G. F. Sanapo, B. Daoust / Tetrahedron Letters 49 (2008) 4196–4199
4199
NMR (200 MHz, CDCl3), J (Hz): d 1.29 (t, J = 7, 3H),
2.80 (s, 4H), 3.8 (q, J = 7, 2H), 5.53 (s, 1H). 13C NMR,
(50 MHz, CDCl3): d 15.1, 28.5, 60.14, 66.9, 143.5, 174.7.
IR (neat, cmꢀ1): 3485 (s), 3260(w), 3087 (s), 2939 (m),
1716 (w), 1346 (m). Mass spectrum: m/e (% relative inten-
sity) 295 (7), 168 (100), 100 (17), 55 (13).
(t, J = 6, 2H), 5.4 (d, J = 14, 1H), 8.0 (d, J = 14, 1H).
13C NMR (50 MHz, CDCl3): d 20.6, 22.5, 32.9, 45.1,
55.3, 137.7, 167.9. IR (neat, cmꢀ1): 3258 (s), 3073 (s),
2948 (s), 2872 (s), 2357 (s), 1646 (w), 1600 (s), 1475 (s),
1455 (s), 1427 (s), 1401 (s), 1345 (s). Mass spectrum: m/e
(% relative intensity): 251 (27), 153 (9), 124 (100), 96 (9),
82 (41), 69 (17), 55 (48), 41 (43). HRMS: m/z calcd for
C7H10INO: 250.981; found 250.981.
8. General procedure for the copper-catalyzed coupling
between amide derivatives and 1,2-diiodoethene
8.4. N-(2-Iodoethene) acetanilide ð13Þ
1,2-Diiodoethene was prepared from acetylene accord-
ing to the method described by Wright and Lowe-Ma.9
A screw cap test tube was charged with CuI (0.4 mmol,
13 mol %), N,N0-dimethyl ethylenediamine (0.6 mmol, 20
mol %) and THF (1 mL). The mixture was stirred for 15
min. Cesium carbonate (6 mmol) and a solution containing
the amide (3 mmol), 1,2-diiodoethene (4.2 mmol) and THF
(2.6 mL) were added. The reaction tube was capped in a
nitrogen filled bag. The reaction tube was immersed in a
preheated oil bath, and the reaction mixture was stirred
for 24 h at 55 °C. The reaction mixture was cooled to room
temperature, and the resulting suspension was diluted with
methylene chloride (10 mL) and filtrated. The solvent was
evaporated under reduced pressure and the crude product
was purified by flash chromatography to provide the
desired product.
Yellow solid. Mp.103–104 °C. 1H NMR (200 MHz,
CDCl3), J (Hz): d 1.8 (s, 3H), 4.75 (d, J = 14, 1H), 7.14
(m, 2H), 7.42 (m, 3H), 8.10 (d, J = 14, 1H). 13C NMR
(50 MHz, CDCl3): d 23.0, 58.3, 128.9, 129.5, 130.6,
138.6, 168.0. IR (neat, cmꢀ1): 3326 (s), 3060 (d), 1676
(w), 1608 (s), 1591 (s), 1487 (s), 1451 (s), 1371 (s). Mass
spectrum: m/e (% relative intensity) 287 (6), 245 (9), 160
(100), 118 (83), 117 (53), 91 (34), 77 (25), 51 (24), 43
(60). HRMS: m/z calcd for C10H10INO: 286.981; found
286.981.
Acknowledgments
Acknowledgment is made to the Natural Sciences and
Engineering Council of Canada for financial support.
8.1. N-(2-Iodoethene)-2-pyrrolidinone ð12aÞ
References and notes
Yellow solid. Mp 85–87 °C. 1H NMR (200 MHz,
CDCl3), J (Hz): d 2.35 (m, 2H), 2.40 (t, J = 8, 2H), 3.46
(d, J = 7, 2H), 5.3 (d, J = 14, 1H), 7.5 (d, J = 14, 1H).
13C NMR (50 MHz, CDCl3): d 17.5, 30.8, 44.7, 55.4,
134.7, 172.4. IR (neat, cmꢀ1): 3338 (s), 3062 (s), 2959
(m), 2884 (s), 1690 (w), 1611 (s), 1482 (s), 1454 (s), 1393
(s), 1325 (s). Mass spectrum: m/e (% relative intensity):
237 (87), 182 (63), 153 (21), 127 (30), 110 (100), 82 (47),
55 (68), 41 (57). HRMS: m/z calcd for C6H8INO:
236.965; found 236.965.
1. (a) Kohno, J.; Koguchi, Y.; Nishio, M.; Nakao, K.; Kuroda, M.;
Shimizu, R.; Ohnuki, T.; Komatsubara, S. J. Org. Chem. 2000, 65,
990; (b) Toske, S. G.; Jensen, P. R.; Kauffman, C. A.; Fenical, W.
Tetrahedron 1998, 54, 13459.
2. (a) Jiang, L.; Job, G. E.; Kaplars, A.; Buchwald, S. L. Org. Lett. 2003,
5, 3667; (b) Pan, X.; Cai, Q.; Ma, D. Org. Lett. 2004, 6,
1809.
3. Abreu, A. S.; Ferreira, P. M. T.; Monteiro, L. S.; Queiroz, M.-J. R.
P.; Ferreira, I. C. F. R.; Calhelha, R.; Estevinho, L. M. Tetrahedron
2004, 60, 11821–11828; Roff, G. J.; Lloyd, R. C.; Turner, N. J. J. Am.
Chem. Soc. 2004, 126, 4098–4099; Chakrabarty, M.; Basak, R.;
Harigaya, Y. Synthesis 2003, 2011–2014; Barkin, J. L.; Faust, M. D.,
Jr.; Trenkle, W. C. Org. Lett. 2003, 5, 3333–3335.
4. (a) Driguez, H.; Vermes, J. P.; Lessard, J. Can. J. Chem. 1978, 56, 119;
(b) Tuaillon, J.; Couture, Y.; J.Lessard Can. J. Chem. 1987, 65, 2194;
(c) Daniher, F. A.; Butler, P. E. J. Org. Chem. 1968, 33,
4336.
5. De Luca, L.; Giacomelli, G.; Nieddu, G. Synlett 2005,
223.
6. Bachand, C.; Driguez, H.; Paton, J. M.; Touchard, D.; Lessard, J.
J. Org. Chem. 1974, 39, 3136.
7. Moyano, A.; Charbonier, F.; Greene, A. J. Org. Chem. 1987, 52,
2919.
8. Keegstra, M. A. Tetrahedron 1992, 48, 2681.
8.2. N-(2-Iodoethene)-2-oxazolidinone ð12bÞ
Yellow solid. Mp dec 71 °C. 1H NMR (200 Hz, CDCl3),
J (Hz): d 3.69 (t, J = 8, 2H), 4.40 (t, J = 8, 2H), 5.21 (d,
J = 14, 1H), 7.23 (d, J = 14, 1H). 13C NMR (50 Hz,
CDCl3): d 42.1, 53.1, 62.6, 134.6, 154.4.IR (neat, cmꢀ1):
3077 (s), 1761 (w), 1613 (s), 1474 (s), 1409 (s). Mass spec-
trum: m/e (% relative intensity) 239 (59), 180 (56), 153
(61), 127 (41), 112 (100), 41 (70). HRMS: m/z calcd for
C5H6INO2: 238.944; found 238.944.
9. Wright, M. E.; Lowe-Ma, C. K. Organometallics 1990, 9,
347.
10. Compounds previously reported in the literature were characterized
by comparing their 1H NMR spectra to the published data.
11. Enamides 7a and 7b were not sufficiently stable to allow HRMS
characterization.
8.3. N-(2-Iodoethene)-2-piperidinone ð12cÞ
Yellow solid. Mp dec 140 °C. 1H NMR (200 MHz,
CDCl3), J (Hz): d 1.83 (m, 4H), 2.45 (t, J = 6, 2H), 3.38