Paper
Organic & Biomolecular Chemistry
1
3
CDCl
3
) δ 18.1, 21.5, 32.8, 49.1, 118.1, 126.4, 138.5, 139.3, 174.2.
C NMR (100 MHz, CDCl
3
) δ 62.6, 118.1, 119.5, 121.0, 122.0,
+
+
HRMS calcd for C H NNaO: 212.1046 [M + Na] , found: 124.0, 132.8, 138.8. MS (EI): 347, 349 [M] . HRMS (APCI) calcd
1
2
15
+
2
12.1040.
for C10
3-Iodo-1-(p-tolyl)-1H-pyrrole (3e). Syrup (83 mg, 59%).
3%). H NMR (600 MHz, CDCl ) δ 2.12 (quint, J = 7.8 Hz, 2H), NMR (600 MHz, CDCl ) δ 2.37 (s, 3H), 6.39 (dd, J = 3.0 Hz, J =
.52 (t, J = 7.8 Hz, 2H), 3.78 (t, J = 7.2 Hz, 2H), 7.19–7.21 (m, 1.2 Hz, 1H), 6.91 (t, J = 2.4 Hz, 1H), 7.08 (d, J = 1.8 Hz, 1H), 7.22
3
(s, 4H). C NMR (100 MHz, CDCl ) δ 20.9, 61.5, 117.3, 120.5,
δ 18.0, 32.0, 48.9, 108.9, 120.4, 124.8, 138.0, 173.1. HRMS calcd 121.3, 124.2, 130.2, 136.2, 137.6. MS (EI): 283 [M] . HRMS
8
H BrIN: 347.8879 [M + H] , found: 347.8886.
8
c
1
1
-(Thiophen-3-yl)pyrrolidin-2-one (2l). White solid (36 mg,
H
1
4
2
2
3
3
1
2
1
3
13
H), 7.45 (d, J = 3.6 Hz, 1H). C NMR (150 MHz, CDCl
3
)
+
+
+
for C
8
H
9
NNaOS: 190.0297 [M + Na] , found: 190.0299.
(APCI) calcd for C11
H11IN: 283.9931 [M + H] , found: 283.9940.
2
3
1
-(4-Methoxyphenyl)-3-methylpyrrolidin-2-one (2m). White
1-(4-Ethylphenyl)-3-iodo-1H-pyrrole (3f). Syrup (92 mg,
1
1
solid (41 mg, 40%). H NMR (600 MHz, CDCl ) δ 1.29 (d, J = 62%). H NMR (600 MHz, CDCl ) δ 1.25 (t, J = 7.8 Hz, 3H), 2.67
3
3
7
.2 Hz, 3H), 1.74–1.78 (m, 1H), 2.34–2.37 (m, 1H), 2.63–2.67 (q, J = 7.8 Hz, 2H), 6.40 (t, J = 1.8 Hz, 1H), 6.92 (d, J = 2.4 Hz,
13
(m, 1H), 3.70–3.76 (m, 2H), 3.80 (s, 3H), 6.90 (dd, J
1 3
= 7.2 Hz, 1H), 7.09 (s, 1H), 7.24 (s, 4H). C NMR (150 MHz, CDCl ) δ
J
= 1.8 Hz, 2H), 7.52 (dd, J1 = 7.2 Hz, J2 = 2.4 Hz, 2H). 15.6, 28.3, 61.5, 117.3, 120.7, 121.3, 124.3, 129.0, 137.8, 142.6.
C NMR (150 MHz, CDCl ) δ 16.3, 27.1, 38.1, 47.0, 55.5, 114.0, MS (EI): 297 [M] . HRMS (APCI) calcd for C12H13IN: 298.0087
3
2
1
3
+
+
1
2
21.5, 133.0, 156.4, 176.4. HRMS calcd for C12
28.0995 [M + Na] , found: 228.0996.
H
15NNaO
2
:
[M + H] , found: 298.0100.
3-Iodo-1-(4-methoxyphenyl)-1H-pyrrole (3g). Syrup (75 mg,
+
1
5
0%). H NMR (600 MHz, CDCl
.0 Hz, J = 1.2 Hz, 1H), 6.79 (t, J = 2.4 Hz, 1H), 6.87 (dd, J
3
) δ 3.76 (s, 3H), 6.32 (dd, J
1
=
=
Typical procedure for the synthesis of 3a
3
2
1
A tube containing 1-phenylpiperidine (1a, 81 mg, 0.5 mmol), 6.6 Hz, J = 1.8 Hz, 2H), 6.96 (t, J = 1.8 Hz, 1H), 7.18 (d, J = 6.6
2
1
3
Cu(OAc)
2
(181 mg, 1 mmol), I
2
(127 mg, 0.5 mmol) and DMAP Hz, 2H). C NMR (100 MHz, CDCl
3
) δ 55.6, 61.1, 114.7, 117.1,
+
(61 mg, 0.5 mmol) was evacuated and back-filled with O
2
three 121.6, 122.3, 124.5, 133.6, 158.2. MS (EI): 299 [M] . HRMS
+
times. Then, CH CN (5 mL) was added, and the mixture was (APCI) calcd for C H INO: 299.9880 [M + H] , found:
3
11 11
2
stirred at 80 °C under O (balloon) for 10 h. Upon completion, 299.9883.
it was quenched with saturated ammonium chloride (5 mL),
and extracted with EtOAc (10 mL × 3). The combined organic 59%). H NMR (600 MHz, CDCl ) δ 6.43 (s, 1H), 6.95–6.99 (m,
1-(3-Fluorophenyl)-3-iodo-1H-pyrrole (3h). Syrup (85 mg,
1
3
phases were dried over anhydrous Na
under reduced pressure. The residue was purified by column 1H). C NMR (150 MHz, CDCl
chromatography on silica gel with petroleum ether/ethyl Hz), 113.1 (d, J
acetate (100 : 1) as the eluent to give 3a in 65% yield. 3b–3n 121.0, 124.1, 131.0 (d, JC–F = 9.9 Hz), 141.2 (d, JC–F = 9.9 Hz),
2
SO
4
, and concentrated 2H), 7.06 (d, J = 9.6 Hz, 1H), 7.13–7.14 (m, 2H), 7.37–7.41 (m,
1
3
2
3
) δ 62.7, 107.9 (d, JC–F = 25.2
2
4
= 20.9 Hz), 115.8 (d, J
= 3.3 Hz), 118.1,
C–F
C–F
3
3
1
19
were obtained in a similar manner.
163.3 (d,
J
C–F = 246.0 Hz). F NMR (376 MHz, CDCl
3
)
1
3b
1
+
3
-Iodo-1-phenyl-1H-pyrrole (3a).
Syrup (87 mg, 65%). H δ −110.55. MS (EI): 287 [M] . HRMS (APCI) calcd for C H FIN:
1
0
8
+
NMR (400 MHz, CDCl
3
) δ 6.42 (t, J = 1.2 Hz, 1H), 6.96 (t, J = 2.0 287.9680 [M + H] , found: 287.9674.
Hz, 1H), 7.13 (t, J = 2.0 Hz, 1H), 7.28 (t, J = 7.2 Hz, 1H), 7.34 (d,
J = 7.6 Hz, 2H), 7.43 (t, J = 7.6 Hz, 2H). C NMR (100 MHz, 60%). H NMR (400 MHz, CDCl ) δ 6.35 (s, 1H), 6.86 (t, J = 2.4
1-(3-Bromophenyl)-3-iodo-1H-pyrrole (3i). Syrup (104 mg,
1
3
1
3
CDCl
3
) δ 62.0, 117.6, 120.6, 121.2, 124.2, 126.4, 129.7, 139.9. Hz, 1H), 7.04 (s, 1H), 7.19–7.23 (m, 2H), 7.32–7.34 (m, 1H),
+
13
MS (EI): 269 [M] . HRMS (APCI) calcd for C10
9 3
H IN: 269.9774 7.44 (s, 1H). C NMR (100 MHz, CDCl ) δ 62.8, 118.2, 118.9,
+
[M + H] , found: 269.9760.
121.0, 123.2, 123.6, 124.0, 129.3, 131.0, 140.9. MS (EI): 347 349
+
+
1
-(4-Fluorophenyl)-3-iodo-1H-pyrrole (3b). Brown solid [M] . HRMS (APCI) calcd for C10
H
8
BrIN: 347.8879 [M + H] ,
1
(
1
95 mg, 66%). H NMR (400 MHz, CDCl
3
) δ 6.33 (d, J = 1.6 Hz, found: 347.8877.
H), 6.80 (t, J = 2.4 Hz, 1H), 6.97 (s, 1H), 7.02–7.06 (m, 2H), 3-Iodo-1-(m-tolyl)-1H-pyrrole (3j). Syrup (89 mg, 63%).
) δ 62.0, 116.5 (d, NMR (400 MHz, CDCl
C–F = 23.1 Hz), 117.7, 121.5, 122.5 (d, JC–F = 8.9 Hz), 124.5, 1H), 7.00 (d, J = 7.2 Hz, 1H), 7.03–7.06 (m, 3H), 7.21 (t, J = 7.6
1
H
1
3
7
.20–7.23 (m, 2H). C NMR (150 MHz, CDCl
J
3
3
) δ 2.31 (s, 3H), 6.32 (s, 1H), 6.85 (s,
2
3
4
1
19
13
1
36.3 (d, J
= 2.3 Hz), 161.0 (d, J
= 245.1 Hz). F NMR Hz, 1H). C NMR (100 MHz, CDCl ) δ 21.5, 61.8, 117.4, 117.7,
C–F
C
–
F
3
+
(
376 MHz, CDCl
calcd for C10 FIN: 287.9680 [M + H] , found: 287.9687.
-(4-Chlorophenyl)-3-iodo-1H-pyrrole (3c). Syrup (103 mg, found: 283.9909.
3
) δ −115.78. MS (EI): 287 [M] . HRMS (APCI) 121.2, 121.3, 124.2, 127.1, 129.5, 139.8, 139.9. MS (EI): 283
+
+
+
H
8
[M] . HRMS (APCI) calcd for C11
H
11IN: 283.9931 [M + H] ,
1
1
1
6
6
7
1
8%). H NMR (600 MHz, CDCl
.91 (t, J = 2.4 Hz, 1H), 7.08 (s, 1H), 7.27 (d, J = 8.4 Hz, 2H), NMR (400 MHz, CDCl ) δ 2.13 (s, 3H), 6.31 (t, J = 2.4 Hz, 1H),
.39 (d, J = 9.0 Hz, 2H). C NMR (150 MHz, CDCl ) δ 62.5, 6.59 (t, J = 2.4 Hz, 1H), 6.76 (t, J = 2.0 Hz, 1H), 7.12–7.13 (m,
3
) δ 6.42 (d, J = 0.6 Hz, 1H),
3-Iodo-1-(o-tolyl)-1H-pyrrole (3k). Syrup (85 mg, 60%).
H
3
1
3
3
1
3
3
18.0, 121.1, 121.7, 124.1, 129.8, 131.9, 138.4. MS (EI): 303, 305 1H), 7.15–7.23 (m, 3H). C NMR (150 MHz, CDCl ) δ 17.7,
+
+
[M] . HRMS (APCI) calcd for C10
H
8
ClIN: 303.9385 [M + H] , 60.1, 116.2, 123.9, 126.6, 126.7, 128.1, 131.2, 133.8, 139.7. MS
+
found: 303.9393.
(EI): 283 [M] . HRMS (APCI) calcd for C H IN: 283.9931 [M +
1
1
11
+
1
-(4-Bromophenyl)-3-iodo-1H-pyrrole (3d). Syrup (106 mg, H] , found: 283.9903.
1
6
1%). H NMR (600 MHz, CDCl
3
) δ 6.42 (s, 1H), 6.91 (s, 1H),
3-Iodo-1-(2-methoxyphenyl)-1H-pyrrole (3l). Syrup (76 mg,
1
7
.09 (s, 1H), 7.21 (d, J = 7.2 Hz, 2H), 7.54 (d, J = 7.8 Hz, 2H). 51%). H NMR (600 MHz, CDCl ) δ 3.77 (s, 3H), 6.30 (s, 1H),
3
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