S. J. Coles et al. / Tetrahedron 61 (2005) 4447–4452
4451
1
bromoester as a clear oil (95%). H NMR (CDCl3) d 8.05
63.3, 37.4, 32.9, 27.9, 27.8, 27.0, 26.9, 19.9. MS (EI)
m/zZ232 (MC).
(2H, d, JZ7.0 Hz), 7.56 (1H, t, JZ7.0 Hz), 7.45 (2H, m),
4.35 (2H, m), 4.20 (1H, m), 2.05–1.85 (4H, m), 1.71 (3H, d
JZ6.0 Hz); 13C NMR (CDCl3) d 166.7, 133.1, 130.3, 129.6,
128.5, 64.4, 51.0, 37.7, 27.5, 26.6; nmax(liquid film) 2960,
1719, 1277, 1115, 712 cmK1; HRMS calcd for C12H15O2-
BrNa (MCNaC) 293.0147. Found 293.0155.
3.3. Data retrieval
Crystal structures were located within version 5.25
(November 2003 release) of the Cambridge Structural
Database (CSD) which contained 298,097 entries.29
3.2.4. 4-Chloropentyl phenoxyacetate (7b). Reaction of 4
and phenoxyacetyl chloride in the presence of BiCl3 (5%)
afforded the chloroester as a clear oil (92%). 1H NMR
(CDCl3) d 7.31 (2H, m), 7.06 (1H, t, JZ7.0 Hz, p-Ph), 6.90
(2H, d JZ7.0 Hz), 4.64 (2H, s), 4.28 (2H, m), 4.05 (1H, m),
1.98–1.65 (4H, m), 1.47 (3H, d JZ6.0 Hz). 13C NMR
(CDCl3) d 169.4, 157.8, 129.7, 121.9, 114.7, 65.4, 64.9,
58.2, 36.6, 25.9, 25.5; nmax(liquid film) 2969, 2928, 1807,
1600, 1495, 1216, 754 cmK1; HRMS calcd for C13H17O3-
ClNa (MCNaC) 279.0758. Found 279.0763.
Acknowledgements
The author thanks the Leverhulme Trust, the EPSRC and
UWE for financial support. J. F. C. thanks Prof. Guy Lloyd-
Jones for helpful comments in the preparation of this
manuscript.
3.2.5. 4-Chloropentyl (S)-(K)-2-acetoxypropionate (7c).
Reaction of 4 and (S)-(K)-2-acetoxypropionyl chloride in
the presence of BiCl3 (5%) afforded the chloroester as a
clear oil (96%). 1H NMR (CDCl3) d 5.10 (1H, m), 4.18 (2H,
m), 4.05 (1H, m), 2.08 (3H, s), 1.95–1.65 (4H, m), 1.48, 1.45
(3H, 2!d JZ6.0 Hz), 1.49 (3H, d JZ5.0 Hz); 13C NMR
(CDCl3) d. 175.9, 171.1, 170.7*, 68.8, 68.3, 64.8*, 58.0,
36.5*, 25.8, 25.5, 20.7*, 17.0, 16.8; nmax(liquid film) 3476
(br), 2991, 1743, 1238, 1101 cmK1; HRMS calcd for
C10H17O4ClNa (MCNaC) 259.0708. Found 259.0712.
References and notes
1. Barucki, H.; Coles, S. J.; Costello, J. F.; Hursthouse, M. B.
Chem. Eur. J. 2003, 6, 2877. Coles, S. J.; Costello, J. F.;
Hursthouse, M. B.; Smith, S. J. Organomet. Chem. 2002, 662,
98. Barucki, H.; Coles, S. J.; Costello, J. F.; Hursthouse, M. B.
J. Organomet. Chem. 2001, 622, 265. Barucki, H.; Coles, S. J.;
Costello, J. F.; Gelbrich, T.; Hursthouse, M. B. J. Chem. Soc.,
Dalton Trans. 2000, 2319.
2. Le Roux, C.; Dubac, J. Synlett 2002, 2, 181. Leonard, N. M.;
Wieland, L. C.; Mohan, R. S. Tetrahedron 2002, 58, 8373.
Suzuki, H. In Organobismuth Chemistry; Suzuki, H., Matano,
Y., Eds.; Elsevier: Amsterdam, 2001.
3.2.6. 4-Chloropentyl 20-furoate (7d). Reaction of 4 and
2-furoyl chloride in the presence of BiCl3 (5%) afforded the
1
chloroester as a clear oil (90%). H NMR (CDCl3) d 7.59
(1H, m), 7.18 (1H, m), 6.52 (1H, m), 4.35 (2H, m), 4.15 (1H,
m), 2.05–1.75 (4H, m), 1.52 (3H, d JZ6.0 Hz); 13C NMR
(CDCl3) d 158.8, 146.5, 118.1, 111.9, 64.4, 58.2, 36.7, 30.4,
26.1, 25.5; nmax(liquid film) 2966, 1727, 1475, 1298, 1181,
3. Johnson, F. In Olah, G. A., Ed.; Friedel–Crafts and Related
Reactions; Interscience: New York, 1965; Vol. 4, pp 1–109.
4. Cloke, J. B.; Pilgrim, F. J. J. Am. Chem. Soc. 1939, 61, 2667.
5. Ganem, B.; Small, V. R., Jr J. Org. Chem. 1974, 39, 3728.
6. Goldsmith, D. J.; Kennedy, E.; Campbell, R. G. J. Org. Chem.
1975, 40, 3571.
1120, 764 cmK1
; HRMS calcd for C10H13O3ClNa
(MCNaC) 239.0445. Found 239.0451.
7. Green, L.; Hemeon, I.; Singer, R. D. Tetrahedron Lett. 2000,
41, 1343.
3.2.7. 4-Chloropentyl norborn-20-ene-50-carboxylate
(7e). Reaction of 4 with a 1:1 mixture of endo/exo
norborn-2-ene-5-carboxylic acid chloride in the presence
of BiCl3 (5%) afforded a 1:1 mixture of endo/exo
chloroesters (GC retention timesZ30.72/30.98 min). 1H
NMR (CDCl3) d 6.10–5.95 (2H, m), 4.10–3.95 (4H, m),
3.12 (1H, br s), 2.95–2.85 (1H, m), 2.15 (2H, m), 1.95–1.56
(5H, m), 1.44 (3H, d JZ6.0 Hz), 1.42–1.20 (2H, m); 13C
NMR (CDCl3) d 176.1, 174.6, 138.0, 137.8, 135.7, 132.3,
63.9, 63.7, 58.1, 49.6, 46.6, 46.4, 45.7, 43.3, 43.1, 42.5,
41.6, 36.8, 36.7, 30.3, 29.2, 26.0, 25.9, 25.4; nmax(liquid
film) 2973, 2874, 1731, 1446, 1174 cmK1; HRMS calcd for
C13H19O2ClNa (MCNaC) 265.0966. Found 265.0976.
8. Malladi, R. R.; Kabalka, G. W. Synth. Commun. 2002, 32,
1997.
9. Delaney, P. A.; Johnstone, R. A. W.; Entwistle, I. D. J. Chem.
Soc. Perkin Trans. 1 1986, 1855.
10. Luzzio, F. A.; Bobb, R. A. Tetrahedron 1999, 55, 1851.
11. Kwon, D. W.; Kim, Y. H.; Lee, K. J. Org. Chem. 2002, 67,
9488.
12. Qian, C.; Qiu, A.; Huang, Y.; Chen, W. J. Organomet. Chem.
1991, 412, 53.
13. Alper, H.; Huang, C.-C. J. Org. Chem. 1973, 38, 64. Guo, Q.;
Miyaji, T.; Gao, G.; Hara, R.; Takahashi, T. J. Chem. Soc.,
Chem. Commun. 2001, 1018. Iqbal, J.; Srivastava, R. R.
Tetrahedron 1991, 47, 3155.
3.2.8. Tetralin (10).26 To a mixture of 8 (250 mg,
1.32 mmol) and acetyl chloride (103 mg, 1.32 mmol) in
DCM (25 mL) was added BiCl3 (20 mg, 5%). The solution
was stirred at room temperature for 6 h, concentrated in
vacuo and subjected to flash chromatography (SiO2/CHCl3)
14. Guo, Q.; Miyaji, T.; Hara, R.; Shen, B.; Takahashi, T.
Tetrahedron 2002, 58, 7377.
15. Pri-Bar, I.; Stille, J. K. J. Org. Chem. 1982, 47, 1215.
16. Fitch, J. W.; Payne, W. G.; Westmoreland, D. J. Org. Chem.
1983, 48, 751.
1
to afford a clear oil characterised as 10 (213 mg, 87%). H
17. Ionisation Constants of Organic Acids in Aqueous Solution;
Serjent, E. P., Dempsey, B., Eds.; I.U.P.A.C Chemical Data
Series; Pergamon: Oxford, 1979; Vol. 23.
NMR (CDCl3) d 7.35–7.05 (4H, m), 3.68 (2H, m), 3.02 (1H,
m), 2.83 (2H, m), 2.04 (3H, s), 1.72–1.45 (8H, m); 13C NMR
(CDCl3) d 171.2, 136.2, 136.0, 129.2, 128.8, 125.7, 125.6,
18. BiCl3 has been shown to be an effective reagent for