Full Paper
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of around 12:1. H NMR (300 MHz, CDCl ): d=8.38 (s, 1H), 7.48–
3.25–3.06 (m, 0.24H), 1.75–1.50 (m, 5H), 1.31–0.75 ppm (m, 9H);
C NMR (75 MHz, CDCl ): d=164.0 (minor), 160.6 (major), 53.0,
3
3
13
7
7
3
1
4
.39 (m, 2H), 7.36–7.28 (m, 1H), 7.23–7.13 (m, 2H), 3.89 (q, J=
.2 Hz, 1.85H), 3.75 (q, J=7.2 Hz, 0.15H), 1.18 ppm (t, J=7.2 Hz,
H); C NMR (75 MHz, CDCl ): d=162.08 (minor), 162.01 (major),
38.29, 129.64, 129.25, 126.86, 126.09, 124.99, 124.24, 124.23,
4.94, 40.08, 15.04, 13.07 ppm; MS (EI): m/z (%): 149 (27) [M] , 121
48.0, 43.5, 42.6, 29.3, 28.8, 28.7, 28.2, 26.1, 26.1, 26.0, 25.9, 25.9,
1
3
+
25.8, 25.8, 19.1, 17.6 ppm; MS (EI): m/z (%): 155 (1) [M] , 140 (13),
3
110 (13), 72 (95), 55 (31), 44 (100), 29 (42).
+
N,N’-(Pentane-1,5-diyl)diformamide (2q): The product was ob-
tained by column chromatography (acetone) as a colorless crystal-
(
17), 106 (100), 93 (21), 77 (68), 65 (23), 51 (35), 39 (28), 29 (79).
N-[2-(4-Formylpiperazin-1-yl)ethyl]formamide (2k): The product
line solid in a yield of 85% (269 mg) as a mixture of rotamers in
1
was obtained by column chromatography (EtOH) as a white solid
a ratio of 7:1. H NMR (300 MHz, CDCl ): d=7.97 (d, J=2.0 Hz,
3
1
in a yield of 73% (272 mg). H NMR (300 MHz, [D ]DMSO): d=8.0
1.74H), 7.87 (d, J=11.9 Hz, 0.26H), 7.28 (s, 1.7H), 7.14–7.00 (m,
6
(
6
s, 1H), 7.98 (s, 1H), 7.97 (s, 1H), 3.42–3.28 (m, 4H), 3.20 (q, J=
0.3H), 3.19–2.97 (m, 4H), 1.51–1.32 (m, 4H), 1.30–1.13 ppm (m,
1
3
13
.4 Hz, 2H), 2.44–2.26 ppm (m, 6H); C NMR (75 MHz, [D ]DMSO):
2H); C NMR (75 MHz, CDCl ): d=164.7 (minor), 161.5 (major),
6
3
d=165.3, 161.7, 161.7, 161.3, 161.2, 59.0, 57.2, 53.8, 53.7, 52.5, 45.3,
41.3, 37.4, 37.3, 30.1, 28.4, 28.3, 23.5, 23.1 ppm; MS (EI): m/z (%):
158 (1) [M] , 127 (1), 113 (13), 100 (13), 87 (16), 73 (18), 59 (34), 58
+
+
3
9.8, 35.1 ppm; MS (EI): m/z (%): 185 (1) [M] , 140 (4), 127 (100), 98
(
17), 99 (17), 70 (35), 56 (48), 42 (51), 29 ppm (57); HRMS (ESI): m/z
(68), 30 (100), 29 (50).
+
calcd for C H N O : 186.12370 [M+H] ; found: 186.12383.
8
16
3
2
N-Nonylformamide (2r): The product was obtained by column
N-(4-Chlorobenzyl)formamide (2l): The product was obtained by
column chromatography (pentane/EtOAc, 1:2) as a white solid in
chromatography (pentane/EtOAc, 2:1) as a colorless oil in a yield
of 97% (333 mg) as a mixture of rotamers in a ratio of 4:1. H NMR
1
a yield of 72% (245 mg) as a mixture of rotamers in a ratio of
(300 MHz, CDCl ): d=8.09 (d, J=1.9 Hz, 0.8H), 7.97 (d, J=12.0 Hz,
3
1
around 9:1. H NMR (300 MHz, [D ]DMSO): d=8.56 (s, 1H), 8.17 (d,
0.2H), 6.21 (s, 1H), 3.32–2.98 (m, 2H), 1.47 (t, J=7.1 Hz, 2H), 1.33–
6
13
J=1.7 Hz, 1H), 7.37 (d, J=8.4 Hz, 2H), 7.29 (d, J=8.5 Hz, 2H),
1.13 (m, 12H), 0.88–0.77 ppm (m, 3H); C NMR (75 MHz, CDCl3):
1
3
4
1
1
.31 ppm (d, J=6.2 Hz, 2H); C NMR (75 MHz, [D ]DMSO): d=
d=164.6 (major), 161.3 (minor), 41.7, 38.1, 31.7, 29.4, 29.1, 29.1,
6
+
65.5 (minor), 161.7 (major), 138.6, 132.0, 129.7, 129.6, 129.4, 128.9,
28.8, 44.4 (minor), 40.7 ppm (major).
26.7, 22.5, 14.0 ppm; MS (EI): m/z (%): 171 (1) [M] , 142 (5), 128 (7),
100 (23), 72 (21), 58 (82), 41 (84), 30 (100), 29 (64). HRMS (ESI): m/z
+
calcd for C H NONa: 194.15154 [M+Na] ; found: 194.15148.
10
21
N-Phenethylformamide (2m): The product was obtained by
column chromatography (EtOAc) as a thick oil in a yield of 92%
N-Formylgeranylamine (2s): The product was obtained by column
1
(
(
275 mg) as a mixture of rotamers in a ratio of around 5:1. H NMR
chromatography (pentane/EtOAc, 3:1) as a colorless oil in a yield
1
300 MHz, CDCl ): d=8.09 (d, J=1.8 Hz, 0.81H), 7.84 (d, J=11.9 Hz,
of 84% (305 mg) as a mixture of rotamers in a ratio of 9:1. H NMR
3
0
1
.14H), 7.40–7.17 (m, 5H), 6.46–6.00 (m, 1H), 3.56 (q, J=6.6,
.68H), 3.47 (q, J=6.7 Hz, 0.31H), 2.86 ppm (t, J=7.1 Hz, 2H);
(300 MHz, CDCl ): d=7.99 (s, 0.9H), 7.91 (d, J=12.0 Hz, 0.1H), 6.76
(s, 0.9H), 6.32 (s, 0.1H), 5.12–5.01 (m, 1H), 5.01–4.88 (m, 1H), 3.72
3
13
C NMR (75 MHz, CDCl ): d=164.5 (minor), 161.2 (major), 138.4,
(t, J=8.1 Hz, 2H), 2.02–1.81 (m, 4H), 1.61–1.50 (m, 6H), 1.47 ppm
3
13
1
4
37.5, 128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.4, 126.7, 126.4,
(d, J=1.6 Hz, 3H); C NMR (75 MHz, CDCl ) d=164.4 (minor), 161.0
3
+
3.0, 39.1, 37.5, 35.3, 35.3 ppm; MS (EI): m/z (%): 149 (7) [M] , 104
(major), 139.4, 131.3, 123.5, 123.3, 119.9, 119.3, 119.2, 39.1, 35.7,
31.6, 26.1, 26.0, 25.9, 25.3, 25.3, 25.3, 23.0, 17.3, 15.9 ppm; MS (EI):
(
100), 91 (36), 58 (18); HRMS (ESI): m/z calcd for C H NO:
9 11
+
+
1
49.08352[M] ; found: 149.08374.
m/z (%): 181 (1) [M] , 136 (21), 69 (51), 41 (100), 29 (22); HRMS
+
(
ESI): m/z calcd for C H NO: 182.15394 [M+H] ; found: 182.15411.
11
20
N-Formyl-1-adamantylmethylamine (2n): The product was ob-
tained by column chromatography (pentane/EtOAc, 1:1) as a white
N-(2-Pyridylmethyl)formamide (2t): The product was obtained by
solid in a yield of 75% (291 mg) as a mixture of rotamers in a ratio
column chromatography (EtOAc/EtOH, 6:1) as a colorless thick oil
1
1
of 7:2. H NMR (300 MHz, CDCl ): d=8.06 (d, J=2.2 Hz, 0.77H), 7.77
in a yield of 86% (234 mg). H NMR (300 MHz, CDCl ): d=8.27 (dd,
3
3
(
d, J=11.9 Hz, 0.22H), 7.01–6.71 (m, 1H), 2.81 (d, J=6.5 Hz, 1.56H),
J=5.0, 2.2 Hz, 1H), 8.08 (d, J=2.2 Hz, 1H), 7.87 (s, 1H), 7.53–7.36
2
1
5
.67 (d, J=6.8 Hz, 0.44H), 1.88–1.75 (m, 3H), 1.64–1.42 (m, 6H),
(m, 1H), 7.07 (d, J=7.9 Hz, 1H), 7.03–6.89 (m, 1H), 4.36 ppm (d, J=
1
3
13
.42–1.20 ppm (m, 6H); C NMR (75 MHz, CDCl ): d=165.3, 161.6,
5.6 Hz, 2H); C NMR (75 MHz, CDCl ): d=165.2, 161.2, 156.1, 148.4,
3
3
+
3.8, 49.2, 39.7, 39.4, 36.5, 36.4, 33.2, 33.1, 27.8, 27.7 ppm; HRMS
136.4, 121.9, 121.4, 46.7, 42.7 ppm; MS (EI): m/z (%): 136 (6) [M] ,
+
(
ESI): m/z calcd for C H NO: 194.15394 [M+H] ; found:
107 (100), 93 (43), 92 (38), 80 (52), 79 (57), 63 (21), 52 (70), 51 (60),
129 (100).
1
2
20
1
94.15406.
(S)-N-(1-Phenylethyl)formamide (2o): The product was obtained
N-(1-Adamantyl)formamide (2u): The product was obtained by
by column chromatography (acetone) as a colorless oil in a yield of
column chromatography (pentane/EtOAc, 1:1) as a white solid in
22
9
0% (268 mg) as a mixture of rotamers in a ratio of 4:1. [a] =
a yield of 34% (73 mg) as a mixture of rotamers in a ratio of 7:3.
D
2
4
1
À201.3 (c=1, EtOH) {lit.: [a] =À190 (c=1, EtOH), see ref. [10] in
H NMR (300 MHz, CDCl ): d=8.15 (d, J=12.3 Hz, 0.7H), 7.91 (d, J=
D
3
1
the Supporting Information}; H NMR (300 MHz, CDCl ): d=8.10 (d,
2.1 Hz, 0.3H), 7.09 (s, 0.7H), 5.81 (s, 0.3H), 2.07–1.88 (m, 5H), 1.82–
3
13
J=12.0 Hz, 0.18H), 8.06 (d, J=1.9, 0.82H), 7.43–7.22 (m, 5H), 7.13–
1.68 (m, 4H), 1.67–1.49 ppm (m, 6H); C NMR (75 MHz, CDCl ): d=
3
6
6
.87 (m, 1H), 5.24–5.07 (m, 1H), 4.74–4.58 (m, 0.86H), 1.56 (d, J=
.9 Hz, 0.14H), 1.48 ppm (d, J=7.0 Hz, 3H); C NMR (75 MHz,
162.3, 160.2, 51.6, 50.3, 43.7, 41.4, 36.0, 35.6, 29.1, 29.0 ppm; HRMS
1
3
+
(ESI): m/z calcd for C H NO: 179.13047 [M] ; found: 179.13066.
11
17
CDCl ): d=164.2 (minor), 160.5 (major), 142.6, 128.6, 128.4, 127.4,
3
N-{[1-(Thieno[3,2-d]pyrimidin-4-yl)piperidin-4-yl]methyl}formam-
ide (2v): The reaction was performed using 1t
127 mg, 0.511 mmol) and the resulting product was obtained by
1
27.1, 125.9, 125.6, 124.7, 51.6, 47.3, 23.3, 21.7 ppm; MS (EI): m/z
+
(
(
%): 149 (66) [M] , 148 (57), 134 (54), 106 (80), 79 (87), 77 (100), 51
67), 42 (49), 29 (7).
(
column chromatography (EtOAc/EtOH, 2:1) as a brown solid in
1
N-(1-Cyclohexylethyl)formamide (2p): The product was obtained
a yield of 61% (86 mg). H NMR (300 MHz, CDCl ): d=8.48 (d, J=
3
by column chromatography (pentane/EtOAc, 2:1) as a colorless oil
5.3 Hz, 1H), 8.14 (d, J=2.0 Hz, 1H), 7.95 (d, J=11.8 Hz, 0.8H), 7.66
(dd, J=5.6, 4.5 Hz, 0.2H), 7.32 (dd, J=5.6, 4.6 Hz, 1H), 6.77 and
6.63 (s, 1H), 4.87–4.66 (m, 2H), 3.17 (t, J=6.3 Hz, 2H), 3.11–2.94 (m,
in a yield of 87% (271 mg) as a mixture of rotamers in a ratio of
1
7
7
:2. H NMR (300 MHz, CDCl ): d=8.04 (dd, J=2.1, 1.1 Hz, 0.72H),
3
13
.91 (d, J=11.9 Hz, 0.23H), 6.48–6.12 (m, 1H), 3.91–3.68 (m, 0.76H),
2H), 1.91–1.70 (m, 3H), 1.38–1.12 ppm (m, 2H); C NMR (75 MHz,
Chem. Eur. J. 2015, 21, 14943 – 14948
14947 ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim