10.1002/ejoc.201701060
European Journal of Organic Chemistry
FULL PAPER
CD3OD) δ 8.12 (d, J = 8.2 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.34 – 7.22 (m,
2H), 6.03 (s, 1H), 4.09 (t, J = 7.3 Hz, 2H), 3.04 (t, J = 7.7 Hz, 2H), 2.28 –
2.18 (m, 2H) ppm; 13C NMR (1 25 MHz, CD3OD) δ 179.4, 158.9, 139.6,
133.2, 126.3, 125.9, 124.8, 117.5, 105.0, 51.8, 32.6, 21.5 ppm; HRMS
(ESI) m/z calcd for [C12H11NONa]+ (M + Na)+: 208.0733; found: 208.0731.
15e-b: pale yellow oil, Rf = 0.3 (10% MeOH/ethyl acetate). IR (film) max:
2932, 2858, 1635, 1545, 1268, 1170, 925, 678 cm-1; 1H NMR (500 MHz,
CDCl3) δ 3.43 (t, J = 9.9 Hz, 2H), 3.07 (t, J = 6.0 Hz, 2H), 2.89 (t, J = 6.4
Hz, 2H), 2.78 (t, J = 9.9 Hz, 2H), 2.06 (s, 3H), 1.83 – 1.77 (m, 2H), 1.68 –
1.62 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3) δ 190.6, 162.3, 106.3, 52.9,
46.6, 28.6, 27.1, 25.5, 22.6, 19.6 ppm; HRMS (ESI) m/z calcd for
[C10H15NONa]+ (M + Na)+: 188.1046; found: 188.1040.
1,2,3,4-Tetrahydro-6H-pyrido[1,2-a]quinolin-6-one (15b). Following
general procedure A, the one-pot reaction of tertiary amide 14b (109 mg,
0.5 mmol) afforded 15b (72 mg, yield: 72%) and the recovered starting
material 14b (ca. 8%). Following general procedure B, the two-step
reaction afforded silyl enol ether SEE2 and 15b in 86% and 83% yield,
respectively. In addition, about 2% of starting material was observed. 15b:
beige solid, Rf = 0.4 (10% MeOH/ethyl acetate). Mp: 189-190 °C. IR (film)
(2,3,5,6-Tetrahydro-1H-pyrrolizin-7-yl)(phenyl)methanone
(15f).
Following general procedure A, the one-pot reaction of tertiary amide 14f
(58 mg, 0.25 mmol) afforded 15c (35 mg, yield: 65%) and the recovered
starting material 14f (ca. 15%). Following general procedure B, the two-
step reaction afforded silyl enol ether SEE6 and 15f in 89% and 95% yield,
respectively. 15f: Rf = 0.3 (10% MeOH/ethyl acetate). IR (film) max: 3053,
2925, 2854, 1680, 1445, 1260, 1049, 876, 704, 658 cm-1; 1H NMR (500
MHz, CD3OD) δ 7.41 – 7.36 (m, 5H), 3.58 (t, J = 9.2 Hz, 2H), 3.35 – 3.32
(m, 2H), 3.22 (t, J = 9.2 Hz, 2H), 2.22 – 2.15 (m, 2H), 2.09 – 1.98 (m, 2H)
ppm; 13C NMR (125 MHz, CD3OD) δ 189.0, 178.0, 143.7, 130.2, 129.2
(2C), 128.2 (2C), 104.9, 32.8, 28.6 (2C), 26.7 (2C) ppm; HRMS (ESI) m/z
calcd for [C14H15NONa]+ (M + Na)+: 236.1046; found: 236.1049.
max: 3410, 3098, 3068, 2939, 1619, 1596, 1567, 1494, 1470, 1313, 1173,
1075, 1036, 845, 763 cm-1; 1H NMR (500 MHz, CD3OD) δ 8.19 (d, J = 8.1
Hz, 2H), 7.63 – 7.57 (m, 2H), 7.37 – 7.31 (m, 1H), 6.00 (s, 1H), 4.01 (t, J
= 6.4 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H), 2.00 – 2.00 (m, 2H), 1.82 – 1.75 (m,
2H) ppm; 13C NMR (125 MHz, CD3OD) δ 178.1, 155.5, 142.4, 133.3, 127.0,
126.3, 125.1, 116.9, 110.0, 47.3, 31.1, 23.7, 19.4 ppm; HRMS (ESI) m/z
calcd for [C13H13NONa]+ (M + Na)+: 222.0889; found: 222.0883.
2,3,5,6-Tetrahydroindolizin-7(1H)-one
(15c).
Following
general
(2,3,5,6,7,8-Hexahydroindolizin-1-yl)(phenyl)methanone
(15g).
procedure A, the one-pot reaction of tertiary amide 14c (39 mg, 0.25 mmol)
afforded 15c (16 mg, yield: 48%) and the recovered starting material 14c
(ca. 13%). Following general procedure B, the two-step reaction afforded
silyl enol ether SEE3 and 15c in 83% and 68% yield, respectively. In
addition, about 11% of starting material was observed. 15c: Rf = 0.3 (10%
MeOH/ethyl acetate). IR (film) max: 2933, 2843, 1668, 1575, 1418, 1264,
1171, 1098 cm-1; 1H NMR (500 MHz, CDCl3) δ 5.00 (s, 1H), 3.46 (t, J = 7.9
Hz, 2H), 3.38 (t, J = 6.9 Hz, 2H), 2.69 (t, J = 7.7 Hz, 2H), 2.51 (t, J = 7.9
Hz, 2H), 2.01 – 2.04 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3) δ 190.9,
169.2, 93.3, 53.3, 45.4, 35.1, 31.8, 21.3 ppm; HRMS (ESI) m/z calcd for
[C8H11NONa]+ (M + Na)+: 160.0733; found: 160.0733.
Following general procedure A, the one-pot reaction of tertiary amide 14g
(58 mg, 0.25 mmol) afforded 15c (35 mg, yield: 65%) and the recovered
starting material 14g (ca. 15%). Following general procedure B, the two-
step reaction afforded silyl enol ether SEE7 and 15g in 83% and 88% yield,
respectively. 15g: Rf = 0.3 (10% MeOH/ethyl acetate). IR (film) max: 3056,
2920, 2843, 1503, 1501, 1444, 1269, 1175, 1088, 707 cm-1; 1H NMR (500
MHz, CD3OD) δ 7.40 – 7.31 (m, 5H), 3.58 (t, J = 9.6 Hz, 2H), 3.23 (t, J =
6.1 Hz, 2H), 2.85 (t, J = 9.6 Hz, 2H), 2.28 – 2.19 (m, 2H), 1.80 – 1.75 (m,
2H), 1.52 – 1.47 (m, 2H) ppm; 13C NMR (126 MHz, CD3OD) δ 188.7, 169.1,
144.9, 130.0, 129.3 (2C), 128.0 (2C), 108.8, 54.1, 47.2, 27.4, 27.3, 23.0,
20.0 ppm; HRMS (ESI) m/z calcd for [C15H17NONa]+ (M + Na)+: 250.1202;
found: 250.1198.
3,4,6,7,8,9-Hexahydro-2H-quinolizin-2-one (15d). Following general
procedure A, the one-pot reaction of tertiary amide 14d (43 mg, 0.25 mmol)
afforded 15c (16 mg, yield: 42%) and the recovered starting material 14d
(ca. 19%). Following general procedure B, the two-step reaction afforded
silyl enol ether SEE4 and 15d in 85% and 65% yield, respectively. In
addition, about 12% of starting material was observed. 15d: Rf = 0.3 (10%
MeOH/ethyl acetate). IR (film)max: 2939, 2846, 1617, 1552, 1501, 1312,
1245, 1168, 1114, 803, 630 cm-1; 1H NMR (500 MHz, CDCl3) δ 5.00 (s,
1H), 3.40 (t, J = 7.7 Hz, 2H), 3.21 (t, J = 6.1 Hz, 2H), 2.47 – 2.42 (m, 4H),
1.90 – 1.84 (m, 2H), 1.70 – 1.63 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3)
δ 190.6, 163.7, 98.5, 50.5, 50.3, 35.2, 29.8, 23.2, 19.7 ppm; HRMS (ESI)
m/z calcd for [C9H13NONa]+ (M + Na)+: 174.0889; found: 174.0883.
Acknowledgements
The authors are grateful for financial support from the National
Natural Science Foundation of China (21332007 and 21672176)
and the Program for Changjiang Scholars and Innovative
Research Team in University of Ministry of Education, China.
Keywords: Cyclization Reaction • Keto-lactams • Condensation
Reaction • Heterocycles • Amides
1,2,3,4,7,8-Hexahydropyrido[1,2-a]azepin-9(6H)-one (15e-a) and 1-
(2,3,5,6,7,8-Hexahydroindolizin-1-yl)ethan-1-one (15e-b). Following
general procedure A, the one-pot reaction of tertiary amide 14e (46 mg,
0.25 mmol) afforded 15e-a (13 mg, yield: 30%) and 15e-b (10 mg, yield:
23%) in a combined yield of 53%. Following general procedure B, the two-
step reaction afforded silyl enol ether SEE5, 15e-a and 15e-b in 70%, 38%
and 24% yield, respectively.
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15e-a: pale yellow oil, Rf = 0.27 (10% MeOH/ethyl acetate). IR (film) max
:
2920, 2850, 1543, 1444, 1349, 1285, 1235, 1139 cm-1; 1H NMR (500 MHz,
CDCl3) δ 4.95 (s, 1H), 3.45 – 3.41 (m, 2H), 3.30 (t, J = 6.2 Hz, 2H), 2.57 (t,
J = 6.7 Hz, 2H), 2.42 (t, J = 6.5 Hz, 2H), 2.02 –1.96 (m, 2H), 1.83 – 1.78
(m, 2H), 1.68 – 1.63 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3) δ 198.3,
158.1, 101.8, 56.7, 52.0, 41.4, 32.5, 23.6, 23.2, 19.8 ppm; HRMS (ESI)
m/z calcd for [C10H15NONa]+ (M + Na)+: 188.1046; found: 188.1045.
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