Oxygen switch in visible-light photoredox catalysis: Radical additions and cyclizations and unexpected C-C-bond cleavage reactions

Article abstract of DOI:10.1021/ja309580a

Visible light photoredox catalyzed inter- and intramolecular C-H functionalization reactions of tertiary amines have been developed. Oxygen was found to act as chemical switch to trigger two different reaction pathways and to obtain two different types of products from the same starting material. In the absence of oxygen, the intermolecular addition of N,N-dimethyl-anilines to electron-deficient alkenes provided γ-amino nitriles in good to high yields. In the presence of oxygen, a radical addition/cyclization reaction occurred which resulted in the formation of tetrahydroquinoline derivatives in good yields under mild reaction conditions. The intramolecular version of the radical addition led to the unexpected formation of indole-3-carboxaldehyde derivatives. Mechanistic investigations of this reaction cascade uncovered a new photoredox catalyzed C-C bond cleavage reaction.

Full text of DOI:10.1021/ja309580a

The Oxygen Switch in Visible-Light Photoredox Catalysis: Radical
Additions and Cyclizations and Unexpected C-C-Bond Cleavage
Reactions
Shaoqun Zhu,a Arindam Das,a Lan Bui,a Hanjun Zhou,a Dennis P. Curranb and Magnus Ruepinga,*
a RWTH Aachen University, Institute of Organic Chemistry, Landoltweg 1, D-52074 Aachen, Germany.
b University of Pittsburgh, Department of Chemistry, Pittsburgh, Pennsylvania 15260, United States.
E-mail: magnus.rueping@rwth-aachen.de; Fax: +49 241 8092665
Supporting Information
General: Unless otherwise noted, all commercially available compounds were used as provided
without further purification. Solvents used in reactions were p.A. grade and dried only if
indicated. Solvents for chromatography were technical grade and distilled prior to use. Analytical
thin-layer chromatography (TLC) was performed on Merck silica gel aluminium plates with F-
254 indicator, visualised by irradiation with UV light. Column chromatography was performed
using silica gel Merck 60 (particle size 0.063 – 0.2 mm). Solvent mixtures are understood as
volume/volume.
13
1H-NMR and C-NMR were recorded on a Varian VNMR 400, VNMR 600 and Mercury 300
spectrometer in CDCl3. Data are reported in the following order: chemical shift (δ) in ppm;
multiplicities are indicated br (broadened singlet), s (singlet), d (doublet), t (triplet), q (quartet),
quint (quintet), m (multiplet); coupling constants (J) are in Hertz (Hz). Mass spectra (MS-EI, 70
eV) were conducted on Finnigan SSQ 7000. IR spectra were recorded on a Perkin Elmer
Spectrum 100 FT-IR spectrometer and are reported in terms of frequency of absorption (cm-1).
S1

Table 1SI. Catalyst screening for the photoredox reaction.
NC CN
Photocatalyst
(x mol %)
NC
CN
Ph
CN
CN
+
+
Ph Solvent, Blue LED
N
N
N
Ph
1a
2a
3a
4a
PF6
PF6
(PF6)3
tBu
N
Ir
N
Ir
N
N
N
N
N
N
N
N
Ir
N
N
N
N
tBu
Cat - 3
PF6
Cat - 1
Cat - 2
PF6
But
Cl2
F3C
PF6
tBu
tBu
F
F
N
Ir
N
N
Ir
N
N
N
N
N
N
N
N
tBu
tBu
F
F
Ru
N
Ir
N
N
N
N
N
N
But
Cat - 6
F3C
Cat - 4
Cat - 5
Cat - 7
Entry[a]
Catalyst
time
Major product
Yield (%)[b]
1
2
Cat-1 (1 mol %)
Cat-2 (1 mol %)
Cat-3 (1 mol %)
Cat-4 (1 mol %)
Cat-5 (1 mol %)
Cat-6 (1 mol %)
Cat-7 (1 mol %)
Cat-1 (1 mol %)
--
32
24
28
26
24
24
24
48
48
8
62
54
42
47
50
54
62
0
3a
3a
3a
3a
3a
3a
3a
--
3
4
5
6
7
8[c]
9[d]
10
11[e]
12[e]
0
--
Cat-1 (5 mol %)
Cat-1 (1 mol %)
Cat-1 (5 mol %)
68
67
91
3a
4a
4a
48
20
[a] Reaction conditions: 1a (0.26 mmol), 2a (0.20 mmol), catalyst (1-5 mol%), Blue LED irradiation, MeCN (1.5
mL) and reaction mixture was degassed [b] Yield of the isolated product. [c] Reaction was carried out in the dark.
[d] Reaction was carried out without catalyst. [e] Reaction was carried out under argon.
S2

Representative procedure for the radical addition/cyclization reaction: An oven-dried test
tube equipped with a stir bar was charged with [Ir(ppy)2bpy](PF6)2 (5 mol%) and 2-
benzylidenemalononitrile (2a; 0.2 mmol). The tube was sealed with a rubber stopper, evacuated
and backfilled with argon for three times, then dry CH3CN (1.5 mL) and N,N-dimethyl-4-
methylaniline (1a; 0.26 mmol) were added under argon. The solution was stirred at room
temperature under irradiation with visible light. After 2a was completely consumed (monitored
by TLC), the crude mixture was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate 20:1) to yield the corresponding product 3a.
General procedure for radical addition of tertiary amines with electron-deficient alkenes:
An oven-dried Schlenk tube was charged with 2-benzylidenemalononitrile (2a, 0.2 mmol) and
[Ir(ppy)2bpy]PF6 (0.01 mmol) and was sealed with a rubber stopper, evacuated and backfilled
with argon for three times, then dry CH3CN (1.5 ml) and N,N-dimethyl-4-methylaniline (1a, 0.26
mmol) were added under argon. The solution was stirred at room temperature under irradiation
with Blue LEDs. After 2a was completely consumed (monitored by TLC), the crude mixture was
purified by column chromatography (hexanes: ethyl acetate) to yield the corresponding product
4a.
Experimental procedure for the synthesis of (E)-4-(2-(dibenzylamino)phenyl)but-3-en-2-one:
O
Me
I
I
BnBr, K2CO3
MVK, P(o-tolyl)3
DMF
120oC, 56h
Pd(OAc)2, Et3N
CH3CN, Reflux, 24h
NBn2
NH2
NBn2
To a solution of o-iodoaniline (3.55 g, 16.2 mmol) in DMF (32.3 mL) was added K2CO3 (11.2 g,
80.8 mmol) and BnBr (7.69 mL, 64.6 mmol) at room temperature, followed by heating at 120 °C.
After stirring for 48 h at 120 °C, the reaction was stopped by adding Et2NH (4.20 mL, 40.4
mmol) at 0 °C. The crude products were extracted with ethyl acetate (x4) and the combined
organic extracts were washed with brine, dried (Na2SO4) and concentrated in vacuo. The residue
was purified by flash column chromatography (silica gel, hexane/EtOAc = 30/1) to afford
dibenzylaniline (6.2 g, quant.) as a colorless oil.
S3

Mizoroki-Heck reaction of N,N-dibenzyl-2-iodoaniline: A N2-purged 100 mL three-necked
flask was charged with tri-o-tolyl phosphine (457 mg, 1.5 mmol), palladium (II) acetate (168 mg,
0.75 mmol), N,N-dibenzyl-2-iodoaniline (5.18 g, 13 mmol), methyl vinyl ketone (1.5 mL, 18
mmol), NEt3 (2.29 mL, 16.5 mmol) and CH3CN (60 mL). The system was immersed in an oil
bath at reflux. After 24 h, it was removed from the oil bath, diluted with EtOAc (180 mL) and
extracted with water (2 x 60 mL) and brine (60 mL). The organic layer was dried over Na2SO4
and volatiles were removed in vacuo. The residue was subjected to column chromatography on
silica-gel (eluent; hexane/EtOAc = 5/1) to give (E)-4-(2-(dibenzylamino)phenyl)but-3-en-2-one
(5a) (2.53 g, 7.41 mmol, 57% yield) as a viscous liquid.
Standard procedure for the photoredox catalyzed intramolecular Michael addition followed
by oxidative cleavage reaction:
O
CHO
Ar
Me
10 mol% ([Ir(ppy)2(dtb-bpy)]PF6
R
R
CHCl3, Blue LED (455nm)
room temp, air balloon
N
N
Ar
Ar
Ar
Photoredox catalyst [Ir(ppy)2(dtb-bpy)]PF6 (10 mol%) was transferred into a dried Schlenk tube.
The sealed tube was fitted with an air balloon. A solution of the starting compound 5a (0.2
mmol) in 2 mL chloroform (anhydrous) was added via syringe. After stirring for 22 h at room
temperature, the reaction mixture was filtered through a short silica plug and the silica was
washed with DCM. The organic solvents were evaporated in vacuo and the product was purified
by column chromatography.
S4

Table 2SI.
O
CHO
Ph
Me
10 mol% Catalyst
N
CH3CN, Blue LED
rt, air balloon
N
Ph
Ph
6a
Ph
5a
tBu
(PF6)3
PF6
PF6
F3C
tBu
tBu
tBu
tBu
tBu
tBu
F
F
N
N
Ir
N
Ir
N
N
N
N
N
N
N
Ir
F
F
N
N
N
N
F3C
tBu
Cat-5
Cat-2
Cat-8
PF6
PF6
F3C
F3C
Cl2
F
F
CF3
N
N
Ir
N
Ru
N
N
N
N
N
N
N
Ir
N
N
N
N
CF3
F3C
F3C
Cat-10
Cat-7
Cat-9
Entry[a]
Time[b] (h)
Yield[c] (%)
Catalyst
22
48
48
48
48
48
1.
2.
3.
4.
5.
6.
Cat-2
Cat-5
Cat-8
Cat-9
Cat-10
Cat-7
51
5a as mixture of E,Z-Isomer (1:1)
5a as mixture of E,Z-Isomer (1:1)
5a as mixture of E,Z-Isomer (1:1)
5a as mixture of E,Z-Isomer (1:1)
5a as mixture of E,Z-Isomer (1:1)
TiO2 (1.1 equiv.)
ZnO (1.1 equiv.)
5a as mixture of E,Z-Isomer (1:1)
5a as mixture of E,Z-Isomer (1:1)
7.
8.
72
72
[a] Reaction conditions: 0.1 mmol substrate 10 mol% catalyst, 1 mL solvent.
[b] Refers to the time until all starting material is consumed.
[c] Yield of the isolated product.
S5

Photoredox radical addition/cyclization reaction:
1,6-dimethyl-3-phenyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3a):
1H-NMR (400 MHz, CDCl3): δ = 7.50 – 7.41 (m, 5H), 7.35 – 7.31 (m, 1H), 7.15
N
(dd, J = 8.5, 2.0 Hz, 1H), 6.67 (d, J = 8.5 Hz, 1H), 3.90 (dd, J = 12.2, 11.4 Hz,
1H), 3.61 (dd, J = 11.4, 3.7 Hz, 1H), 3.48 (dd, J = 12.2, 3.7 Hz, 1H), 2.99 (s, 3H),
2.29 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 142.2, 135.1, 132.3, 129.5, 129.3,
NC CN
128.6, 127.8, 127.4, 115.5, 114.4, 113.0, 112.8, 51.7, 45.9, 42.6, 39.1, 20.3; IR (neat): ν = 3361, 3035,
2919, 2850, 2230, 1960, 1888, 1816, 1706, 1622, 1520, 1454, 1294, 1212, 1118, 1000, 875, 809, 769,
700, 618, 500; MS-EI: m/z(%): 288 (23), 287 (100), 286 (10), 197 (12), 196 (86), 183 (20), 181 (15), 171
(14), 156 (10), 155 (10), 105 (11), 104 (15), 91 (23), 77 (14).
3-(4-(tert-butyl)phenyl)-1,6-dimethyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3b):
1H-NMR (600 MHz, CDCl3): δ = 7.48 – 7.44 (m, 2H), 7.41 – 7.37 (m, 2H),
N
7.33 (s, 1H), 7.14 (dd, J = 8.5, 1.5 Hz, 1H), 6.66 (d, J = 8.5 Hz, 1H), 3.92 –
3.85 (m, 1H), 3.59 (dd, J = 11.5, 3.7 Hz, 1H), 3.46 (dd, J = 12.3, 3.7 Hz, 1H),
2.98 (s, 3H), 2.29 (s, 3H), 1.35 (s, 9H); 13C-NMR (150.8 MHz, CDCl3): δ =
NC CN
152.4, 142.2, 132.5, 132.0, 129.3, 128.3, 127.3, 126.2, 115.7, 114.5, 112.9,
51.8, 45.5, 42.7, 39.1, 34.8, 31.4, 20.3; IR (neat): ν =3037, 2965, 2917, 2850, 2230, 1907, 1731, 1621,
1588, 1516, 1455, 1260, 1211, 1108, 1017, 887, 813, 705, 656; MS-EI: m/z(%): 344 (29), 343 (100), 328
(17), 197 (12), 196 (80), 181 (8), 171 (7), 164 (6), 145 (13), 117 (9), 115 (4), 105 (5), 91 (6), 77 (3).
1,6-dimethyl-3-(o-tolyl)-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3c):
1H-NMR (400 MHz, CDCl3): δ = 7.62 – 7.48 (m, 1H), 7.40 – 7.24 (m, 4H), 7.16
N
(ddd, J = 8.5, 2.1, 0.6 Hz, 1H), 6.68 (d, J = 8.5 Hz, 1H), 3.99 (dd, J = 11.3, 3.7 Hz,
1H), 3.90 – 3.81 (m, 1H), 3.37 (dd, J = 12.3, 3.7 Hz, 1H), 2.99 (s, 3H), 2.48 (s,
NC CN
3H), 2.30 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 142.0, 137.2, 133.7, 132.6,
131.5, 129.0, 128.9, 127.3, 127.1, 126.8, 115.5, 114.6, 113.5, 112.9, 52.3, 41.7, 40.6, 38.9, 20.3, 20.2; IR
(neat): ν = 3029, 2852, 2333, 2242, 1815, 1708, 1622, 1574, 1521, 1459, 1384, 1344, 1292, 1248, 1208,
1164, 1121, 1075, 1000, 959, 911, 874, 769, 731, 622, 561, 512, 458; MS-EI: m/z(%): 302 (22), 301
(100), 300 (7), 286 (4), 197 (10), 196 (70), 195 (4), 183 (10), 182 (3), 181 (10), 171 (8), 169 (4), 168 (2)
156 (5), 155 (5), 130 (3), 129 (3), 128 (3), 118 (7), 117 (13), 116 (5), 115 (10), 105 (8), 103 (4), 102 (2),
91 (12), 89 (3), 79 (3), 78 (3), 77 (8), 65 (7), 63 (2), 51 (3).
S6

3-(2,4-dimethylphenyl)-1,6-dimethyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3d):
1H-NMR (300 MHz, CDCl3): δ = 7.46 – 7.41 (m, 1H), 7.35 – 7.32 (m, 1H), 7.18
N
– 7.07 (m, 3H), 6.67 (d, J = 8.5 Hz, 1H), 3.95 (dd, J = 11.4, 3.4 Hz, 1H), 3.91 –
3.77 (m, 1H), 3.35 (dd, J = 11.9, 3.4 Hz, 1H), 2.98 (s, 3H), 2.44 (s, 3H), 2.34 (s,
NC CN
3H), 2.30 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 142.0, 138.8, 137.0, 132.5,
132.2, 130.6, 128.9, 127.8, 127.2, 126.7, 115.4, 114.7, 113.5, 112.9, 52.4, 40.4, 38.9, 21.2, 20.3, 20.1; IR
(neat): ν = 3312, 3026, 2920, 2832, 2239, 2086, 1900, 1693, 1621, 1575, 1518, 1448, 1411, 1380, 1344,
1291, 1255, 1213, 1168, 1112, 1071, 1034, 999, 947, 887, 808, 732, 680 MS-EI: m/z(%): 316 (16), 315
(80), 197 (14), 196 (100), 195 (7), 183 (9), 181 (11), 171 (8), 132 (9), 117 (12), 115 (10), 91 (9), 77 (4).
3-(4-bromophenyl)-1,6-dimethyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3e):
1H-NMR (400 MHz, CDCl3): δ = 7.58 (d, J = 8.5 Hz, 2H), 7.35 – 7.30 (m,
N
3H), 7.15 (dd, J = 8.5, 2.0 Hz, 1H), 6.67 (d, J = 8.5 Hz, 1H), 3.84 (dd, J =
12.2, 11.2 Hz, 1H), 3.59 (dd, J = 11.2, 3.7 Hz, 1H), 3.47 (dd, J = 12.2, 3.7 Hz,
1H), 2.99 (s, 3H), 2.29 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 142.1,
NC CN
Br
134.1, 132.7, 132.5, 130.2, 129.3, 127.7, 123.8, 115.4, 114.2, 113.0, 112.4, 51.5, 45.4, 42.3, 39.1, 20.3; IR
(neat): ν = 3426, 2922, 2852, 2051, 1903, 1708, 1620, 1568, 1520, 1487, 1448, 1406, 1346, 1294, 1239,
1213, 1113, 1072, 1005, 941, 873, 812, 726, 676; MS-EI: m/z(%): 368 (21), 367 (100), 366 (32), 365 (97),
364 (9), 197 (12), 196 (93), 184 (9), 183 (19), 182 (12), 181 (17), 171 (15), 169 (10), 156 (11) 155 (13),
129 (4), 128 (5), 115 (7), 105 (9), 103 (11), 102 (7), 91 (6), 90 (5), 89 (7), 77 (16), 76 (6), 75 (5), 63 (5),
51 (5), 50 (4).
1,6-dimethyl-3-(p-tolyl)-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3f):
1H-NMR (400 MHz, CDCl3): δ = 7.36 – 7.29 (m, 3H), 7.26 – 7.21 (m, 2H), 7.12
N
(ddd, J = 8.5, 2.0, 0.6 Hz Hz, 1H), 6.64 (d, J = 8.5 Hz, 1H), 3.86 (dd, J = 12.2,
11.5 Hz, 1H), 3.56 (dd, J = 11.5, 3.7 Hz, 1H), 3.44 (dd, J = 12.2, 3.7 Hz, 1H),
NC CN
2.97 (s, 3H), 2.37 (s, 3H), 2.27 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ =
142.2, 139.4, 132.5, 132.1, 123.0, 129.3, 128.4, 127.4, 115.6, 114.5, 112.9, 51.7, 45.6, 42.8, 39.1, 21.3,
20.3; IR (neat): ν =3025, 2920, 2854, 2248, 1904, 1806, 1719, 1621, 1519, 1456, 1345, 1293, 1252, 1208,
1118, 1000, 911, 812, 732, 569, 509; MS-EI: m/z(%): 302 (18), 301 (93), 300 (7), 197 (13), 196 (100),
195 (6), 182 (4), 171 (10), 118 (17), 117 (16), 105 (12), 91 (10), 77 (7).
S7

6-(tert-butyl)-1-methyl-3-(o-tolyl)-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3g):
1H-NMR (400 MHz, CDCl3): δ = 7.60 – 7.55 (m, 1H), 7.52 (d, J = 2.3 Hz, 1H),
N
7.39 (dd, J = 8.7, 2.3 Hz, 1H), 7.34 – 7.29 (m, 3H), 6.72 (d, J = 8.8 Hz, 1H),
4.00 (dd, J = 11.5, 3.7 Hz, 1H), 3.94 – 3.85 (m, 1H), 3.36 (dd, J = 12.2, 3.7 Hz,
1H), 3.00 (s, 3H), 2.48 (s, 3H), 1.33 (s, 9H); 13C-NMR (100.6 MHz, CDCl3): δ =
NC CN
141.9, 140.9, 137.2, 133.7, 131.5, 129.0, 127.1, 126.8, 125.2, 115.3, 114.7, 113.1, 112.6, 52.3, 42.1, 40.7,
38.8, 34.2, 31.5, 20.3; IR (neat): ν = 3434, 2922, 2246, 1735, 1618, 1521, 1460, 1373, 1292, 1216, 1119,
907, 757, 668, 577, 457; MS-EI: m/z(%): 344 (13), 343 (53), 342 (3), 330 (3), 329 (24), 328 (100), 327
(4), 182 (3), 169 (2), 160 (6), 117 (5), 116 (2), 115 (4), 105 (4), 91 (4), 77 (3), 65 (2), 57 (5).
6-(tert-butyl)-1-methyl-3-(p-tolyl)-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3h):
1H-NMR (300 MHz, CDCl3): δ = 7.42 (d, J = 2.3 Hz, 1H), 7.29 (dd, J = 8.7,
N
2.3 Hz, 3H), 7.24 – 7.15 (m, 3H), 6.63 (d, J = 8.7 Hz, 1H), 3.89 – 3.77 (m,
1H), 3.50 (dd, J = 11.5, 3.7 Hz, 1H), 3.37 (dd, J = 12.2, 3.7 Hz, 1H), 2.92 (s,
NC CN
3H), 2.32 (s, 3H), 1.24 (s, 9H); 13C-NMR (75.4 MHz, CDCl3): δ = 142.1,
141.0, 139.4, 132.1, 130.0, 129.0, 128.4, 127.8, 125.6, 114.4, 112.7, 51.7, 45.7, 39.0, 31.4, 31.1, 21.4; IR
(neat): ν = 3438, 2919, 2853, 2421, 2237, 1731, 1675, 1617, 1579, 1540, 1462, 1382, 1248, 1201, 1113,
926, 876, 819, 725, 525, 459; MS-EI: m/z(%): 344 (13), 343 (53), 342 (3), 330 (3), 329 (24), 328 (100),
327 (4), 182 (3), 169 (2), 160 (6), 117 (5), 116 (2), 115 (4), 105 (4), 91 (4), 77 (3), 65 (2), 57 (5).
6-(tert-butyl)-3-(2,4-dimethylphenyl)-1-methyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3i):
1H-NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 2.3 Hz, 1H), 7.45 (d, J = 8.7
N
Hz, 1H), 7.38 (dd, J = 8.7, 2.3 Hz, 1H), 7.10 – 7.15 (m, 2H), 6.71 (d, J = 8.7
Hz, 1H), 3.96 (dd, J = 11.5, 3.5 Hz, 1H), 3.91 – 3.83 (m, 1H), 3.34 (dd, J =
NC CN
12.0, 3.5 Hz, 1H), 3.00 (s, 3H), 2.44 (s, 3H), 2.35 (s, 3H), 1.32 (s, 9H); 13C-
NMR (100.6 MHz, CDCl3): δ = 141.9, 140.8, 138.8, 137.0, 132.3, 130.7, 128.9, 127.8, 126.7, 125.2,
115.3, 114.7, 113.1, 112.6, 52.4, 42.2, 40.4, 38.8, 34.2, 31.5, 21.2, 20.2; IR (neat): ν = 3427, 2959, 2855,
2243, 1896, 1705, 1617, 1578, 1520, 1461, 1383, 1347, 1293, 1218, 1127, 1000, 961, 883, 817, 757, 665,
620, 546, 518, 459; MS-EI: m/z(%): 359 (3), 358 (20), 357 (72), 356 (7), 344 (4), 343 (21), 342 (100), 341
(4), 238 (6), 182 (7), 160 (4), 157 (2), 132 (2), 131 (2), 119 (3), 117 (4), 115 (3), 91 (3), 57 (8).
S8

3-(4-(tert-butyl)phenyl)-1,7-dimethyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3j):
1H-NMR (600 MHz, CDCl3): δ = 7.47 – 7.44 (m, 2H), 7.41 – 7.38 (m, 3H),
N
6.64 (d, J = 7.8 Hz, 1H), 6.54 (s, 1H), 3.93 (t, J = 11.8Hz, 1H ), 3.56 (dd, J =
3.8, J = 11.5 Hz, 1H), 3.47 (dd, J = 3.8, 12.4 Hz 1H), 3.01 (s, 3H), 2.34 (s,
3H), 1.34 (s, 9H); 13C-NMR (150.8 MHz, CDCl3): δ = 152.3, 143.9, 141.9,
NC CN
131.8, 128.7, 128.1, 126.0, 118.6, 115.4, 114.3, 113.0, 110.2, 51.5, 45.2, 42.3,
38.8, 34.7, 31.2, 21.8; IR (neat): ν = 3742, 2957, 2865, 2324, 1736, 1606, 1508, 1360, 1250, 1112, 1019,
836, 785, 687; MS-EI: m/z = 196 (83), 197 (12), 343 (100), 344 (28), 345 (5).
3-(4-bromophenyl)-1,7-dimethyl-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3k):
1H-NMR (600 MHz, CDCl3): δ = 7.59 – 7.57 (m, 2H), 7.39 (d, J = 7.9, 1H),
N
7.34 – 7.32 (m, 2H), 6.66 (d, J = 8.7 Hz, 1H), 6.55 (s, 1H), 3.88 (dd, J = 11.3, J
= 12.3 Hz, 1H), 3.56 (dd, J = 3.8, J = 11.2 Hz, 1H), 3.48 (dd, J = 3.8, J = 12.4
NC CN
Hz 1H), 3.01 (s, 3H), 2.35 (s, 3H); 13C-NMR (150.8 MHz, CDCl3): δ = 143.8,
Br
142.2, 133.8, 132.3, 130.0, 128.7, 123.7, 118.9, 115.1, 114.0, 113.1, 109.7, 51.2, 45.2, 41.9, 38.8, 21.8; IR
(neat): ν = 2923, 2852, 1695, 1605, 1570, 1490, 1459, 1305, 1246, 1109, 1074, 1008, 950, 804, 728, 661;
MS-EI: m/z = 196 (92), 197 (13), 365 (100), 366 (26), 367 (99), 368 (23).
1,7-dimethyl-3-(p-tolyl)-2,3-dihydroquinoline-4,4(1H)-dicarbonitrile (3l):
1H-NMR (600 MHz, CDCl3): δ = 7.39 (d, J = 7.9 Hz, 1H), 7.34 (d, J = 8.0 Hz,
N
2H), 7.24 (d, J = 7.9 Hz, 1H), 6.64 (d, J = 7.9 Hz, 1H), 6.54 (s, 1H), 3.91 (t, J =
11.5Hz, 1H ), 3.57 (dd, J = 3.8, J = 11.4 Hz, 1H), 3.48 (dd, J = 3.9, J = 12.4 Hz
NC CN
1H), 3.01 (s, 3H), 2.39 (s, 3H), 2.34 (s, 3H); 13C-NMR (150.8 MHz, CDCl3): δ =
143.9, 142.0, 139.2, 131.8, 129.8, 128.7, 128.3, 118.6, 115.4, 114.3, 113.0, 110.1, 51.5, 45.3, 42.4, 38.8,
21.8, 21.2; IR (neat): ν = 3741, 3208, 2924, 2842, 2606, 2330, 2157, 1607, 1571, 1508, 1412, 1301, 1245,
1114, 1016, 809, 725, 668; MS-EI: m/z = 117 (19), 196 (100), 197 (14), 301 (100), 302 (25).
Photoredox radical addition reaction:
2-(2-(methyl(p-tolyl)amino)-1-phenylethyl)malononitrile (4a):
1H-NMR (300 MHz, CDCl3): δ = 7.49 – 7.38 (m, 5H), 7.12 (d, J = 8.7 Hz, 2H),
N
6.76 (d, J = 8.7 Hz, 2H), 4.29 (d, J = 4.3 Hz, 1H), 3.89 – 3.75 (m, 1H), 3.70 – 3.54
(m, 2H), 2.95 (s, 3H), 2.30 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 146.7,
NC CN
135.0, 130.3, 129.5, 129.5, 128.8, 128.3, 114.8, 112.4, 111.9, 55.7, 45.0, 41.5,
27.1, 20.5; IR (neat): ν = 3435, 2919, 2850, 2254, 1882, 1724, 1616, 1577, 1519, 1452, 1382, 1240, 1183,
S9

1119, 1031, 806, 760, 700, 611, 524; MS-EI: m/z(%): 290 (2), 289 (10), 135 (9), 134 (100), 119 (6), 118
(7), 91 (12), 78 (3), 77 (6), 65 (5).
2-(1-(4-fluorophenyl)-2-(methyl(p-tolyl)amino)ethyl)malononitrile (4b):
1H-NMR (600 MHz, CDCl3): δ = 7.42 – 7.36 (m, 2H), 7.17 – 7.10 (m, 4H),
N
6.75 (d, J = 8.5 Hz, 2H), 4.31 – 4.28 (m, 1H), 3.81 – 3.73 (m, 1H), 3.64 – 3.56
(m, 2H), 2.95 (s, 3H), 2.29 (s, 3H); 13C-NMR (150.8 MHz, CDCl3): δ = 163.3
NC CN
F
(d, JCF = 249 Hz), 146.7, 130.3, 130.1, 129.1, 116.6, 116.5, 115.0, 112.3,
111.73, 55.8, 44.3, 41.6, 27.1, 20.5; IR (neat): ν = 3436, 2920, 2851, 2230, 1890, 1726, 1608, 1515, 1457,
1382, 1235, 1163, 1120, 1045, 942, 835, 809, 760, 604, 524; MS-EI: m/z(%): 307 (6), 135 (10), 134 (100),
119 (7), 118 (7), 91 (11), 77 (3), 65 (5).
2-(1-(4-bromophenyl)-2-(methyl(p-tolyl)amino)ethyl)malononitrile (4c):
1H-NMR (300 MHz, CDCl3): δ = 7.59 (d, J = 8.5 Hz, 2H), 7.29 (d, J = 8.4 Hz,
N
2H), 7.12 (d, J = 8.4 Hz, 2H), 6.75 (d, J = 8.5 Hz, 2H), 4.29 (d, J = 4.4 Hz,
1H), 3.77 (dd, J = 14.7, 10.5 Hz, 1H), 3.60 (dd, J = 14.7, 5.0 Hz, 1H), 3.58 –
3.54 (m, 1H), 2.94 (s, 3H), 2.29 (s, 3H); 13C-NMR (150.8 MHz, CDCl3): δ =
NC CN
Br
146.0, 133.9, 132.7, 130.3, 129.9, 129.1, 123.7, 115.0, 112.2, 111.6, 55.6, 44.5, 41.6, 26.9, 20.5; IR (neat):
ν = 2914, 2254, 1901, 1708, 1616, 1519, 1488, 1346, 1238, 1183, 1122, 1074, 1010, 910, 811, 732, 520;
MS-EI: m/z(%): 369 (4), 367 (4), 135 (11), 134 (100), 133 (4), 119 (7), 118 (7), 91 (12), 77 (4), 65 (6).
2-(2-(methyl(p-tolyl)amino)-1-(p-tolyl)ethyl)malononitrile (4d):
1H-NMR (300 MHz, CDCl3): δ = 7.31 – 7.14 (m, 4H), 7.04 (d, J = 8.7 Hz, 2H),
N
6.68 (d, J = 8.7 Hz, 2H), 4.19 (d, J = 4.1 Hz, 1H), 3.77 – 3.67 (m, 1H), 3.59 –
3.45 (m, 2H), 2.87 (s, 3H), 2.31 (s, 3H), 2.21 (s, 3H); 13C-NMR (75.4 MHz,
NC CN
CDCl3): δ = 146.8, 139.4, 132.0, 130.2, 130.1, 128.7, 128.1, 114.8, 112.5, 112.0,
55.8, 44.7, 41.5, 27.2, 21.3, 20.5; IR (neat): ν = 3665, 3031, 2917, 2228, 1908, 1802, 1709, 1615, 1587,
1518, 1451, 1349, 1240, 1185, 1119, 1043, 911, 811, 731, 613, 520; MS-EI: m/z(%): 304 (2), 303 (9), 135
(11), 134 (100), 119 (6), 118 (6), 117 (3), 91 (10), 77 (3), 65 (5).
S10

2-(2-(methyl(p-tolyl)amino)-1-(o-tolyl)ethyl)malononitrile (4e):
1H-NMR (300 MHz, CDCl3): δ = 7.43 – 7.37 (m, 1H), 7.27 – 7.15 (m, 3H), 7.03
N
(dd, J = 8.8, 0.7 Hz, 2H), 6.64 (d, J = 8.8 Hz, 2H), 4.08 (d, J = 5.5 Hz, 1H), 3.97 –
3.86 (m, 1H), 3.76 (dd, J = 14.7, 9.4 Hz, 1H), 3.50 (dd, J = 14.7, 5.4 Hz, 1H), 2.82
(s, 3H), 2.25 (s, 3H), 2.20 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 146.4, 137.1,
NC CN
134.0, 131.6, 130.2, 128.9, 128.3, 127.2, 126.2, 114.4, 112.4, 112.1, 56.2, 41.544, 39.2, 26.6, 20.4, 19.9;
IR (neat): ν = 3411, 3065, 3032, 2956, 2920, 2850, 2229, 1711, 1622, 1528, 1519, 1457, 1384, 1345
,1294, 1209, 1163, 1121, 1032, 998, 911, 874, 809, 733, 618, 479; MS-EI: m/z(%): 302 (20), 301 (100),
300 (6), 286 (4), 273 (3), 197 (11), 196 (77), 183 (10), 181 (12), 171 (9), 169 (4), 167 (3), 156 (5), 155 (5),
130 (6), 118 (6), 117 (12), 115 (9), 105 (9), 103 (5), 91 (9), 77 (8), 65 (5).
2-(1-(4-methoxyphenyl)-2-(methyl(p-tolyl)amino)ethyl)malononitrile (4f):
1H-NMR (400 MHz, CDCl3): δ = 7.33 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 8.7
N
Hz, 2H), 6.97 (d, J = 8.7 Hz, 2H), 6.75 (d, J = 8.7 Hz, 2H), 4.26 (d, J = 4.2
Hz, 1H), 3.86 – 3.74 (m, 4H), 3.64 – 3.52 (m, 2H), 2.94 (s, 3H), 2.29 (s, 3H);
NC CN
13C-NMR (100.6 MHz, CDCl3): δ = 160.2, 146.6, 133.4, 130.1, 129.3, 128.5,
O
126.7, 114.7, 114.6, 114.5, 112.4, 111.8, 55.7, 55.3, 44.2, 41.3, 27.2, 20.3; IR (neat): ν = 3434, 3011,
2919, 2849, 2226, 2053, 1882, 1713, 1615, 1579, 1515, 1460, 1381, 1252, 1180, 1117, 1030, 808, 730,
528, 461; MS-EI: m/z(%): 319 (6), 317 (3), 196 (4), 135 (10), 134 (100), 133 (7), 119 (7), 118 (6), 91 (10),
77 (3), 65 (4).
2-(2-(methyl(p-tolyl)amino)-1-(4-(trifluoromethyl)phenyl)ethyl)malononitrile (4g):
1H-NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 8.2 Hz, 2H), 7.55 (d, J = 8.2
N
Hz, 2H), 7.13 (d, J = 8.2 Hz, 2H), 6.76 (d, J = 8.6 Hz, 2H), 4.35 (d, J = 4.3
Hz, 1H), 3.81 (dd, J = 15.7, 11.7 Hz, 1H), 3.69 – 3.61 (m, 2H), 2.95 (s, 3H),
2.30 (s, 3H); 13C-NMR (100.6 MHz, CDCl3): δ = 146.6, 138.9, 132.7, 132.0,
NC CN
F
F
F
130.4, 129.4, 128.9, 126.5 (q, JCF = 4 Hz), 115.2, 112.0, 111.5, 55.6, 44.7,
41.8, 26.8, 20.5; IR (neat): ν =2919, 2234, 1708, 1618, 1575, 1519, 1426, 1382, 1325, 1241, 1173, 1115,
1069, 1017, 840, 809, 731, 610, 517; MS-EI: m/z(%): 358 (2), 357 (10), 135 (10), 134 (100), 119 (7), 118
(8), 91 (14), 77 (4), 65 (6).
S11

2-(1-([1,1'-biphenyl]-4-yl)-2-(methyl(p-tolyl)amino)ethyl)malononitrile (4h):
1H-NMR (400 MHz, CDCl3): δ = 7.67 (d, J = 8.3 Hz, 2H), 7.63 – 7.59 (m,
N
2H), 7.51 – 7.44 (m, 4H), 7.41 – 7.36 (m, 1H), 7.13 (d, J = 8.7 Hz, 2H),
6.78 (d, J = 8.7 Hz, 2H), 4.33 (d, J = 4.3 Hz, 1H), 3.91 – 3.80 (m, 1H),
3.72 – 3.61 (m, 2H), 2.98 (s, 3H), 2.30 (s,3H); 13C-NMR (100.6 MHz,
CDCl3): δ = 146.8, 142.4, 140.3, 133.9, 130.3, 129.0, 128.9, 128.7, 128.1,
NC CN
127.9, 127.3, 114.9, 112.4, 111.9, 55.8, 44.7, 41.6, 27.1, 20.5; IR (neat): ν = 3437, 3030, 2918, 2854,
2254, 1882, 1710, 1616, 1576, 1519, 1450, 1381, 1339, 1215, 1189, 1116, 836, 807, 761, 697, 514; MS-
EI: m/z(%): 366 (2), 365 (8), 230 (3), 165 (3), 135 (10), 134 (100), 119 (6), 118 (5), 91 (8), 77(3), 65 (3),
57 (3).
2-(1-(4-(tert-butyl)phenyl)-2-(methyl(p-tolyl)amino)ethyl)malononitrile (4i):
1H-NMR (400 MHz, CDCl3): δ = 7.45 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4
N
Hz, 2H), 7.11 (d, J = 8.7 Hz, 2H), 6.76 (d, J = 8.7 Hz, 2H), 4.29 (d, J = 4.2
Hz, 1H), 3.79 (dd, J = 14.7, 10.8 Hz, 1H), 3.67 – 3.54 (m, 2H), 2.96 (s, 3H),
NC CN
2.29 (s, 3H), 1.34 (s, 9H); 13C-NMR (100.6 MHz, CDCl3): δ = 152.5, 146.8,
131.9, 130.3, 128.7, 128.0, 126.4, 114.9, 112.5, 112.0, 55.7, 44.6, 41.5, 34.8,
31.4, 27.2, 20.5; IR (neat): ν =3435, 2961, 2919, 2255, 1706, 1616, 1574, 1518, 1461, 1367, 1269, 1212,
1188, 1113, 1018, 807, 757, 569, 516; MS-EI: m/z(%): 346 (2), 345 (8), 135 (10), 134 (100), 133 (2), 119
(5), 118 (5), 117 (2), 91 (7), 77 (2), 65 (2), 57 (2).
2-(2-((4-(tert-butyl)phenyl)(methyl)amino)-1-(p-tolyl)ethyl)malononitrile (4j):
1H-NMR (600 MHz, CDCl3): δ = 7.36 – 7.29 (m, 4H), 7.26 (d, J = 7.3 Hz,
N
2H), 6.79 (d, J = 8.8 Hz, 2H), 4.28 (d, J = 4.4 Hz, 1H), 3.82 (dd, J = 14.8,
10.6 Hz, 1H), 3.65 (dd, J = 14.8, 4.9 Hz, 1H), 3.62 – 3.57 (m, 1H), 2.97 (s,
3H), 2.40 (s, 3H), 1.32 (s, 9H); 13C-NMR (151.8 MHz, CDCl3): δ = 146.4,
NC CN
141.7, 139.2, 131.8, 130.0, 128.0, 126.4, 113.9, 112.4, 111.9, 55.6, 44.6, 41.0, 33.9, 31.5, 27.1, 21.2; IR
(neat): ν = 3436, 3020, 2960, 2920, 2856, 1713, 1613, 1518, 1215, 757, 668; MS-EI: m/z(%): 345 (8), 328
(10), 177 (13), 176 (100), 161 (5), 146 (10), 118 (4), 91 (3), 77 (2).
S12

2-(2-((4-(tert-butyl)phenyl)(methyl)amino)-1-(2,4-dimethylphenyl)ethyl)malononitrile (4k):
1H-NMR (400 MHz, CDCl3): δ = 7.38 (d, J = 7.9 Hz, 1H), 7.33 (d, J = 8.9
N
Hz, 2H), 7.17 – 7.08 (m, 2H), 6.76 (d, J = 8.9 Hz, 2H), 4.19 (d, J = 5.4 Hz,
1H), 3.99 (m, 1H), 3.82 (dd, J = 14.9, 9.7 Hz, 1H), 3.59 (dd, J = 14.9, 5.2 Hz,
NC CN
1H), 2.95 (s, 3H), 2.34 (s, 3H), 2.33 (s, 3H), 1.32 (s, 9H); 13C-NMR (100.6
MHz, CDCl3): δ = 146.2, 141.5, 138.6, 136.7, 132.2, 130.7, 127.7, 126.3, 126.0, 113.5, 112.3, 112.1, 56.1,
41.2, 39.1, 33.9, 31.4, 26.6, 21.0, 19.7; IR (neat): ν = 3440, 2958, 2252, 1881, 1708, 1613, 1518, 1460,
1372, 1203, 1126, 1038, 912, 819, 732, 560; MS-EI: m/z(%): 359 (8), 177 (13), 176 (100), 146 (9), 91 (3),
77 (2).
2-(2-((4-(tert-butyl)phenyl)(methyl)amino)-1-(o-tolyl)ethyl)malononitrile (4l):
1H-NMR (400 MHz, CDCl3): δ = 7.52 – 7.45 (m, 1H), 7.36 – 7.23 (m, 5H),
N
6.75 (d, J = 8.9 Hz, 2H), 4.19 (d, J = 5.5 Hz, 1H), 4.06 – 3.98 (m, 1H), 3.84
(dd, J = 14.9, 9.6 Hz, 1H), 3.60 (dd, J = 14.9, 5.3 Hz, 1H), 2.93 (s, 3H), 2.36
(s, 3H), 1.31 (s, 9H); 13C-NMR (100.6 MHz, CDCl3): δ = 146.2, 141.5, 134.0,
NC CN
133.8, 131.4, 128.8, 127.0, 126.4, 126.1, 113.6, 112.2, 112.0, 56.1, 41.2, 39.3, 33.9, 31.4, 26.5, 19.8; IR
(neat): ν = 3468, 3031, 2960, 2568, 2253, 1879, 1710, 1613, 1519, 1462, 1363, 1205, 1130, 1048, 911,
818, 732, 649, 555, 498; MS-EI: m/z(%): 345 (12), 177 (14), 176 (100), 146 (12), 118 (5), 91 (3), 77 (2).
2-(1-(4-(tert-butyl)phenyl)-2-((4-(tert-butyl)phenyl)(methyl)amino)ethyl)malononitrile (4m):
1H-NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.5 Hz, 2H), 7.38 – 7.31 (m,
N
4H), 6.79 (d, J = 8.9 Hz, 2H), 4.30 (d, J = 4.2 Hz, 1H), 3.81 (dd, J = 14.8,
10.8 Hz, 1H), 3.69 – 3.57 (m, 2H), 2.99 (s, 3H), 1.35 (s, 9H), 1.31 (s, 9H);
13C-NMR (100.6 MHz, CDCl3): δ = 152.3, 146.4, 141.7, 131.6, 127.8,
NC CN
126.4, 126.2, 113.9, 112.4, 111.9, 55.5, 44.6, 41.1, 34.7, 33.9, 31.4, 31.2,
27.0; IR (neat): ν = 3437, 3020, 2919, 2401, 1580, 1519, 1425, 1383, 1215, 1034, 928, 758, 669; MS-EI:
m/z(%): 387 (7), 177 (13), 176 (100), 161 (5), 160 (3), 146 (8), 57 (7).
2-(2-(methyl(phenyl)amino)-1-phenylethyl)malononitrile (4n):
1H-NMR (300 MHz, CDCl3): δ = 7.51 – 7.39 (m, 5H), 7.36 – 7.28 (m, 2H), 6.91 –
N
6.79 (m, 3H), 4.24 (d, J = 4.6 Hz, 1H), 3.92 (dd, J = 14.8, 10.1 Hz, 1H), 3.76 – 3.59
(m, 2H), 2.98 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 148.7, 135.0, 129.7, 129.5,
NC CN
128.2, 127.7, 118.9, 114.0, 112.3, 111.9, 55.5, 44.9, 41.0, 27.1; IR (neat): ν = 3063,
3034, 2895, 2254, 1709, 1599, 1502, 1453, 1353, 1198, 1122, 1034, 993 911, 752, 698, 518; MS-EI:
m/z(%): 276 (2), 275 (7), 121 (10), 120 (100), 119 (3), 105 (5), 104 (6), 103 (2), 91 (4), 77 (13), 51 (4).
S13

2-(2-((3-bromophenyl)(methyl)amino)-1-phenylethyl)malononitrile (4o):
1H-NMR (300 MHz, CDCl3): δ = 7.48 – 7.36 (m, 5H), 7.14 (t, J = 8.2 Hz, 1H),
6.99 – 6.93 (m, 1H), 6.88 (t, J = 2.3 Hz, 1H), 6.70 (dd, J = 8.2, 2.3 Hz, 1H), 4.14
(d, J = 4.9 Hz, 1H), 3.94 (dd, J = 15.0, 9.3 Hz, 1H), 3.71 (dd, J = 15.0, 5.7 Hz,
1H), 3.66 – 3.56 (m, 1H), 2.93 (s, 3H); 13C-NMR (75.4 MHz, CDCl3): δ = 149.7,
Br
N
NC CN
134.9, 130.9, 129.6, 128.1, 127.7, 123.9, 121.3, 116.3, 112.0, 111.9, 111.8, 55.3, 44.7, 40.7, 27.1; IR
(neat): ν = 3658, 3469, 3069, 3033, 2904, 2579, 2377, 2255, 1814, 1708, 1593, 1555, 1493, 1454, 1428,
1357, 1292, 1243, 1181, 1125, 986, 911, 836, 799, 763, 733, 700, 571, 522; MS-EI: m/z(%): 355 (8), 353
(8), 201 (8), 200 (100), 199 (14), 198 (98), 197 (4), 184 (3), 183 (3), 182 (3), 157 (3), 155 (3).
2-(2-(methyl(o-tolyl)amino)-1-phenylethyl)malononitrile (4p):
1H-NMR (300 MHz, CDCl3): δ = 7.46 – 7.34 (m, 5H), 7.28 – 7.19 (m, 2H), 7.13 –
N
7.07 (m, 2H), 4.44 (d, J = 4.3 Hz, 1H), 3.56 (dd, J = 13.1, 4.9 Hz, 1H), 3.51 – 3.41
(m, 1H), 3.38 – 3.28 (m, 1H), 2.71 (s, 3H), 2.33 (s, 3H); 13C-NMR (75.4 MHz,
NC CN
CDCl3): δ = 149.5, 135.3, 134.2, 131.9, 129.3, 129.3, 128.2, 127.2, 125.1, 120.6,
112.6, 111.7, 56.3, 44.9, 44.5, 27.0, 18.0; IR (neat): ν = 3660, 3064, 3029, 2950, 2916, 2851, 2801, 2255,
1705, 1594, 1495, 1454, 1380, 1290, 1217, 1169, 1113, 1050, 984, 936, 763, 700, 667, 579,459; MS-EI:
m/z(%): 289 (3), 135 (11), 134 (100), 133 (3), 119 (3), 118 (9), 91 (10), 77 (4), 65 (6).
2-(1-(4-(tert-butyl)phenyl)-2-((3,5-dimethylphenyl)(methyl)amino)ethyl)malononitrile (4q):
1H-NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.5
N
Hz, 2H), 6.53 (s, 1H), 6.45 (s, 2H), 4.24 (d, J = 4.3 Hz, 1H), 3.85 (dd, J =
14.9, 10.5 Hz, 1H), 3.66 (dd, J = 14.9, 4.7 Hz, 1H), 3.62 – 3.56 (m, 1H), 2.97
NC CN
(s, 3H), 2.30 (s, 6H), 1.34 (s, 9H); 13C-NMR (100.6 MHz, CDCl3): δ = 152.5,
148.9, 139.4, 131.9, 128.0, 126.4, 120.9, 112.5, 112.0, 55.4, 44.8, 41.1, 34.8, 31.4, 27.2, 21.9; IR (neat): ν
= 3781, 3435, 2960, 2918, 2254, 1906, 1721, 1598, 1481, 1379, 1269, 1233, 1178, 1114, 1045, 918, 824,
757, 691, 563; MS-EI: m/z(%): 360 (2), 359 (9), 149 (11), 148 (100), 147 (5), 133 (4), 132 (3), 117 (2),
105 (3), 91 (4), 79 (2), 77 (2), 57 (2).
2-(2-((4-bromophenyl)(methyl)amino)-1-(4-(trifluoromethyl)phenyl)ethyl)malononitrile (4r):
1H-NMR (300 MHz, CDCl3): δ = 7.73 (d, J = 8.1 Hz, 2H), 7.53 (d, J = 8.1
N
Hz, 2H), 7.38 (d, J = 9.2 Hz, 2H), 6.66 (d, J = 9.2 Hz, 2H), 4.21 (d, J = 4.4
Hz, 1H), 3.97 – 3.86 (m, 1H), 3.75 – 3.62 (m, 2H), 2.94 (s, 3H); 13C-NMR
Br
NC CN
F
F
(75.4 MHz, CDCl3): δ = 147.4, 138.7, 132.6, 131.9 (q, JCF = 33 Hz), 128.8,
F
S14

127.8, 126.6 (q, JCF = 4 Hz), 125.6, 115.6, 111.7, 111.4, 55.2, 44.5, 41.1, 26.8; IR (neat): ν = 3079, 2907,
2256, 1925, 1867, 1804, 1709, 1591, 1499, 1425, 1327, 1240, 1171, 1116, 1070, 911, 839, 811, 733, 604,
517; MS-EI: m/z(%): 422 (13), 420 (13), 201 (8), 200 (100), 199 (5), 198 (100), 185 (5), 184 (6), 183 (7),
182 (6), 157 (4), 155 (5), 119 (19), 118 (27), 104 (8), 103 (4), 91 (4), 90 (4), 78 (4), 77 (10), 76 (7), 75 (9),
69 (5), 63 (6), 57 (4), 51 (4), 50 (4).
Characterization of substrates 5a-m and products 5a’ and 6a-l
(E)-4-(2-(dibenzylamino)phenyl)but-3-en-2-one (5a):
1H NMR (600 MHz, CDCl3): δ = 8.18 (d, J = 16.5 Hz, 1H), 7.58 (d, J = 7.8 Hz, 1H),
O
7.33 – 7.20 (m, 11H), 7.07 (t, J = 7.5 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 6.64 (d, J = 16.5
Hz, 1H), 4.21 (s, 4H), 2.31 (s, 3H); 13C NMR (151.8 MHz, CDCl3): δ = 199.2, 151.1,
Me
141.5, 137.8, 130.8, 129.9, 128.5, 128.5, 127.9, 127.6, 127.3, 123.6, 122.5, 58.0, 26.9;
IR (neat): ν =3248, 2921, 1734, 1667, 1597, 1456, 1362, 989, 757cm–1; EI-MS: m/z =
Bn
N
Bn
342 (M++1, 8%), 341 (M+, 29%), 250 (53%), 208 (56%), 91 (100%).
(E)-4-(2-(bis(4-methylbenzyl)amino)phenyl)but-3-en-2-one (5b):
1H NMR (300 MHz, CDCl3): δ = 8.27 (d, J = 16.6 Hz, 1H), 7.64 (d, J = 7.8
O
Hz, 1H), 7.40 – 7.27 (m, 1H), 7.25 – 7.01 (m, 10H), 6.72 (dd, J = 16.6, 1.5
Hz, 1H), 4.23 (s, 4H), 2.41(s, 3H), 2.40 (s, 6H); 13C NMR (75 MHz, CDCl3):
δ = 199.1, 151.2, 141.6, 136.8, 134.7, 130.6, 129.8, 129.1, 129.0, 128.6,
128.5, 127.7, 127.3, 123.3, 122.5, 57.5, 26.8, 21.2; IR (neat): ν = 3246, 2921,
1733, 1667, 1599, 1255, 755 cm–1; EI-MS: m/z = 370.2 (M++1, 16%), 369.1
Me
N
p-MeC6H4
p-MeC6H4
(M+, 32%), 264.1 (39%), 222.2 (29%), 105.2 (100%).
(E)-4-(3,5-dichloro-2-(dibenzylamino)phenyl)but-3-en-2-one (5c):
1H NMR (400 MHz, CDCl3): δ = 7.45 (s, 1H), 7.43 (d, J = 16.0 Hz, 1H), 7.30 – 7.22
O
(m, 9H), 7.17 (m, 4H), 6.20 (d, J = 16.0 Hz, 1H), 4.26 (s, 4H), 2.14 (s, 3H); 13C
NMR (100.6 MHz, CDCl3): δ = 198.5, 145.3, 140.8, 138.4, 138.3, 136.2, 132.0,
131.8, 129.4, 129.3, 129.2, 128.5, 127.7, 125.6, 57.4, 26.5; IR (neat): ν = 3247,
2920, 1731, 1459, 1216, 756 cm–1; EI-MS: m/z = 411 (M++2, 7%), 410 (M+1, 4%),
Me
Cl
Bn
N
Cl
Bn
409 (M+, 11%), 276 (13%), 91.2 (100%).
S15

(E)-4-(2-(dibenzylamino)-5-fluorophenyl)but-3-en-2-one (5d):
1H NMR (600MHz, CDCl3): δ = 8.12 (d, J = 16.6 Hz, 1H), 7.32-7.26 (m, 4H), 7.25-
O
7.18 (m, 7H),7.01-6.93 (m, 2H), 6.53 (d, J = 16.5 Hz, 1H), 4.12 (s, 4H), 2.32 (s, 3H);
Me
1
13C NMR (150MHz, CDCl3): δ =198.6, 159.1(d, JC-F = 243.5 Hz), 146.9, 139.8,
F
3
2
137.4, 128.6, 128.4, 128.3, 128.2, 127.3, 124.5 (d, JC-F = 8.3 Hz), 117.4 (d, JC-F
=
Bn
N
22.5 Hz), 113.4 (d, 2JC-F = 22.8 Hz), 58.5, 27.0; IR (neat): ν = 3433, 3064, 3021, 1668,
Bn
1606, 1488, 1452, 1216, 757 cm-1; EI-MS: m/z = 360.3 (M+ +1, 15%), 359.2 (M+, 41%), 268.2 (47%),
226.2 (47.3%), 91.1 (100%).
(E)-4-(5-chloro-2-(dibenzylamino)phenyl)but-3-en-2-one (5e)
1H NMR (300 MHz, CDCl3): δ = 8.10 (d, J = 16.5 Hz, 1H), 7.54 (d, J = 2.5 Hz, 1H),
O
7.41 – 7.14 (m, 11H), 6.94 (d, J = 8.7 Hz, 1H), 6.63 (d, J = 16.5 Hz, 1H), 4.20 (s,
4H), 2.33 (s, 3H); 13C NMR (75 MHz, CDCl3): δ = 198.5, 149.4, 139.7, 137.3,
Me
Cl
131.6, 130.3, 128.8, 128.7, 128.5, 128.5, 128.2, 127.5, 123.9, 58.0, 27.3; IR (neat): ν
= 3304, 2921, 1732, 1668, 1475, 1215, 756 cm–1; EI-MS: m/z = 376 (M++1, 7%),
Bn
N
Bn
369.1 (M+, 19%), 284 (17%), 242 (26%), 91 (100%).
(E)-4-(2-(1,3-bis(3-chlorophenyl)propan-2-yl)phenyl)but-3-en-2-one (5f)
1H NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 16.5 Hz, 1H), 7.57 (dd, J = 1.5,
O
Me
7.8 Hz, 1H), 7.29 (m, 1H), 7.22 (dd, J = 0.9, 4.8 Hz, 6H), 7.12 (d, J =7.8 Hz,
1H), 7.07 (m, 2H), 7.00 (dd, J = 1.0, 8.1 Hz, 1H), 6.62 (d, J = 16.5 Hz, 1H),
N
m-ClC6H4 4.12 (s, 4H), 2.35 (s, 3H); 13C NMR (100.6 MHz, CDCl3): δ = 197.9, 148.6,
138.8, 135.4, 133.3, 131.8, 130.4, 130.0, 129.9, 129.4, 128.7, 128.6, 128.0,
m-ClC6H4
127.5, 127.9, 57.2, 27.9; IR (neat): = ν = 3440, 3059, 2924, 2850, 1944, 1672, 1598, 1472, 1369 cm-1; EI-
MS: m/z = 410 (M+ +1, 7%), 409 (M+, 20%), 284 (46%), 242 (70%), 125 (100%).
(E)-4-(2-(bis(4-methylbenzyl)amino)-5-fluorophenyl)but-3-en-2-one (5g):
1H NMR (600 MHz, CDCl3): δ = 8.15 (dd, J = 16.6, 1.3 Hz, 1H), 7.28 – 7.18
O
(m, 1H), 7.13-7.11 (m, 8H), 7.04 – 6.89 (m, 2H), 6.56 (d, J = 16.6 Hz, 1H),
4.09 (s, 4H), 2.37 (s, 3H), 2.33 (s, 6H); 13C NMR (151 MHz, CDCl3): δ =
Me
F
198.7, 159.1 (d, JCF = 241.8 Hz), 147.1, 140.0 (d, JCF = 1.59 Hz), 136.9,
N
p-MeC6H4
134.5, 132.3 (d, JCF = 7.38 Hz), 129.1, 128.7, 128.1, 124.6 (d, JCF = 8.12 Hz),
117.4 (d, JCF = 22.35 Hz), 113.4 (d, JCF = 22.64 Hz), 58.2, 27.0, 21.2; IR
p-MeC6H4
(neat): ν = 3458, 2923, 1739, 1671, 1484, 1178, 812 cm–1; EI-MS: m/z = 388 (M++1, 5%), 387 (M+, 14%),
282 (14%), 240 (12%), 105 (100%).
S16

(E)-4-(2-(dibenzylamino)-4-fluorophenyl)but-3-en-2-one (5h):
1H NMR (600 MHz, CDCl3): δ = 8.05 (d, J = 16.5 Hz, 1H), 7.54 (dd, J = 8.6, 6.7 Hz,
O
1H), 7.33-7.30 (m, 4H), 7.27 – 7.23 (m, 4H), 6.76 (dt, J = 8.3, 2.4 Hz, 1H), 6.68 (dd,
J = 10.8, 2.4 Hz, 1H), 6.60 (d, J = 16.5 Hz, 1H), 4.20 (s, 4H), 2.28 (s, 3H); 13C NMR
(151.8 MHz, CDCl3): δ = 198.9, 164.4 (d, J = 249.0 Hz), 153.1 (d, J = 9.0 Hz), 153.1,
140.5, 137.3, 129.5 (d, J = 9.0 Hz), 128.6, 128.4, 127.5, 127.1 (d, J = 1.5 Hz), 125.7
Me
Bn
F
N
Bn
(d, J = 3.0 Hz), 110.6 (d, J = 22.5 Hz), 109.5 (d, J = 22.5 Hz), 57.8, 27.0; IR (neat): ν = 3437, 2920, 1733,
1578, 1385, 1072, 721 cm–1; EI-MS: m/z = 360 (M++1, 4%), 359 (M+, 12%), 268 (29%), 226 (31%), 91
(100%).
(E)-4-(2-(bis(4-chlorobenzyl)amino)-5-chlorophenyl)but-3-en-2-one (5i):
H NMR (400 MHz, CDCl3): δ = 8.00 (d, J = 16.4 Hz, 1H), 7.05(d, J = 2.5 Hz,
O
1H), 7.24 (d, J = 8.4 Hz, 4H), 7.18 (dd, J = 2.5, 8.6 HZ, 1H), 7.08 (d, J = 8.4
Me
Hz, 4H), 6.83 (d, J = 8.7 Hz, 1H), 6.62 (d, J = 16.3 Hz, 1H), 4.05 (s, 4H), 2.32
Cl
(S, 3H); 13C NMR (100.6 MHz, CDCl3): δ = 197.9, 148.6, 138.8, 135.4, 133.3,
N
p-ClC6H4
131.8, 130.4, 129.95, 129.87, 129.4, 128.7, 128.6, 128.0, 127.5, 123.9, 55.2,
p-ClC6H4
27.9; IR (neat): ν = 3426, 2922, 2852, 1897, 1672, 1605, 1464, 1384, 1090 cm-
1; EI-MS: m/z = 444.1 (M+ +1, 7%), 443.1 (M+, 20%), 318.2 (18%), 276. 1 (33%), 125 (100%).
(E)-4-(2-(bis(4-fluorobenzyl)amino)phenyl)but-3-en-2-one (5j):
1H NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 16.5 Hz, 1H), 7.57 (dd, J = 7.8, 1.6
O
Hz, 1H), 7.30 – 7.21 (m, 1H), 7.18 – 7.11 (m, 4H), 7.11 – 7.03 (m, 1H), 7.01 –
Me
6.91 (m, 5H), 6.66 (d, J = 16.4 Hz, 1H), 4.11 (s, 4H), 2.35 (s, 3H); 13C NMR
(100.6 MHz, CDCl3): δ = 198.8, 162.2 (d, J = 244.0 Hz), 150.6, 140.9, 133.3 (d,
N
p-FC6H4
J = 3.0 Hz), 130.8, 130.2 (d, J = 244.0 Hz), 127.9, 127.4, 124.0, 122.8, 115.4 (d,
J = 244.0 Hz), 57.2, 27.4; IR (neat): ν = 3302, 2922, 1668, 1602, 1507, 1222,
p-FC6H4
830, 756 cm–1; EI-MS: m/z = 378 (M++1, 30%), 377 (M+, 49%), 268 (48%), 226 (53%), 109 (100%).
(E)-4-(2-(bis(4-fluorobenzyl)amino)-5-chlorophenyl)but-3-en-2-one (5k):
1H NMR (600 MHz, CDCl3 as E:Z= 1.6:1): δ = 8.05 (d, J = 16.4 Hz, 1H), 7.53
O
(d, J = 2.4 Hz, 1H), 7.28 – 7.23 (m, 2H), 7.22 (dd, J = 8.6, 2.4 Hz, 1H), 7.18 –
Me
7.12 (m, 4H), 7.09 (d, J = 2.2 Hz, 1H), 7.02 – 6.93 (m, 6H), 6.88 (d, J = 8.6
Hz, 1H), 6.81 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 16.4 Hz, 1H), 4.09 (s, 4H), 4.00
Cl
N
p-FC6H4
p-FC6H4
S17

(s, 4H), 2.36 (s, 3H), 2.22 (s, 3H); 13C NMR (151.8 MHz, CDCl3): δ = 206.2, 198.2, 162.2 (d, JCF = 245.0
Hz), 162.2 (d, JCF = 244.0 Hz), 149.0, 145.9, 139.1, 137.1, 133.4 (d, JCF = 2.97 Hz), 132.8 (d, JCF = 3.06
Hz), 131.9, 130.6, 130.4, 130.4 (d, JCF = 7.97 Hz), 130.2 (d, JCF = 7.89 Hz), 129.4, 128.1, 127.6, 124.8,
124.7, 124.4, 124.2, 115.5 (d, JCF = 21.20 Hz), 115.1 (d, JCF = 21.1 Hz), 57.2, 56.0, 30.2, 27.9; IR (neat): ν
= 3301, 2921, 1726, 1671, 1604, 1470, 1222, 828, 758 cm–1; EI-MS: m/z = 412 (M++1, 3%), 411 (M+,
11%), 109 (100%), 43 (35%).
(E)-4,4'-(2-(3-oxobut-1-enyl)phenylazanediyl)bis(methylene)dibenzonitrile (5l):
1H NMR (400 MHz, CDCl3): δ = 8.11 (d, J = 16.3 Hz, 1H), 7.57 (d, J = 12.0
O
Hz, 4H), 7.32 (d, J = 12 Hz, 4H), 7.27-7.23 (m, 1H), 7.10 (t, J = 8.0 Hz, 1H),
Me
6.92 (dd, J = 8.0, 1.0 Hz, 1H), 6.69 (d, J = 16.3 Hz, 1H), 4.20 (s, 4H), 2.32
(s, 3H); 13C NMR (100.6 MHz, CDCl3): δ = 198.2, 149.4, 142.7, 139.7,
N
p-CNC6H4
132.4, 130.9, 130.1, 129.2, 128.1, 127.5, 124.6, 122.3, 118.6, 111.5, 57.9,
p-CNC6H4
28.1; IR (neat): ν = 3243, 2919, 1731, 1468, 1215, 756 cm–1; EI-MS: m/z =
392 (M++1, 5%), 391 (M+, 17%), 275 (30%), 233 (51%), 116 (61%), 43 (100%).
3-(2-(Dibenzylamino)benzylidene)pentane-2,4-dione (5m):
1H NMR (400 MHz, CDCl3): δ = 8.07 (s, 1H), 7.34 – 7.20 (m, 12H), 7.05 – 6.97 (m,
O
O
2H), 4.23 (s, 4H), 2.34 (s, 3H), 2.23 (s, 3H); 13C NMR (100.6 MHz, CDCl3): δ = 205.0,
196.9, 151.3, 141.8, 139.5, 137.6, 131.1, 130.2, 128.6, 128.5, 128.4, 127.5, 123.3, 122.3,
57.8, 31.6, 26.7; IR (neat): ν = 3438, 2922, 1706, 1382, 1216, 756 cm–1; EI-MS: m/z =
384 (M++1, 17%), 383 (M+1, 47%), 340 (50%), 283 (47%), 91(100%).
Me
Me
Bn
N
Bn
(Z)-4-(2-(dibenzylamino)phenyl)but-3-en-2-one (5a’):
1H NMR (400 MHz, CDCl3): δ = 7.44 (d, J = 12.3 Hz, 1H), 7.38 (dd, J = 7.6, 1.4 Hz, 1H),
O
7.34 – 7.28 (m, 4H), 7.28 – 7.20 (m, 7H), 7.01 (m, 1H), 6.93 (dd, J = 8.1, 0.9 Hz, 1H), 6.25
(d, J = 12.3 Hz, 1H), 4.18 (s, 4H), 2.17 (s, 3H); 13C NMR (100.6 MHz, CDCl3): δ = 200.9,
150.2, 140.4, 137.8, 131.6, 130.7, 129.7, 128.8, 128.5, 128.4, 127.3, 122.5, 121.6,
56.9(2C), 30.6; IR (neat): ν = 3433, 2922, 1736, 1666, 1596, 1216, 757 cm–1; EI-MS: m/z =
Me
Bn
N
Bn
342 (M++1, 11%), 341 (M+, 47%), 250 (31%), 208 (50%), 91 (100%).
S18

1-Benzyl-2-phenyl-1H-indole-3-carbaldehyde (6a):1
1
reaction time: 20h, H NMR (600 MHz, CDCl3): δ = 9.79 (s, 1H), 8.49 (d, J = 7.9 Hz,
CHO
1H), 7.53 (m,1H), 7.49 (t, J = 7.6 Hz, 2H), 7.44 (m, 2H), 7.37 (t, J= 7.5 Hz, 1H), 7.32 –
7.24 (m, 5H), 6.99 (dd, J = 7.3, 0.8 Hz, 2H), 5.31 (s, 2H);13C NMR (151.8 MHz, CDCl3):
δ = 187.0, 151.8, 137.0, 136.6, 130.9, 130.1, 129.1, 128.8, 128.7, 127.9, 126.1, 125.6,
Ph
N
Ph
124.4, 123.5, 122.4, 116.4, 110.9, 47.9; IR (neat): ν = 3433, 2921, 2254, 1714, 1648, 1461, 1384, 908, 734
cm–1; EI-MS: m/z = 312 (M++1, 100%).
1-(4-Methylbenzyl)-2-p-tolyl-1H-indole-3-carbaldehyde (6b):
1
reaction time: 34h, H NMR (400 MHz, CDCl3): δ = 9.78 (s, 1H), 8.46 (d, J =
7.8 Hz, 1H), 7.36 – 7.21 (m, 7H), 7.08 (d, J = 8.2 Hz, 2H), 6.88 (d, J = 8.2 Hz,
2H), 5.25 (s, 2H), 2.44 (s, 3H), 2.31 (s, 3H); 13C NMR (100.6 MHz, CDCl3): δ
= 187.1, 152.1, 140.3, 137.5, 137.0, 133.6, 130.9, 129.7, 129.5, 126.0, 125.7,
CHO
p-MeC6H4
N
p-MeC6H4
124.2, 123.4, 122.3, 116.2, 111.0, 47.7, 21.6, 21.2; IR (neat): ν = 3437, 2919, 1733, 1577, 1385, 1071, 721
cm–1; EI-MS: m/z = 340 (M++1, 31%), 339 (M+, 100%), 238 (28%), 105 (96%).
1-Benzyl-5,7-dichloro-2-phenyl-1H-indole-3-carbaldehyde (6c):
1
reaction time: 30h, H NMR (600 MHz, CDCl3): δ = 9.67 (s, 1H), 8.46 (d, J = 2.0
CHO
Cl
Hz, 1H), 7.56 – 7.49 (m, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.36 (dd, J = 8.2, 1.2 Hz, 2H),
7.27- 7.23 (m, 4H), 6.81 – 6.75 (m, 2H), 5.65 (s, 2H); 13C NMR (151.8 MHz,
Ph
N
Cl
CDCl3): δ = 186.5, 154.3, 138.1, 131.2, 130.9, 130.6, 130.6, 129.4, 129.0, 128.9,
Ph
127.8, 127.7, 126.3, 125.4, 120.7, 117.9, 116.1, 49.3; IR (neat): ν = 3438, 2921, 1578, 1544, 1436, 1215,
757 cm–1; EI-MS: m/z = 381 (M++2, 22%), 379 (M+, 34%), 91 (100%).
1-Benzyl-5-fluoro-2-phenyl-1H-indole-3-carbaldehyde (6d):
1
reaction time: 30h, H-NMR (300 MHz, CDCl3): δ = 9.74 (s, 1H), 8.14 (dd, J = 2.5,
CHO
F
9.2 Hz, 2H), 7.48 (m, 7H), 7.28 (m, 7H), 7.14 (dd, J = 8.9, 4.3 Hz, 2H), 7.02 (dd, J =
9.0, 2.7 Hz, 1H), 6.96 (dd, J = 7.7, 1.9 Hz, 3H), 5.28 (s, 2H); 13C NMR (150 MHz,
Ph
N
CDCl3): δ = 186.6, 160.1 (d, JC-F = 239.6 Hz), 152.5, 136.1, 133.3, 130.1, 130.2,
Ph
129.0, 128.8, 127.8, 125.9, 116.1, 112.5 (d, JC-F = 26.2 Hz), 111.7 (d, JC-F = 9.6 Hz), 107.8 (d, JC-F = 24.9
Hz), 48.0; IR (neat): ν = 3435, 2931, 2853, 1634, 1452, 1384, 1153, 1068 cm-1; EI-MS: m/z =330.3
(M++1, 26%), 329.3 (M+, 87%), 238.3(15%), 183.2(11%), 91.3(100%).
S19

1-Benzyl-5-chloro-2-phenyl-1H-indole-3-carbaldehyde (6e):
1
reaction time: 34h, H NMR (600 MHz, CDCl3): δ = 9.74 (s, 1H), 8.46 (d, J = 1.99
CHO
Cl
Hz, 1H), 7.55 – 7.42 (m, 5H), 7.32 – 7.26 (m, 3H), 6.93(dd, J = 8.92, 1.99 Hz, 1H),
7.13 (d, J = 8.92 Hz, 1H), 6.94 (d, J = 5.94 Hz, 2H), 5.27 (s, 2H); 13C NMR (151.8
MHz, CDCl3): δ = 186.5, 152.3, 136.0, 135.2, 130.7, 130.2, 129.3, 129.0, 128.9,
Ph
N
Ph
128.8, 128.1, 127.9, 126.4, 125.9, 124.6, 121.9, 111.8, 47.9; IR (neat): ν = 3305, 2920, 1734, 1579, 1459,
1052, 723 cm–1; EI-MS: m/z = 347 (M++2, 28%), 346 (M++1, 33%), 345 (M+, 100%), 91 (99%).
1-(1-Benzyl-5-chloro-2-phenyl-1H-indol-3-yl)propan-2-one (7e):
1H NMR (600 MHz, CDCl3): δ = 7.50 (d, J = 1.0 Hz, 1H), 7.44 – 7.39 (m, 3H),
O
7.29 (dd, J = 6.4, 3.0 Hz, 2H), 7.26-7.21 (m, 3H), 7.12 – 7.09 (m, 2H), 6.90 (d, J =
6.8 Hz, 2H), 5.21 (s, 2H), 3.71 (s, 2H), 2.10 (s, 3H); 13C NMR (151.8 MHz,
Me
Cl
Ph
N
CDCl3): δ = 207.1, 140.9, 137.8, 135.3, 130.9, 130.5, 129.1, 129.0, 128.9, 127.5,
126.1, 126.0, 122.8, 118.6, 111.7, 106.6, 48.0, 40.5, 29.3; IR (neat): ν = 3246,
Ph
2920, 1732, 1577, 1384, 1053, 720 cm–1; EI-MS: m/z = 375 (M++2, 8%), 373 (M+, 22%), 332 (25%), 330
(62%), 91 (100).
1-(3-Chlorobenzyl)-2-(3-chlorophenyl)-1H-indole-3-carbaldehyde (6f):
1
reaction time: 36h, H NMR (600 MHz, CDCl3): δ = 9.78 (s, 1H), 8.47 (d, J =
7.7 Hz, 1H), 7.54 – 7.50 (m, 1H), 7.43 (t, J = 7.9 Hz, 1H), 7.41 – 7.36 (m, 2H),
7.36 – 7.32 (m, 1H), 7.31 – 7.27 (m, 1H), 7.25-7.23 (m, 2H), 7.21 (t, J = 7.8 Hz,
1H), 6.98 (s, 1H), 6.79 (d, J = 7.5 Hz, 1H), 5.25 (s, 2H); 13C NMR (151.8 MHz,
CHO
m-ClC6H4
N
m-ClC6H4
CDCl3): δ = 186.4, 149.4, 138.4, 137.0, 135.2, 135.0, 130.9, 130.5, 130.3, 130.2, 129.0, 128.4, 126.4,
125.4, 124.9, 124.2, 123.9, 122.7, 116.8, 110.6, 47.4; IR (neat): ν = 3438, 2921, 1733, 1655, 1384, 1084,
752 cm–1; EI-MS: m/z = 381 (M++2, 60%), 380 (M++1, 47%), 379 (M+, 100%), 378 (48%), 125 (95%).
5-Fluoro-1-(4-methylbenzyl)-2-p-tolyl-1H-indole-3-carbaldehyde (6g):
reaction time: 34h, 1H NMR (600 MHz, CDCl3): δ = 9.75 (s, 1H), 8.12 (dd, J
CHO
F
= 9.3, 2.5 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.29 (d, J = 7.9 Hz, 2H), 7.14 –
p-MeC6H4
N
7.07 (m, 3H), 6.98 (dt, J = 9.0, 2.6 Hz, 1H), 6.86 (d, J = 8.0 Hz, 2H), 5.23 (s,
2H), 2.44 (s, 3H), 2.31 (s, 3H); 13C NMR (151.8 MHz, CDCl3): δ = 186.8,
p-MeC6H4
160.2 (d, JCF = 238.35 Hz), 153.0, 140.5, 137.7, 133.4 (d, JCF = 18.98 Hz), 133.3, 130.7, 129.8, 129.6,
126.3, 126.0, 125.4, 116.1, 112.4 (d, JCF = 26.03 Hz), 111.8 (d, JCF = 9.48 Hz), 107.8 (d, JCF = 24.75 Hz),
47.9, 21.6, 21.2; IR (neat): ν = 3436, 2920, 1579, 1545, 1439, 1215, 758 cm–1; EI-MS: m/z = 358 (M++1,
15%), 357 (M+, 54%), 105 (100%).
S20

1-Benzyl-6-fluoro-2-phenyl-1H-indole-3-carbaldehyde (6h):
1
reaction time: 28h, H NMR (600 MHz, CDCl3): δ = 9.65 (s, 1H), 8.30 (dd, J = 8.7,
CHO
5.5 Hz, 1H), 7.44-7.42 (m, 1H), 7.40 – 7.35 (m, 2H), 7.35 – 7.31 (m, 2H), 7.22 – 7.14
(m, 3H), 7.02 – 6.96 (m, 1H), 6.89 – 6.85 (m, 2H), 6.80 (dd, J = 9.3, 2.1 Hz, 1H), 5.14
(s, 2H); 13C NMR (151.8 MHz, CDCl3): δ = 186.9, 160.8 (d, JCF = 240.23 Hz), 152.2,
Ph
N
F
Ph
136.0, 130.9, 130.3, 129.2, 128.9, 128.7, 128.4, 128.1, 126.1, 123.6 (d, JCF = 9.7 Hz), 121.9, 116.2, 112.0
(d, JCF = 23.63 Hz), 97.8 (d, JCF = 26.5Hz), 48.1; IR (neat): ν = 3437, 2920, 1737, 1654, 1384, 1078, 705
cm–1; EI-MS: m/z = 330 (M++1, 12%), 329 (M+, 52%), 328 (23%), 91 (100%).
5-Chloro-1-(4-chlorobenzyl)-2-(4-chlorophenyl)-1H-indole-3-carbaldehyde (6i):
1
reaction time: 30h, H-NMR (600 MHz, CDCl3): δ = 9.73 (d, J = 2.2, 1H),
8.46 (t, J = 2.0 Hz, 1H), 7.49-7.46 (m, 2H), 7.33 (td, J = 8.9, 2.4 Hz, 2H),
7.29-7.24 (m, 4H), 7.12 (dd, J = 8.7, 1.9 Hz, 1H), 6.85 (d, J = 8.5 Hz, 2H),
5.21 (s, 2H); 13C NMR (150 MHz, CDCl3): δ = 185.9, 150.4, 136.9, 135.1,
CHO
Cl
p-ClC6H4
N
p-ClC6H4
134.3, 134.0, 131.8, 129.6, 129.3, 129.2, 129.0, 127.1, 125.0, 122.0, 116.0, 111.6, 47.3; IR (neat): ν =
3433, 2920, 2854, 1650, 1582, 1450, 1384, 1070 cm-1; EI-MS: m/z = 414.1 (M++1, 7%), 413.1 (M+, 15%),
253.2 (10%), 139.1 (16%), 125.1 (100%).
1-(4-Fluorobenzyl)-2-(4-fluorophenyl)-1H-indole-3-carbaldehyde (6j):
1
CHO
reaction time: 34h, H NMR (400 MHz, CDCl3): δ = 9.75 (s, 1H), 8.46 (dd, J =
7.0, 1.0 Hz, 1H), 7.41 – 7.34 (m, 3H), 7.34 – 7.29 (m, 1H), 7.28 – 7.23 (m, 2H),
7.18 (t, J = 8.6 Hz, 1H), 7.00 – 6.88 (m, 4H), 5.24 (s, 2H); 13C NMR (100.6 MHz,
CDCl3): δ = 186.5, 163.9 (d, JCF = 250.0 Hz), 162.4 (d, JCF = 245.0 Hz), 150.2,
p-FC6H4
N
p-FC6H4
136.9, 132.8 (d, JCF = 9.0 Hz), 132.2 (d, JCF = 3.0 Hz), 127.8 (d, JCF =8.0 Hz), 125.5, 124.6, 123.9, 123.7,
122.5, 116.7, 116.3 (d, JCF = 5.0 Hz), 116.0 (d, JCF = 5.0 Hz), 110.7, 47.2; IR (neat): ν = 3342, 2919, 1737,
1385, 838, 747 cm–1; EI-MS: m/z = 348 (M++1, 31%), 347 (M+, 89%), 346 (44%), 109 (100%).
S21

5-Chloro-1-(4-fluorobenzyl)-2-(4-fluorophenyl)-1H-indole-3-carbaldehyde (6k):
reaction time: 30h, 1H NMR (600 MHz, CDCl3): δ = 9.71 (s, 1H), 8.45 (d, J =
CHO
Cl
1.9 Hz, 1H), 7.41 – 7.35 (m, 2H), 7.28 – 7.23 (m, 1H), 7.22 – 7.16 (m, 2H),
7.14 (d, J = 8.7 Hz, 1H), 7.01 – 6.94 (m, 2H), 6.91 – 6.87 (m, 2H), 5.22 (s,
2H); 13C NMR (151.8 MHz, CDCl3): δ = 186.2, 164.0 (d, JCF = 250.62 Hz),
p-FC6H4
N
p-FC6H4
162.4 (d, JCF = 245.94 Hz), 150.9, 135.3, 132.7 (d, JCF = 8.51 Hz), 131.7 (d, JCF = 3.15 Hz), 129.7, 127.7
(d, JCF = 8.15Hz), 126.5, 125.0, 124.2 (d, JCF = 3.39 Hz), 122.1, 116.4 (d, JCF = 21.74 Hz), 116.2 (d, JCF
=
21.68 Hz), 116.2, 111.7, 47.3; IR (neat): ν = 3338, 2920, 1736, 1584, 1451, 1227, 838 cm–1; EI-MS: m/z =
383 (M++2, 18%), 382 (M++1, 16%), 381 (M+, 43%), 109 (100%).
4-(1-(4-Cyanobenzyl)-3-formyl-1H-indol-2-yl)benzonitrile (6l):
reaction time: 36h, 1H NMR (600 MHz, CDCl3): δ = 9.78 (s, 1H), 8.48 (d, J =
CHO
7.8 Hz, 1H), 7.79 (dd, J = 6.7, 1.7 Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 7.52 (dd,
p-CNC6H4
N
J = 6.7, 1.7 Hz, 2H), 7.43 – 7.33 (m, 2H), 7.20 (d, J = 8.2 Hz, 1H), 7.04 (d, J
= 8.5 Hz, 2H), 5.33 (s, 2H); 13C NMR (151.8 MHz, CDCl3): δ = 185.8, 148.0,
p-CNC6H4
141.3, 137.0, 133.1, 133.1, 132.7, 131.5, 126.6, 125.4, 124.3, 122.9, 118.2, 117.8, 117.2, 114.4, 112.4,
110.4, 47.6; IR (neat): ν = 3304, 2920, 2232, 1730, 1656, 1422, 1216, 756 cm–1; EI-MS: m/z = 362
(M++1, 26%), 361 (M+, 88%), 360 (49%), 116 (100%).
3-(1-Benzyl-2-phenyl-1H-indol-3-yl)pentane-2,4-dione (6m):
1H NMR (600 MHz, CDCl3): δ = 8.41 (d, J = 7.9 Hz, 1H), 7.70
H
O
O
O
O
(dd, J = 7.0, 1.0 Hz, 1H), 7.55 – 7.34 (m, 11H), 7.34 – 7.15 (m,
14H), 6.95 (m, 4H), 6.15 (s, 1H), 5.25 (s, 2H), 5.23(s, 2H), 2.21
(s, 3H), 2.08 (s, 3H), 1.99 (s, 3H); 13C NMR (151.8 MHz,
CDCl3): δ = 201.5, 201.2, 191.2, 170.6, 149.4, 141.8, 139.9,
137.6, 137.0, 137.0, 136.3, 130.9, 130.8, 130.6, 130.3, 130.2,
Me
Me
Me
Ph
Me
Ph
N
N
Ph
Ph
129.8, 129.5, 129.2, 129.1, 129.0, 128.9, 128.6, 127.9, 127.5, 127.1, 126.2, 126.2, 124.4, 123.7, 123.1,
122.4, 121.2, 120.3, 111.0, 110.8, 75.6, 48.0, 47.9, 26.4, 26.0, 21.0; IR (neat): ν = 3338, 2920, 1736, 1584,
1451, 1227, 838 cm–1; EI-MS: m/z = 382 (M++1, 14%), 354 (87%), 338 (100%).
S22

Crystal structure of 6a.
CHO
Ph
N
Ph
1.
Wu, C.-Y.; Hu, M.; Liu, Y.; Song, R.-J.; Lei, Y.; Tang, B.-X.; Li, R.-J.; Li, J.-H. Chem.
Commun. 2012, 48, 3197.
S23