2396
D. M. Fink
LETTER
5-Chloro-1-propyl-1H-indole (4d):
References
1H NMR (300 MHz, CDCl3): d = 0.81 (t, J = 7.4 Hz, 3 H), 1.75 (app
sextet, J = 7.2 Hz, 2 H), 4.12 (t, J = 6.9 Hz, 2 H), 6.40 (d, J = 3.1 Hz,
1 H), 7.09 (dd, J = 8.7, 2.0 Hz, 1 H), 7.42 (d, J = 3.1 Hz, 1 H), 7.50
(d, J = 8.7 Hz, 1 H), 7.56 (d, J = 2.0 Hz, 1 H) ppm. 13C NMR (75
MHz, CDCl3): d = 11.6, 23.6, 48.2, 100.4, 110.2, 120.0, 121.4,
124.7, 128.9, 129.3, 134.2 ppm. HRMS (ESI+): m/e calcd for
C11H12ClNH (MH+): 194.0736; found: 194.0734.
(1) Gilchrist, T. L. Heterocyclic Chemistry; John Wiley and
Sons: New York, 1985, 67–168.
(2) Epling, G. A.; Kumar, A. Synlett 1991, 347.
(3) See, for example: Galons, H.; Miocque, M.; Combet-
Farnoux, C.; Bensaid, Y.; Decodts, G.; Bram, G. Chem.
Pharm. Bull. 1985, 33, 5108.
(4) Schmolka, S. J.; Zimmer, H. Synthesis 1984, 29.
(5) (a) Kalir, A.; Szara, S. J. J. Med. Chem. 1966, 9, 793.
(b) Kurihara, T.; Fujimoto, T.; Harusara, S.; Yoneda, R.
Synthesis 1987, 396.
(6) Kikugawa, Y.; Miyake, Y. Synthesis 1981, 461.
(7) Bhagwat, S. S.; Gude, C. Tetrahedron Lett. 1994, 35, 1847.
(8) Alkylation of 5-bromoindole under Mitsunobu-like
conditions was recently reported. See: Bombrun, A.; Casi,
G. Tetrahedron Lett. 2002, 43, 2187.
5-Chloro-1-isopropyl-1H-indole (4e):
1H NMR (300 MHz, CDCl3): d = 1.51 (d, J = 6.75 Hz, 6 H), 4.62
(sept, J = 6.8 Hz, 1 H), 6.43 (d, J = 2.9 Hz, 1 H), 7.12 (dd, J = 8.6,
2.0 Hz, 1 H), 7.21–7.27 (m, 2 H), 7.56 (d, J = 2.0 Hz, 1 H) ppm. 13
C
NMR (75 MHz, CDCl3): d = 22.8, 47.4, 100.7, 110.2, 120.1, 121.3,
124.7, 129.3, 133.7 ppm. HRMS (ESI+): m/e calcd for C11H12ClNH
(MH+): 194.0736; found: 194.0733.
(9) Using n-butyllithium as the base in THF as in ref. 2 resulted
in a slow but clean conversion to product (24% conversion
at reflux for 18 h). However, if DMPU was used as solvent,
then the product was formed at r.t. over 48 h.
(10) Macor, J. E.; Ryan, K.; Newman, M. E. Tetrahedron 1992,
48, 1039.
2-(5-Methoxyindol-1-yl)-1-phenylethanol (4f):
1H NMR (300 MHz, CDCl3): d = 3.82 (s, 3 H), 4.14–4.28 (m, 2 H),
4.94 (dd, J = 7.9, 4.2 Hz, 1 H), 6.37 (d, J = 3.1 Hz, 1 H), 6.85 (dd,
J = 8.8, 2.4 Hz, 1 H), 7.00 (d, J = 3.1 Hz, 1 H), 7.06 (d, J = 2.4 Hz,
1 H), 7.22–7.37 (m, 6 H) ppm. 13C NMR (75 MHz, CDCl3): d =
54.5, 56.0, 73.7, 101.2, 102.8, 110.3, 112.1, 126.0, 128.3, 128.8,
129.2, 129.3, 131.6, 141.2, 154.2 ppm. HRMS (ESI+): m/e calcd for
C17H17NO2 (MH+): 268.1338; found: 268.1327.
(11) Mukhopadhyay, T.; Seebach, D. Helv. Chim. Acta 1982, 65,
385.
(12) The products exhibited satisfactory 1H NMR spectra.
(13) Sundberg, R. J. Org. Chem. 1973, 38, 3324.
(14) Shim, S. C.; Youn, Y. Z.; Lee, D. Y.; Kim, T. J.; Cho, C. S.
Synth. Commun. 1996, 26, 1349.
2-(7-Fluoroindol-1-yl)-1-phenylethanol (4g):
1H NMR (300 MHz, DMSO-d6): d = 4.28 (dd, J = 14.0, 8.5 Hz, 1
H), 4.42 (dd, J = 14.0, 4.0 Hz, 1 H), 4.87–4.92 (m, 1 H), 5.62 (d,
J = 4.8 Hz, 1 H), 6.43 (t, J = 2.7 Hz, 1 H), 6.86–6.97 (m, 2 H), 7.12–
7.34 (m, 8 H) ppm. 13C NMR (75 MHz, DMSO-d6) d = 55.8, 72.5,
101.0, 106.4 (JCF = 8.1 Hz), 116.4 (JCF = 3.0 Hz), 119.0 (JCF = 6.6
Hz), 123 (JCF = 9.2 Hz), 125.6, 127.1, 127.9, 131.3, 132.2 (JCF = 5.8
Hz), 142.6, 149.3 (JCF = 241 Hz) ppm. HRMS (ESI+): m/e calcd for
C16H14FNO (MH+): 256.1138; found: 256.1134.
(15) Hary, U.; Roettig, U.; Paal, M. Tetrahedron Lett. 2001, 42,
5187.
Synlett 2004, No. 13, 2394–2396 © Thieme Stuttgart · New York