European Journal of Organic Chemistry
10.1002/ejoc.201701212
FULL PAPER
(
E)-1-(4,5,6,7-tetrahydrooxepin-2-yl)hex-2-en-1-one
yellow oil (39%). R
0.35 (95:5 PE/EtOAc). 1H NMR (200 MHz, CDCl
ppm): 6.98 (dt, 1H, J = 15.4 Hz, 6.8 Hz), 6.71 (d, 1H, J = 15.5 Hz), 6.31
t, 1H, J = 6.2 Hz), 4.04-3.96 (m, 2H), 2.40-2.14 (m, 4H), 1.98-1.85 (m, 2H),
(2o):[31]
Pale
Keywords: gold catalysis, gold catalysed oxidation, lactam
f
3
) δ
derived heterocycles, Nazarov reaction.
(
(
1
[
1]
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.76-1.57 (m, 2H), 1.56-1.40 (m, 2H), 0.93 (t, 3H, J = 7.4 Hz). GC-MS m/z
2
+
(%) = 194 [M] (19), 151 (100), 97 (65), 55 (89).
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3
[
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(
0
E)-1-(1-methyl-1H-indol-2-yl)hex-2-en-1-one (2p): Yellow oil (12%). R
.28 (98:2 PE/EtOAc). H NMR (600 MHz) δ (ppm): 7.69 (dt, 1H, J = 8.0
f
1
Hz, 1.0 Hz), 7.40-7.36 (m, 2H), 7.29 (s, 1H), 7.16-7.13 (m, 1H), 7.07 (dt, J
15.3 Hz, 6.9 Hz), 6.92 (dt, 1H, J = 15.3 Hz, 1.5 Hz), 4.10 (s, 3H), 2.30
qd,2H, J = 7.2 Hz, 1.5 Hz), 1.57 (sext,2H, J = 7.2 Hz), 0.98 (t, 3H, J = 7.2
Hz). 13C NMR (150 MHz) δ (ppm): 183.4 (Cq), 147.7 (CH), 140.5 (Cq),
=
(
1229-1234; e) X. Y. Wang, Z. Z. Li, Chinese J. Org. Chem. 2014,
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1
36.1 (Cq), 127.5 (CH), 126.1 (Cq), 126.0 (CH), 123.1 (CH), 120.8 (CH),
11.6 (CH), 110.5 (CH), 34.8 (CH ), 32.4 (CH ), 21.7 (CH ), 13.9 (CH ).
17NO (227.31): calcd. C
9.26, H 7.54, N 6.16; found C 79.08, H 7.32, N 6.49.
Xiang, Synlett 2013, 24, 1809-1812; g) C. Wu, Z. W. Liang, D.
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1
2
3
2
3
GC-MS m/z (%) = 227 [M]+ (38), 184 (100). C15
H
7
2011, 133, 15372-15375; j) L. M. Zhang, Acc. Chem. Res. 2014,
4
7, 877-888.
5
-benzyl-1-tosyl-1,2,3,4,5,6-hexahydro-7H-cyclopenta[b]pyridin-7-
[
[
4]
5]
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[
32]
one (4b):
dissolved in TFA (0.1-0.2 M) at 0 °C. The mixture was stirred at room
temperature for 1.5 hours, then a saturated NaHCO solution was added.
The mixture was extracted with CH Cl (3x5 ml); the combined organic
layers were dried over Na SO , filtered and the solvent was removed under
reduced pressure. The crude bicyclic ketone was purified by flash
chromatography to give pure 4b as a yellow oil (35%, 2-step). R 0.38 (7:3
PE/EtOAc). H NMR (600 MHz) δ (ppm): 8.00 (d, 2H, J = 8.4 Hz), 7.33-
The crude divinyl ketone 2b was not purified, but was
3
2
2
11775-11779; d) D. Qian, J. Zhang, Chem. Soc. Rev. 2015, 44,
2
4
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[6]
7]
[8]
f
1
[
7
1
.30 (m, 4H), 7.25-7.22 (m, 1H), 7.17 (d, 2H, J = 7.0 Hz), 3.51-3.47 (m,
H), 3.43-3.38 (m, 1H), 3.14-3.10 (m, 1H), 3.12 (dd, 1H, J = 13.4 Hz, 5.0
Hz), 3.09-3.05 (m, 1H), 2.54 (dt,1H, J = 19.8 Hz, 6.8 Hz), 2.48-2.55 (m,
H), 2.42 (s, 3H), 2.30 (dt, 1H, J = 19.8 Hz, 6.4 Hz), 2.19 (dd, 1H, J = 18.4
Hz, 1.9 Hz), 2.05-2.04 (m, 2H). 13C NMR (150 MHz) δ (ppm): 199.6 (Cq),
[
[
9]
1
2010, 839-839.
10]
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1
1
4
61.5 (Cq), 143.7 (Cq), 139.1 (Cq), 138.2 (Cq), 138.0 (Cq), 129.5 (CH),
28.8 (CH), 127.9 (CH), 126.8 (CH), 46.2 (CH ), 40.9 (CH), 40.0 (CH ),
0.0 (CH ), 24.4 (CH ), 22.0 (CH ), 21.7 (CH ). ESI-MS m/z (%) = 785
2
2
2
2
2
3
2M+Na] (93), 404 [M+Na]+ (100), 382 [M+H] (15). MS/MS of 382 m/z
+
+
[
-
1
3
(%): 382 (4), 226 (100), 136 (77). IR (neat): 1709 cm . C23H23NO S: calcd.
C 69.27, H 6.08, N 3.67; found C 69.03, H 6.42, N 3.75.
-methyl-1-propyl-1,4-dihydrocyclopenta[b]indol-3(2H)-one (4p): The
4
same procedure as for 4b, starting from pure divinyl ketone 2p, afforded
pure 4p as a yellow oil (91%). H NMR (600 MHz) δ (ppm): 7.73 (dt, 1H, J
1
=
7
8.1 Hz, 0.9 Hz), 7.43-7.40 (m, 1H), 7.37 (dt, 1H, J = 8.5 Hz, 0.9 Hz),
.19-7.16 (m, 1H), 3.91 (s, 3H), 3.49-3.45 (m, 2H), 3.14 (dd, 1H, J = 18.2
Hz, 6.2 Hz), 2.62 (dd, 1H, J = 18.2 Hz, .9 Hz), 1.99-1.93 (m, 1H), 1.63-1.58
m, 1H), 1.53-1.46 (m, 2H), 0.99 (t, 3H, J = 7.3 Hz). 13C NMR (150 MHz) δ
ppm): 194.7 (Cq), 148.6 (Cq), 145.0 (Cq), 138.5 (Cq), 126.8 (CH), 123.0
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a) A. Oppedisano, C. Prandi, P. Venturello, A. Deagostino, G. Goti,
D. Scarpi, E. G. Occhiato, Journal of Organic Chemistry 2013, 78,
(
(
(
(
11007-11016; b) D. Scarpi, S. Begliomini, C. Prandi, A.
Cq), 122.4 (CH), 120.3 (CH), 111.2 (CH), 48.7 (CH
CH ), 30.2 (CH), 21.2 (CH ), 14.4 (CH
84 (100). C15
8.96, H 7.72, N 6.29.
2
), 38.3 (CH
). GC-MS m/z (%) = 227 [M] (27),
2
), 33.7
Oppedisano, A. Deagostino, E. Gomez-Bengoa, B. Fiser, E. G.
Occhiato, European Journal of Organic Chemistry 2015, 3251-
+
3
2
3
3265.
1
7
H17NO (227.31): calcd. C 79.26, H 7.54, N 6.16; found C
[
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Acknowledgements
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Financial support from the University of Turin is acknowledged.
We thank the Cost Association STREAM FA1206 “Strigolactones:
biological roles and applications”, Compagnia di San Paolo
Foundation for their support (proJect Stritool). EGO thanks the
MIUR and the University of Florence for support. Part of this work
is included in Simone Ghinato MD thesis.
6178.
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See SI for the compelte carachterization of 2b'and 2f'.
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