.71 (s, 2 H), 1.43 (s, 3 H); C NMR:
) δ 178.3, 142.5, 135.6, 131.3, 128.8, 128.6, 127.6, 127.0,
22.9, 122.7, 109.4, 57.3, 48.8, 43.7, 20.6; IR: (KBr) νmax 2927, 2102, 1709,
(
100 MHz, CDCl
3
1
1
-
1
17 4
612, 1490, 1181 cm ; HRMS m/z (ESI) calcd. for C17H N
O (M + H)+
2
93.1397, found 293.1390.
3
-(Azidomethyl)-1,3,5-trimethylindolin-2-one (2f):
1
N3 Yellow oil. H NMR : (400 MHz, CDCl
) δ 7.12-7.09 (m, 2 H), 6.77 (d, J =
3
8
.0 Hz, 1 H), 3.62 (s, 2 H), 3.21 (s, 3 H), 2.36 (s, 3 H), 1.36 (s, 3 H); 13C
NMR: (100 MHz, CDCl ) δ 178.0, 141.0, 132.3, 131.3, 128.8, 123.8, 108.0,
7.2, 48.7, 26.3, 21.0, 20.4; IR: (KBr) νmax 2926, 2102, 1715, 1621, 1603,
O
3
N
5
1
-
1
+
2f
15 4
500, 1062 cm ; HRMS m/z (ESI) calcd. for C12H N O (M + H) 231.1240,
found 231.1235.
3
-(Azidomethyl)-5-(tert-butyl)-1,3-dimethylindolin-2-one (2g):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.36-7.33 (m, 2 H), 6.82 (d, J
=
8.0 Hz, 1 H), 3.65-3.57 (m, 2 H), 3.22 (s, 3 H), 1.39 (s, 3 H), 1.33 (s, 9
H); 13C NMR: (100 MHz, CDCl
) δ 178.3, 146.1, 141.0, 131.0, 125.2,
3
1
1
20.2, 107.7, 57.3, 48.9, 34.6, 31.5, 26.3, 20.4; IR: (KBr) νmax 2963, 2100,
-
1
21 4
716, 1621, 1500, 1061 cm ; HRMS m/z (ESI) calcd. for C15H N O (M
+
+
H) 273.1710, found 273.1709.
3
-(Azidomethyl)-1,3-dimethyl-5-nitroindolin-2-one (2h):
S6

1
Yellow oil. H NMR : (400 MHz, CDCl
H), 8.16 (d, J = 2.0 Hz, 1 H), 6.96 (d, J = 8.8 Hz, 1 H), 3.72 (s, 2 H), 3.30
s, 3 H), 1.42 (s, 3 H); 13C NMR: (100 MHz, CDCl
) δ 178.2, 149.1,
43.5, 132.2, 125.9, 118.9, 107.9, 56.7, 48.6, 26.8, 20.2; IR: (KBr) νmax
3
) δ 8.29 (dd, J = 8.6, 2.0 Hz, 1
(
3
1
2
-
1
932, 2106, 1727, 1614, 1520, 1458 cm ; HRMS m/z (ESI) calcd. for
+
11 12 5 3
C H N O (M + H) 262.0935, found 262.0929.
3
-(Azidomethyl)-1,3-dimethyl-5-(trifluoromethyl)indolin-2-one (2i):
1
Yellow solid. H NMR : (400 MHz, CDCl
3
) δ 7.60 (d, J = 8.0 Hz, 1 H),
7
.51 (s, 1 H), 6.95 (d, J = 8.4 Hz, 1 H), 3.66 (s, 2 H), 3.26 (s, 3 H), 1.39
s, 3 H); 13C NMR: (100 MHz, CDCl
) δ 178.1, 146.4, 132.0, 128.3,
26.4 (q, J = 4.0 Hz), 125.6, 125.5, 125.2, 124.8, 124.5, 122.9, 120.1 (q,
(
3
1
J = 3.5 Hz), 108.1, 56.9, 48.6, 26.5, 20.23, 20.15; IR: (KBr) νmax 2939,
-
1
12 4 3
119, 1728, 1627, 1505, 1456, 840 cm ; HRMS m/z (ESI) calcd. for C12H N OF
(M + H)+
2
2
85.0958, found 285.0949.
3
-(Azidomethyl)-1,3-dimethyl-2-oxoindoline-5-carbonitrile (2j):
1
Yellow solid. H NMR : (400 MHz, CDCl
3
) δ 7.63 (dd, J = 8.2, 1.2 Hz, 1
H), 7.53 (d, J = 1.6 Hz, 1 H), 6.94 (d, J = 8.4 Hz, 1 H), 3.69-3.63 (m, 2 H),
3
1
.24 (s, 3 H), 1.37 (s, 3 H); 13C NMR: (100 MHz, CDCl
3
) δ 177.8, 147.2,
33.9, 132.4, 126.4, 118.9, 108.7, 105.8, 56.7, 48.4, 26.5, 20.1; IR: (KBr)
-
1
ν
max 2936, 2090, 1714, 1615, 1499, 1457, 823 cm ; HRMS m/z (ESI)
+
calcd. for C12H
12
N
5
O (M + H) 242.1036, found 242.1037.
Methyl 3-(azidomethyl)-1,3-dimethyl-2-oxoindoline-5-carboxylate (2k):
1
Yellow solid. H NMR : (400 MHz, CDCl
3
) δ 8.04 (dd, J = 8.4, 1.2
Hz, 1 H), 7.92 (s, 1 H), 6.89 (d, J = 8.0 Hz, 1 H), 3.87 (s, 3 H), 3.65 (s,
2
1
4
H), 3.23 (s, 3 H), 1.36 (s, 3 H); 13C NMR: (100 MHz, CDCl
3
) δ
78.4, 166.6, 147.5, 131.3, 131.2, 124.6, 124.1, 107.8, 56.9, 51.9,
8.4, 26.4, 20.2; IR: (KBr) νmax 2953, 2102, 1729, 1616, 1500, 1456
-
1
+
cm ; HRMS m/z (ESI) calcd. for C13
H N
15 4
O
3
(M + H) 275.1139, found 275.1137.
3
-(Azidomethyl)-1,3-dimethyl-5-(trifluoromethoxy)indolin-2-one (2l):
1
3
Yellow solid. H NMR : (400 MHz, CDCl ) δ 7.21-7.18 (m, 2 H), 6.86
1
3
(
d, J = 8.4 Hz, 1 H), 3.66-3.60 (m, 2 H), 3.23 (s, 3 H), 1.38 (s, 3 H); C
3
NMR: (100 MHz, CDCl ) δ 177.9, 144.88, 144.86, 142.1, 132.9, 121.7,
1
19.2, 117.2, 108.7, 57.0, 49.0, 26.5, 20.2; IR: (KBr) νmax 2935, 2103,
-
1
1
720, 1622, 1495, 1456 cm ; HRMS m/z (ESI) calcd. for
+
C
12 12 4 2 3
H N O F (M + H) 301.0907, found 301.0908.
3
-(Azidomethyl)-5-fluoro-1,3-dimethylindolin-2-one (2m):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.04-6.98 (m, 2 H), 6.79 (dd, J
=
8.4, 4.0 Hz, 1 H), 3.61 (s, 2 H), 3.21 (s, 3 H), 1.35 (s, 3 H); 13C NMR:
(
100 MHz, CDCl
3
) δ 177.7, 160.5, 158.1, 139.3, 133.0, 132.9, 114.9, 114.6,
S7

1
11.4, 111.2, 108.8, 108.7, 57.0, 49.0, 26.4, 20.3; IR: (KBr) νmax 2932, 2105, 1708, 1622, 1496,
-
1
+
1118 cm ; HRMS m/z (ESI) calcd. for C11
12 4
H N OF (M + H) 235.0990, found 235.0986.
3
-(Azidomethyl)-5-chloro-1,3-dimethylindolin-2-one (2n):
1
N3
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.31-7.27 (m, 2 H), 6.81 (d, J
8.4 Hz, 1 H), 3.64 (s, 2 H), 3.23 (s, 3 H), 1.37 (s, 3 H); 13C NMR: (100
Cl
=
O
MHz, CDCl ) δ 177.6, 142.0, 133.0, 128.5, 128.1, 123.6, 109.2, 56.9, 48.9,
3
N
-
1
2
6.4, 20.3; IR: (KBr) νmax 2937, 2095, 1717, 1608, 1489, 1432 cm ;
2n
+
12 4
HRMS m/z (ESI) calcd. for C11H N OCl (M + H) 251.0694, found
2
51.0688.
3
-(Azidomethyl)-5-bromo-1,3-dimethylindolin-2-one (2o):
1
N3 Yellow solid. H NMR : (400 MHz, CDCl
3
) δ 7.43 (dd, J = 8.2, 1.6 Hz, 1
Br
H), 7.38 (d, J = 2.0 Hz, 1 H), 6.74 (d, J = 8.4 Hz, 1 H), 3.62 (s, 2 H), 3.20
O
s, 3 H), 1.35 (s, 3 H); 13C NMR: (100 MHz, CDCl
(
3
) δ 177.5, 142.4, 133.4,
N
1
2
31.4, 126.3, 115.3, 109.7, 56.9, 48.8, 26.4, 20.3; IR: (KBr) νmax 2932,
2o
-1
102, 1715, 1608, 1490, 812 cm ; HRMS m/z (ESI) calcd. for
+
11 12 4
C H N OBr (M + H) 295.0189, found 295.0184.
3
-(Azidomethyl)-5-iodo-1,3-dimethylindolin-2-one (2p):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.61 (dd, J = 8.2, 1.6 Hz, 1 H),
7
.54 (s, 1 H), 6.65 (d, J = 8.0 Hz, 1 H), 3.61 (s, 2 H), 3.19 (s, 3 H), 1.34 (s, 3
H); 13C NMR: (100 MHz, CDCl
) δ 177.3, 143.1, 137.3, 133.7, 131.8, 110.3,
5.2, 56.9, 48.6, 26.3, 20.3; IR: (KBr) νmax 2929, 2104, 1714, 1604,
3
8
1
-
1
12 4
487,1463, 809 cm ; HRMS m/z (ESI) calcd. for C11H N
OI (M + H)+
3
43.0050, found 343.0051.
3
-(Azidomethyl)-6-fluoro-1,3-dimethylindolin-2-one
and
3-(azidomethyl)-4-
fluoro-1,3-dimethylindolin-2-one (2q and 2q’):
1
N3
F
N3 Yellow oil. For 2q: H NMR : (400 MHz, CDCl
3
)
δ 7.21 (dd, J = 8.0, 5.2 Hz, 1 H); 6.77 (t, J = 8.8
O
and
O
Hz, 1 H), 6.62 (dd, J = 9.0, 2.4 Hz, 1 H), 3.61 (s,
N
N
F
1
2
H), 3.22 (s, 3 H), 1.36 (s, 3 H); For 2q’: H
2q
2q'
NMR : (400 MHz, CDCl
Hz, 1 H), 6.78 (t, J = 7.8 Hz, 1 H), 6.69 (d, J = 7.6
Hz, 1 H), 3.84 (d, J = 12.0 Hz, 1 H), 3.74 (d, J = 12.0 Hz, 1 H), 3.24 (s, 3 H), 1.44 (s, 3 H); IR:
3
) δ 7.30 (td, J = 8.3, 5.6
2q : 2q' = 1 : 1.4
-
1
(
12 4
KBr) νmax 2919, 2101, 1727, 1627, 1502, 1460 cm ; HRMS m/z (ESI) calcd. for C11H N OF (M
+
+
H) 235.0990, found 235.0986.
3
-(Azidomethyl)-7-bromo-1,3-dimethylindolin-2-one (2r):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.42 (d, J = 8.0 Hz, 1 H), 7.19 (d, J
=
7.6 Hz, 1 H), 6.93 (t, J = 7.6 Hz, 1 H), 3.65-3.58 (m, 5 H), 1.35 (s, 3 H); 13
C
3
NMR: (100 MHz, CDCl ) δ 178.5, 140.8, 134.5, 134.3, 123.9, 122.0, 102.7,
5
7.3, 48.4, 29.9, 20.7; IR: (KBr) νmax 2930, 2087, 1731, 1606, 1578, 1482, 1061
S8

-
1
+
cm ; HRMS m/z (ESI) calcd. for C11
H
12
N
4
OBr (M + H) 295.0189, found 295.0184.
3
-(Azidomethyl)-1,3,7-trimethylindolin-2-one (2s):
1
Yellow oil. H NMR : (400 MHz, CDCl
7.2 Hz, 1 H), 6.98 (t, J = 7.4 Hz, 1 H), 3.65-3.58 (m, 2 H), 3.52 (s, 3 H), 2.60
s, 3 H), 1.34 (s, 3 H); 13C NMR: (100 MHz, CDCl
) δ 178.9, 141.2, 132.4,
31.9, 122.7, 120.8, 120.0, 57.5, 48.0, 29.7, 20.8, 19.0; IR: (KBr) νmax 2928,
3
) δ 7.10 (d, J = 7.2 Hz, 1 H), 7.05 (d, J
=
(
3
1
2
-
1
099, 1708, 1602, 1460, 1365, 747 cm ; HRMS m/z (ESI) calcd. for
+
C
12
H
15
N
4
O (M + H) 231.1240, found 231.1233.
3
-(Azidomethyl)-4,6-difluoro-1,3-dimethylindolin-2-one (2t):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 6.53-6.45 (m, 2 H), 3.82-3.71
) δ 177.9,
65.1, 164.9, 162.6, 162.5, 160.1, 160.0, 157.6, 157.5, 146.5, 146.4, 146.2,
19.9, 111.82, 111.79, 111.63, 111.59, 109.5, 98.2, 97.9, 97.6, 93.90, 93.87,
3.63, 93.59, 55.6, 48.58, 48.55, 26.8, 19.2; IR: (KBr) νmax 2933, 2105,
13
(
m, 2 H), 3.21 (s, 3 H), 1.41 (s, 3 H); C NMR: (100 MHz, CDCl
3
1
1
9
-
1
+
1
11 4 2
732, 1612, 1508, 1054, 828 cm ; HRMS m/z (ESI) calcd. for C11H N OF (M + H) 253.0895,
found 253.0890.
3
-(Azidomethyl)-1-methyl-3-phenylindolin-2-one (2u):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.43-7.40 (m, 4 H), 7.36-7.29 (m, 3
N3
Ph
H), 7.20 (t, J = 7.6 Hz, 1 H), 6.96 (d, J = 7.6 Hz, 1 H), 4.09 (s, 2 H), 3.25 (s, 3
O
H); 13C NMR: (100 MHz, CDCl
3
) δ 176.2, 144.2, 136.5, 129.3, 129.1, 128.8,
N
1
2
28.0, 127.0, 125.3, 122.8, 108.7, 57.1, 56.6, 26.6; IR: (KBr) νmax 3058, 2930,
-
1
101, 1714, 1612, 1494, 1373 cm ; HRMS m/z (ESI) calcd. for C16
H
15
N
4
O (M
2
u
+
+
H) 279.1240, found 279.1232.
3
-(Azidomethyl)-3-benzyl-1-methylindolin-2-one (2v):
1
Colorless oil. H NMR : (400 MHz, CDCl
3
) δ 7.25-7.21 (m, 2 H), 7.09-7.02 (m,
4
2
1
H), 6.85-6.83 (m, 2 H), 6.63 (d, J = 7.6 Hz, 1 H), 3.82-3.75 (m, 2 H), 3.09 (s,
H), 2.99 (s, 3 H); 13C NMR: (100 MHz, CDCl
) δ 176.8, 143.9, 134.6, 129.8,
28.7, 128.6, 127.6, 126.7, 123.9, 122.3, 108.1, 56.1, 54.5, 40.6, 26.0; IR: (KBr)
3
-
1
ν
max 2921, 2105, 1712, 1613, 1494, 1378 cm ; HRMS m/z (ESI) calcd. for
+
C
17
H
17
N
4
O (M + H) 293.1397, found 293.1396.
(
3-(Azidomethyl)-1-methyl-2-oxoindolin-3-yl)methyl acetate (2w):
1
Yellow oil. H NMR : (400 MHz, CDCl
3
) δ 7.35 (s, 2 H), 7.10 (s, 1 H), 6.89 (d,
J = 6.4 Hz, 1 H), 4.52 (d, J = 10.4 Hz, 1 H), 4.18 (d, J = 10.8 Hz, 1 H),
3
1
2
.83-3.68 (m, 2 H), 3.24 (s, 3 H), 1.95 (s, 3 H); 13C NMR: (100 MHz, CDCl
3
) δ
74.9, 170.1, 144.0, 129.3, 127.1, 124.0, 122.8, 108.4, 64.7, 53.6, 52.3, 26.4,
-
1
0.5; IR: (KBr) νmax 2936, 2105, 1747, 1715, 1614, 1494, 755 cm ; HRMS m/z
+
(ESI) calcd. for C13
H
15
N
4
O
3
(M + H) 275.1139, found 275.1139.
1
-(Azidomethyl)-1-methyl-5,6-dihydro-1H-pyrrolo[3,2,1-ij]quinolin-2(4H)-one (2x):
S9

1
White oil. H NMR : (400 MHz, CDCl
7.6 Hz, 1 H), 6.98 (t, J = 7.6 Hz, 1 H), 3.79-3.68 (m, 2 H), 3.62 (s, 2 H),
.86-2.74 (m, 2 H), 2.06-1.99 (m, 2 H), 1.38 (s, 3 H); 13C NMR: (100 MHz,
CDCl ) δ 176.9, 139.2, 129.9, 127.4, 122.2, 120.8, 120.4, 57.1, 50.0, 38.9, 24.5,
3
) δ 7.12 (d, J = 7.6 Hz, 1 H), 7.07 (d, J
=
2
3
-
1
2
1.1, 20.2; IR: (KBr) νmax 2928, 2100, 1714, 1628, 1601, 1482, 751 cm ;
+
15 4
HRMS m/z (ESI) calcd. for C13H N O (M + H) 243.1240, found 243.1235.
3
-(Azidomethyl)-1,3-dimethyl-1H-benzo[g]indol-2(3H)-one (2y):
1
N3 Yellow solid. H NMR : (400 MHz, CDCl
3
) δ 7.79 (d, J = 8.0 Hz, 1 H),
7
.59-7.54 (m, 2 H), 7.46 (t, J = 8.0 Hz, 2 H), 7.00 (d, J = 7.6 Hz, 1 H), 4.20
d, J = 11.6 Hz, 1 H), 3.68 (d, J = 11.6 Hz, 1 H), 3.57 (s, 3 H), 1.66 (s, 3 H);
13C NMR: (100 MHz, CDCl
) δ 171.3, 136.3, 135.2, 133.3, 126.8, 126.5,
22.83, 122.78, 119.7, 108.9, 61.9, 48.1, 29.8, 27.5; IR: (KBr) νmax 2930,
O
(
N
3
1
2
2y
-
1
100, 1718, 1659, 1586, 1466, 1381 cm ; HRMS m/z (ESI) calcd. for
+
C
15 15 4
H N O (M + H) 267.1240, found 267.1238.
S4]
3
-(Aminomethyl)-1,3-dimethylindolin-2-one (3): [
NH2 To a solution of 2a (0.25 mmol, 54.0 mg) in THF (3.0 mL) was added PPh
0.75 mmol, 196.7 mg) and water (2.5 mmol, 45 μL). The resulting solution
3
(
O
o
was heated to 55 C for 4 h before it was cooled to room temperature. The
N
solvent was removed and the residue was purified by column chromatography
3
1
to give 3 in 98% yield as colorless oil. H NMR : (400 MHz, DMSO-d
6
) δ
7
.31 (d, J = 7.6 Hz, 1 H), 7.27 (t, J = 7.6 Hz, 1 H), 7.04 (t, J = 7.4 Hz, 1 H), 6.99 (d, J = 8.0 Hz, 1
) δ 179.3,
43.6, 132.8, 127.7, 122.7, 121.9, 108.1, 49.9, 49.0, 25.8, 19.9; IR: (KBr) νmax 3428, 2104, 1713,
H), 3.12 (s, 3 H), 2.87-2.78 (m, 2 H), 1.20 (s, 3 H); 13C NMR: (100 MHz, DMSO-d
6
1
1
1
-
1
+
613, 1492, 1469 cm ; HRMS m/z (ESI) calcd. for C11
H
15
N
2
O (M + H) 191.1179, found
91.1185.
,3-Dimethyl-3-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)indolin-2-one (5):[
S5]
1
Ph Azide 2a (0.25 mmol, 54.0 mg) and phenylacetylene (0.3 mmol, 30.6 mg)
N
N
t-
N
was suspended in a mixture of BuOH (0.5 mL) and water (0.5 mL) in a
4 2
Schlenk tube with a magnetic bar. Then CuSO ·5H O (0.005 mmol, 1.2
mg) and sodium ascorbate (0.025 mmol, 5.0 mg) was added to the
mixture. The resulting material was stirred for 12 hours at room
temperature before it was diluted with EtOAc. Water (10 mL) was added
and extracted by EtOAc. The organic layer was combined and washed
O
N
5
4
with brine (10 mL) and dried over anhydrous MgSO . The solvent was removed and the residue
1
was purified by column chromatography to give 5 in 94% yield as white solid. H NMR : (400
MHz, CDCl
H), 7.07 (t, J = 7.4 Hz, 1 H), 6.72 (d, J = 8.0 Hz, 1 H), 4.75 (s, 2 H), 3.12 (s, 3 H), 1.50 (s, 3 H);
13C NMR: (100 MHz, CDCl
) δ 177.8, 147.1, 142.8, 130.3, 129.8, 128.8, 128.7, 127.9, 125.5,
23.4, 122.9, 120.0, 108.3, 55.2, 49.2, 26.2, 21.0; IR: (KBr) νmax 3131, 2996, 1709, 1612, 1466,
3
) δ 7.70 (d, J = 7.2 Hz, 2 H), 7.58 (s, 1 H), 7.36 (t, J = 7.4 Hz, 2 H), 7.30-7.21 (m, 3
3
1
1
-
1
+
19 4
078 cm ; HRMS m/z (ESI) calcd. for C19H N O (M + H) 319.1553, found 319.1546.
S10

3
-((5-Benzoyl-2H-tetrazol-2-yl)methyl)-1,3-dimethylindolin-2-one (7): [S6]
Azide 2a (0.6 mmol, 129.6 mg) and benzoyl cyanide (1.32 mmol,
1
73.1 mg) was added to a capped Schlenk tube with a magnetic bar.
o
The mixture was heated to 130 C for 72 hours before it was cooled to
room temperature. Then the resulting material was dissolved in 5 mL
2 3
EtOAc and added to an aqueous solution of Na CO (10% w/w, 5 mL)
and stirred for 1 hour. The organic layer was separated and the
aqueous phase was extracted with EtOAc. The organic layer was
combined and dried over MgSO
removed in vacuo and purified by column chromatography to give 7 in 62% yield as yellow solid.
1H NMR : (400 MHz, CDCl
) δ 8.05-8.02 (m, 2 H), 7.63 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.8 Hz, 2
H), 7.05 (td, J = 7.6, 0.8 Hz, 1 H), 6.97 (d, J = 6.8 Hz, 1 H), 6.66 (t, J = 8.4 Hz, 2 H), 5.25 (d, J =
3.6 Hz, 1 H), 5.05 (d, J = 13.6 Hz, 1 H), 3.03 (s, 3 H), 1.46 (s, 3 H); 13C NMR: (100 MHz,
CDCl ) δ 181.9, 176.9, 149.5, 143.0, 134.8, 134.6, 130.8, 128.9, 128.6, 128.4, 123.0, 122.6, 108.4,
4
and filtered. The filtrate was
3
1
3
-
1
5
3.2, 48.4, 26.1, 20.4; IR: (KBr) νmax 2932, 1720, 1667, 1613, 1495, 1451 cm ; HRMS m/z (ESI)
+
18 5 2
calcd. for C19H N O (M + H) 348.1455, found 348.1451.
References:
[
[
[
[
[
[
S1]. A. Pinto, Y. Jia, L. Neuville, J. Zhu, Chem. Eur. J. 2007, 13, 961-967.
S2]. A. A.-L. Ayitou, J. Sivaguru, Chem. Commun. 2011, 47, 2568-2570.
S3]. Q.-Q. Zhang, J.-H. Xie, X.-H. Yang, J.-B. Xie, Q.-L. Zhou, Org. Lett. 2012, 14, 6158-6161.
S4]. F. Yokokawa, T. Asano, T. Shioiri, Org. Lett. 2000, 2, 4169-4172.
S5]. C. Tang, N. Jiao, J. Am. Chem. Soc. 2012, 134, 18924-18927.
S6]. Z. P. Demko, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2113-2116.
S11

N3
O
N
2a
8
7
6
5
4
3
2
1
PPM
S12

N3
O
N
2a
180
160
140
120
100
80
60
40
20
PPM
S13

N3
O
N
Et
2
b
8
7
6
5
4
3
2
1
PPM
S14

N3
O
N
Et
2
b
180
160
140
120
100
80
60
40
20
PPM
S15

N3
O
N
Bn
2c
8
7
6
5
4
3
2
1
0PPM
S16

N3
O
N
Bn
2c
180
160
140
120
100
80
60
40
20
PPM
S17

N3
O
N
2
f
8
7
6
5
4
3
2
1
0
PPM
S18

N3
O
N
2
f
180
160
140
120
100
80
60
40
20
PPM
S19

N3
O
t-Bu
N
2g
9
.03
2
.98
3.04
1
.93
2
.00
0
.96
7
6
5
4
3
2
1
PPM
S20

N3
O
t-Bu
N
2g
180
160
140
120
100
80
60
40
20
PPM
S21

N3
O
O2N
N
2
h
9
8
7
6
5
4
3
2
1
PPM
S22

N3
O
O2N
N
2
h
180
160
140
120
100
80
60
40
20
PPM
S23

N3
O
F C
3
N
2i
8
7
6
5
4
3
2
1
0PPM
S24

N3
O
F C
3
N
2i
180
160
140
120
100
80
60
40
20
0 PPM
S25

N3
O
NC
N
2j
8
7
6
5
4
3
2
1
PPM
S26

N3
O
NC
N
2j
180
160
140
120
100
80
60
40
20
PPM
S27

N3
O
MeO C
2
N
2k
8
7
6
5
4
3
2
1
0
PPM
S28