10.1002/adsc.201801028
Advanced Synthesis & Catalysis
(Cq, CO2), 151.7, 149.4, 141.6, 133.6 and 102.5 (Cq),
129.6, 129.1, 129.0, 126.2, 123.2, 120.6 and 113.7
(aromatic CH), 60.5 (OCH2), 14.7 (CH3). HRMS (EI)
calcd for C19H17NO2S [M+H]+: 324.1058; Found:
324.1059.
1.93–1.60 and 1.49 (m each, 3:6:2 H, alkyl CH and CH2),
2.35 (d, J = 12.8 Hz, 1 H, alkyl CH), 1.40 (t, J = 7.1 Hz, 3
H, OCH2CH3), 1.31, 1.30, 1.29, 1.09 (s each, 3:3:3:3 H,
o
CH3). 13C{1H} NMR (100 MHz, 23 C, CDCl3) δ 165.2
(Cq, CO2), 157.3, 149.5, 147.2, 145.6, 134.7 and 133.8
(Cq), 129.0, 128.9, 126.9, 126.1, 124.4 and 123.9
(aromatic CH), 111.9 (thienyl CH), 59.9 (OCH2), 56.9
(NHCH2), 45.9 (NHCH2), 38.4, 38.1, 37.7, 36.4, 33.5, 30.4,
25.5, 24.1, 19.4, 18.8, 18.7 and 14.69 (alkyl CH, CH2 and
CH3). HRMS (EI) calcd for C33H41NO2S [M+H]+:
516.2936; Found: 516.2937.
(E)-Ethyl 5-(3-methylstyryl)-3-(phenylamino)thiophene
-2-carboxylate (3x): 72 mg, yield 66%, yellow solid, m.p.:
o
101-102 oC. 1H NMR (400 MHz, 23 C, CDCl3) δ 8.72 (br
s, 1 H, NH), 7.26 (t, J = 7.8 Hz, 2 H, aromtic CH), 7.17 (m,
3 H, aromtic CH and CH=CH), 7.11 (t, J = 7.5 Hz, 2 H,
aromtic CH), 6.95 (m, 5 H, aromtic CH and CH=CH), 4.25
(q, J = 7.1 Hz, 2 H, OCH2), 2.27 (s, 3 H, CH3), 1.30 (t, J =
N-Benzyl-2,5-diphenylthiophen-3-amine (4a): 88 mg,
o
1
o
7.1 Hz, 3 H, CH2CH3). 13C{1H} NMR (100 MHz, 23 C,
yield 86%, yellow liquid. H NMR (400 MHz, 23 C,
CDCl3) δ 7.65, 7.46 and 7.34 (m each, 4:8:4 H, aromatic
CH and NH), 7.09 (s, 1 H, thienyl CH), 4.48 (s, 2 H, CH2).
CDCl3) δ 164.9 (Cq, CO2), 151.5, 147.6, 141.5, 138.5,
136.1 and 101.4 (Cq), 131.9, 129.5, 129.4, 128.8, 127.6,
124.1, 123.2, 121.17, 120.58, 116.04 (aromtic CH and
CH=CH), 60.4 (OCH2), 21.5 (CH3), 14.7 (CH2CH3).
HRMS (EI) calcd for C22H21NO2S [M+H]+: 364.1371;
Found: 364.1370.
13C{1H} NMR (100 MHz, 23 C, CDCl3) δ 144.4, 141.8,
o
139.8 and 134.5 (Cq), 129.2, 128.8, 128.7, 127.9, 127.6,
127.5, 127.4, 126.5 and 125.4 (aromatic CH), 115.3
(thienyl CH), 51.2 (CH2). HRMS (EI) calcd for C23H19NS
[M+H]+: 342.1316; Found: 342.1316.
Ethyl 5-phenyl-3-((1-phenylethyl)amino)thiophene-2-
carboxylate (3y): 92 mg, yield 87%, yellow solid, m.p.:
N-Benzyl-5-(2-methoxyphenyl)-2-phenylthiophen-3-
amine (4b): 98 mg, yield 88%, yellow solid, m.p.: 95-96
o
87-88 C, 99% ee, [α]20 = +215.78 (c 1.00, CHCl3). 1H
D
NMR (400 MHz, 23 oC, CDCl3) δ 7.38 (dd, J = 7.7 and 1.3
Hz, 2 H, aromatic CH), 7.32–7.09 (m, 9 H, aromatic CH
and NH), 6.50 (s, 1 H, thienyl CH), 4.57 (p, J = 6.6 Hz, 1
H, NHCH), 4.25 (q, J = 7.1 Hz, 2 H, OCH2), 1.50 (d, J =
6.8 Hz, 3 H, CHCH3), 1.30 (t, J = 7.1 Hz, 3 H, CH2CH3).
oC. H NMR (400 MHz, 23 C, CDCl3) δ 7.60, 7.42, 7.31
and 7.15 (m, 2:6:3:1 H, aromatic CH), 7.22 (d, J = 7.9 Hz,
1 H, aromatic CH), 7.05 (s, 1 H, thienyl CH), 6.87 (dd, J =
8.1 and 1.9 Hz, 1 H, aromatic CH), 4.44 (s, 3 H, NHCH2
and NH), 3.88 (s, 3 H, OCH3). 13C{1H} NMR (100 MHz,
1
o
o
o
13C{1H} NMR (100 MHz, 23 C, CDCl3) δ 165.3 (Cq,
23 C, CDCl3) δ 159.9, 144.3, 141.5, 139.7, 135.8, 134.5
CO2), 155.7, 149.5, 144.9 and 133.7 (Cq), 128.9, 128.8,
128.7, 127.3, 126.1 and 125.9 (aromatic CH), 113.0
(thienyl CH), 60.0 (OCH2), 54.9 (NHCH), 25.0 (CHCH3),
and 115.5 (Cq), 129.9, 129.2, 128.8, 127.8, 127.5, 127.4,
126.5, 118.0, 115.4, 113.0 and 111.1 (aromatic CH and
thienyl CH), 55.4 (OCH3), 51.2 (NHCH2). HRMS (EI)
14.7 (CH2CH3). HRMS (EI) calcd for C21H21NO2S [M+H]+: calcd for C24H21NOS [M+H]+: 372.1422; Found: 372.1422.
352.1371; Found: 352.1372. HPLC (AD-H column,
N-Benzyl-5-(3-methoxyphenyl)-2-phenylthiophen-3-
iPrOH/n-hexane 3/97, 0.7 mL/min, 210 nm): t1 = 10.04
1
amine (4c): 96 mg, yield 86%, yellow liquid. H NMR
min (major), t2 = 11.03 min.
(400 MHz, 23 oC, CDCl3) δ 7.47, 7.30–7.18, 7.10, 6.81 (m
Ethyl
4-((1-phenylethyl)amino)-[2,2'-bithiophene]-5-
each, 3:6:4:2 H, aromatic CH), 4.25 (s, 3 H, NHCH2 and
NH), 3.72 (s, 3 H, OCH3). 13C{1H} NMR (100 MHz, 23 oC,
CDCl3) δ 155.9, 143.6, 140.1, 137.2, 134.8, 123.4 and
116.2 (Cq), 129.2, 128.8, 128.4, 128.0, 127.9, 127.6, 127.3,
126.4, 121.1 and 117.8 (aromatic CH), 111.8 (thienyl CH),
55.7 (OCH3), 51.3 (NHCH2). HRMS (EI) calcd for
C24H21NOS [M+H]+: 372.1422; Found: 372.1420.
carboxylate (3z): 90 mg, yield 84%, yellow solid, m.p.:
108-109 C, 99% ee, [α]20 = +176.39 (c 1.00, CHCl3). 1H
o
D
o
NMR (400 MHz, 23 C, CDCl3) δ 7.25, 7.19–7.10, 7.06
and 6.87 (m each, 4:3:1:1H, aromatic CH and NH), 6.37 (s,
1H, thienyl CH), 4.53 (p, J = 6.7 Hz, 1H, NHCH), 4.23 (q,
J = 7.1 Hz, 2H, OCH2), 1.49 (d, J = 6.8 Hz, 3H, CHCH3),
1.28 (t, J = 7.1 Hz, 3H, CH2CH3). 13C{1H} NMR (100
N-Benzyl-5-(4-methoxyphenyl)-2-phenylthiophen-3-
o
MHz, 23 C, CDCl3) δ 165.1 (Cq, CO2), 155.4, 144.8,
1
amine (4d): 98 mg, yield 88%, yellow liquid. H NMR
142.5, 136.9, 128.9, 128.0, 127.3, 126.1, 125.8 and 125.2
(aromatic CH), 113.1 (thienyl CH), 60.1 (OCH2), 54.9
(NHCH), 24.9 (CHCH3), 14.7 (CH2CH3). HRMS (EI)
calcd for C19H19NO2S2 [M+H]+: 358.0935; Found:
358.0935. HPLC (AD-H column, PrOH/n-hexane 3/97,
0.7 mL/min, 210 nm): t1 = 10.13 min (major), t2 = 11.12
min.
o
(400 MHz, 23 C, CDCl3) δ 7.43 (d, J = 7.4 Hz, 2 H,
aromatic CH), 7.38 (d, J = 8.7 Hz, 2 H, aromatic CH), 7.26,
7.14 and 6.78 (m, 6:2:3 H, aromatic CH), 4.27 (s, 3 H,
NHCH2 and NH), 3.70 (s, 3 H, OCH3). 13C{1H} NMR (100
i
o
MHz, 23 C, CDCl3) δ 159.3, 144.3, 141.8, 139.8, 134.7,
127.5 and 114.3 (Cq), 129.2, 128.8, 127.8, 127.6, 127.4,
126.7, 126.3, 114.4 and 114.3 (aromatic CH and thienyl
CH), 55.4 (OCH3), 51.2 (NHCH2). HRMS (EI) calcd for
C24H21NOS [M+H]+: 372.1422; Found: 372.1421.
Ethyl
3-((((1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-
1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)
amino)-5-phenylthiophene-2-carboxylate (3z1): 138 mg,
N-Benzyl-5-(2-fluorophenyl)-2-phenylthiophen-3-amine
(4e): 88 mg, yield 82%, yellow liquid. 1H NMR (400 MHz,
23 C, CDCl3) δ 7.65, 7.45, 7.34, 7.26, 7.19 (m each,
3:6:2:2 H, aromatic CH), 4.46 (s, 3 H, NHCH2 and NH).
13C{1H} NMR (100 MHz, 23 oC, CDCl3) δ 159.2 (d and Cq,
J = 250.3 Hz, C-F), 144.1, 139.7, 134.8 (d, J = 3.3 Hz),
134.3 and 122.4 (d, J = 12.3 Hz, Cq), 129.3, 128.8, 128.6
1
o
yield 89%, colorless liquid. H NMR (400 MHz, 23 C,
CDCl3) δ 7.69 (d, J = 7.1 Hz, 2 H, aromatic CH), 7.42 (m,
3 H, aromatic CH), 7.24 (d, J = 8.3 Hz, 1 H, aromatic CH),
7.12 (br, 1 H, NH), 7.06 (d, J = 8.1 Hz, 1 H, aromatic CH),
6.95 (s, 2 H, aromtic CH), 4.34 (q, J = 7.1 Hz, 2 H, OCH2),
3.26 (qd, J = 13.2 and 6.5 Hz, 2 H, NHCH2), 3.06–2.81,
o
8
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