Synthesis of Benzo[a]quinolizinium Salts
the mixture reaction for 20 h, compound 1c (25.7 mg, 42%) was
obtained as a pale brown solid, m.p. 210–211 °C. 1H NMR
(300 MHz, CD3OD): δ = 9.77 (d, J = 1.8 Hz, 1 H, Ar-H), 9.39 (d,
J = 9.3 Hz, 1 H, Ar-H), 9.12 (d, J = 8.2 Hz, 1 H, Ar-H), 8.85 (d,
J = 7.1 Hz, 1 H, Ar-H), 8.80 (dd, J = 1.8, 9.3 Hz, 1 H, Ar-H), 8.37
(d, J = 7.3 Hz, 1 H, Ar-H), 8.30 (dd, J = 1.3, 7.7 Hz, 1 H, Ar-H),
(15 mol-% , 14.1 mg, 0.022 mmol) by General Procedure B; com-
pound 1h (42.0 mg, 81%) was obtained as a pale green solid, m.p.
1
180–182 °C (CH2Cl2). H NMR (300 MHz, CD3OD): δ = 9.53 (d,
J = 8.9 Hz, 1 H, Ar-H), 9.47 (d, J = 6.7 Hz, 1 H, Ar-H), 9.12 (d,
J = 8.4 Hz, 1 H, Ar-H), 9.02 (d, J = 7.5 Hz, 1 H, Ar-H), 8.74 (ddd,
J = 1.3, 7.3, 8.7 Hz, 1 H, Ar-H), 8.61 (d, J = 7.5 Hz, 1 H, Ar-H),
8.21 (td, J = 1.1, 7.1 Hz, 1 H, Ar-H), 8.15 (td, J = 1.6, 7.1 Hz, 1 8.30 (dd, J = 0.9, 7.7 Hz, 1 H, Ar-H), 8.28 (t, J = 6.4 Hz, 1 H,
H, Ar-H) ppm. 13C NMR (75 MHz, CD3OD): δ = 42.6, 139.7, Ar-H), 8.09 (t, J = 8.0 Hz, 1 H, Ar-H) ppm. 13C NMR (75 MHz,
134.6, 132.2, 131.6, 130.2, 128.5, 125.6, 125.1, 124.6, 123.9, 120.6
CD3OD): δ = 144.7, 142.1, 141.0, 135.5, 133.8, 133.3, 132.7, 130.7,
128.0, 126.1, 126.0, 124.8, 121.8 (q, J = 316.3 Hz), 120.5 ppm. IR
(q, J = 316.3 Hz), 119.2 ppm. IR (NaCl): νmax = 2921, 1475, 1265,
˜
1225, 1131, 754 cm–1. MS (ES+): m/z (%) = 258 (100) [M]+, 260
(99) [M + 2]. C14H9BrF3NO3S·2H2O (444.20): calcd. C 37.85, H
2.95, N 3.15, S 7.22; found C 37.31, H 2.48, N 2.78, S 8.01.
(NaCl): ν
= 3071, 1633, 1263, 1173, 1149, 1033, 806 cm–1. MS
˜
max
(ES+): m/z (%) = 214 (100) [M]+, 216 (54) [M + 2]. C14H9ClF3NO3S
(363.75): calcd. C 46.23, H 2.49, N 3.85, S 8.81; found C 46.35, H
2.83, N 4.01, S 8.98.
1-Methoxybenzo[a]quinolizinium Triflate (1e): This compound was
obtained from 6e (58.0 mg) in the presence of the catalyst (5 mol-
%, 4.7 mg, 0.0075 mmol) by General Procedure A; after heating of
the reaction mixture for 24 h, compound 1e (18.8 mg, 35%) was
obtained as a green pale solid, m.p. 170–171 °C. 1H NMR
(300 MHz, CD3OD): δ = 9.83 (d, J = 8.6 Hz, 1 H, Ar-H), 9.08 (d,
Supporting Information (see footnote on the first page of this arti-
cle): experimental procedures and full spectroscopic data and
NMR spectra for compounds 6b–h, 9b–h, and 11b–h.
J = 6.2 Hz, 1 H, Ar-H), 8.90 (d, J = 7.1 Hz, 1 H, Ar-H), 8.34 (d, Acknowledgments
J = 8.6 Hz, 1 H, Ar-H), 8.24 (t, J = 7.3 Hz, 2 H, Ar-H), 8.18–8.04
(m, 3 H, Ar-H), 4.43 (s, 3 H, O-CH3) ppm. 13C NMR (75 MHz,
The authors acknowledge support of this work from the Ministerio
CD3OD): δ = 158.9, 134.5, 133.7, 133.4, 132.2, 132.0, 131.1, 129.3,
126.3, 125.6, 125.2, 121.8 (q, J = 316.9 Hz), 121.7, 58.4 ppm. IR
de Ciencia e Innovación (project CTQ2008/04313) and the Instituto
de Salud Carlos III (Red de Investigación Renal, REDinREN,
RD06/0016/0016) and grants from the Comunidad de Madrid
(A. N.) and the Universidad de Alcalá (B. A.).
(NaCl): νmax = 2922, 1574, 1436, 1337, 1261, 1159, 1031, 754 cm–1.
˜
MS (ES+): m/z (%) = 210 (100) [M]+, 211 (54) [M + 1].
C15H12F3NO4S (359.33): calcd. C 50.14, H 3.37, N 3.90, S 8.92;
found C 50.35, H 2.87, N 4.11, S 8.90.
[1] a) R. H. Grubbs (Ed.) in Handbook of Metathesis, Wiley-VCH,
Weinheim, Germany, 2003, Vol. 2; b) K. C. Nicolaou, P. G.
Bulger, D. Sarlah, Angew. Chem. 2005, 117, 4564; Angew.
Chem. Int. Ed. 2005, 44, 4490–4527.
[2] a) F.-X. Felpin, J. Lebreton, Eur. J. Org. Chem. 2003, 3693–
3712; b) M. A. Walters in Progress in Heterocyclic Chemistry
(Eds.: G. W. Gribble, J. A. Joule), Pergamon, Amsterdam, 2003,
Vol. 15, pp. 1–36; c) I. Nakamura, Y. Yamamoto, Chem. Rev.
2004, 104, 2127–2198; d) A. Deiters, S. F. Martin, Chem. Rev.
2004, 104, 2199–2238; e) W. A. L. van Otterlo, C. B. de Koning,
Chem. Rev. 2009, 109, 3743–3782.
[3] a) S. S. Kinderman, J. H. van Maarseveen, H. E. Schoemaker,
H. Hiemstra, P. J. T. Rutjes, Org. Lett. 2001, 3, 2045–2048; b)
M. Arisawa, Y. Terada, M. Nakagawa, A. Nishida, Angew.
Chem. 2002, 114, 4926; Angew. Chem. Int. Ed. 2002, 41, 4732–
4734; c) W. A. L. Van Otterlo, R. Pathak, C. B. de Koning,
Synlett 2003, 1859–1861; d) M. Rosillo, G. Domínguez, L. Cas-
arrubios, U. Amador, J. Pérez-Castells, J. Org. Chem. 2004, 69,
2084–2093; e) J. D. Katz, L. E. Overman, Tetrahedron 2004, 60,
9559–9568; f) L. Manzoni, M. Colombo, C. Scolastico, Tetra-
hedron Lett. 2004, 45, 2623–2625; g) W. A. L. Van Otterlo,
G. L. Morgans, S. D. Khanye, B. A. A. Aderibigbe, J. P.
Michael, D. G. Billing, Tetrahedron Lett. 2004, 45, 9171–9175;
h) G. Liu, W.-Y. Tai, Y.-L. Li, F.-J. Nan, Tetrahedron Lett.
2006, 47, 3295–3298.
[4] a) P. Evans, R. Grigg, M. York, Tetrahedron Lett. 2000, 41,
3967–3970; b) M. Arisawa, Y. Terada, M. Nakagawa, A. Nish-
ida, Angew. Chem. 2002, 114, 4926; Angew. Chem. Int. Ed.
2002, 41, 4732–4734.
[5] a) A. Núñez, B. Abarca, A. M. Cuadro, J. Alvarez-Builla, J. J.
Vaquero, J. Org. Chem. 2009, 74, 4166–4176; b) A. Núñez,
A. M. Cuadro, J. Alvarez-Builla, J. J. Vaquero, Chem. Commun.
2006, 2690–2692; c) A. Nuñez, A. M. Cuadro, J. Alvarez-Bu-
illa, J. J. Vaquero, Org. Lett. 2004, 6, 4125–4127.
[6] a) S. Arai, K. Nagakura, M. Ishikawa, M. Hida, J. Chem. Soc.
Perkin Trans. 1 1990, 7, 1915–1917; b) A. Granzhan, H. Ihmels,
Org. Lett. 2005, 7, 5119–5122; c) K. Faulhaber, A. Granzhan,
H. Ihmels, G. Viola, Pure Appl. Chem. 2006, 78, 2325–2331; d)
A. Granzhan, H. Ihmels, G. Viola, J. Am. Chem. Soc. 2007,
129, 1254–1267.
3-(4-Morpholinyl)benzo[a]quinolizinium Triflate (1f): This com-
pound was obtained by General Procedure A from 6f (66.4 mg) in
the presence of the catalyst (5 mol-%, 4.7 mg, 0.0075 mmol); after
heating for 15 h and purification by chromatography, compound 1f
(24.2 mg, 39%) was obtained as a green solid, m.p. 160–161 °C
1
(Cl2CH2/acetone). H NMR (300 MHz, [D6]acetone): δ = 9.23 (d,
J = 9.9 Hz, 1 H, Ar-H), 8.95 (dd, J = 3.5, 4.4 Hz, 1 H, Ar-H), 8.90
(d, J = 2.6 Hz, 1 H, Ar-H), 8.78 (d, J = 7.3 Hz, 1 H, Ar-H), 8.45
(dd, J = 2.6, 9.9 Hz, 1 H, Ar-H), 8.24–8.20 (m, 2 H, Ar-H), 8.11–
8.08 (m, 2 H, Ar-H), 4.04 (t, J = 4.9 Hz, 4 H, N-CH2-CH2-O), 3.65
(t, J = 4.9 Hz, 4 H, N-CH2-CH2-O) ppm. 13C NMR (75 MHz,
[D6]acetone): δ = 147.6, 135.5, 132.9, 131.7, 131.2, 130.7, 129.0,
128.9, 125.9, 124.9, 124.4, 123.7, 122.9, 122.1 (q, J = 320.0 Hz),
66.4, 47.6 ppm. IR (NaCl): ν
= 2922, 1624, 1254, 1223, 1128,
˜
max
777 cm–1. MS (ES+): m/z (%) = 265 (100) [M]+. C18H17F3N2O4S
(414.41): calcd. C 52.17, H 4.13, N 6.76, S 7.74; found C 51.87, H
4.48, N 6.85, S 8.07.
[1,3]Benzodioxolo[5,6-a]quinolizinium Triflate (1g): This compound
was obtained by General Procedure A from 6g (60.2 mg) in the
presence of the catalyst (5 mol-%, 4.7 mg, 0.0075 mmol); after heat-
ing for 2 h, compound 1g (49.3 mg, 88%) was obtained as a pale-
brown solid, m.p. 181–182 °C (Cl2CH2/acetone). 1H NMR
(300 MHz, CD3OD/[D6]acetone): δ = 9.24 (d, J = 6.8 Hz, 1 H, Ar-
H), 9.20 (d, J = 9.1 Hz, 1 H, Ar-H), 8.82 (d, J = 7.1 Hz, 1 H, Ar-
H), 8.48 (t, J = 8.0 Hz, 1 H, Ar-H), 8.44 (s, 1 H, Ar-H), 8.18 (d, J
= 7.1 Hz, 1 H, Ar-H), 8.05 (t, J = 6.8 Hz, 1 H, Ar-H), 7.62 (s, 1
H, Ar-H), 6.40 (s, 2 H, O-CH2-O) ppm. 13C NMR (75 MHz,
CD3OD/[D6]acetone): δ = 155.6, 153.4, 143.5, 139.4, 132.4, 130.8,
124.1, 123.9, 123.2, 121.8 (q, J = 319.9 Hz), 119.7, 106.2, 105.3,
103.6 ppm. IR (NaCl): ν
= 2921, 1621, 1478, 1260, 1159, 1030,
˜
max
638 cm–1. MS (ES+): m/z (%) = 224 (100) [M]+. C15H10F3NO5S
(373.31): calcd. C 48.26, H 2.70, N 3.75, S 8.59; found C 48.66, H
3.08, N 3.42, S 8.70.
8-Chlorobenzo[a]quinolizinium Triflate (1h): This compound was
obtained from 6h (58.7 mg) in the presence of the H-G catalyst
Eur. J. Org. Chem. 2011, 1280–1290
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1289