◦
(3-Pyridyl)methanol (6c). From substrate 2c (500 mg), 6c was
isolated as a colourless oil (11 mg, 2%). Spectroscopic data were
in accordance with those published in the literature.21
(lit.,27a 164–165 C). Spectroscopic data were in accordance with
those published in the literature.27b
2-Bromo-3-hydroxypyridine (4e). From substrate 1e (100 mg),
4e was isolated as a pale yellow resin (11 mg, 10%). Spectroscopic
data were in accordance with those published in the literature.28
1-(3-Hydroxy-2-pyridyl)ethanol (10). From ( )-1-(2-pyridyl)-
ethanol, ( )-5a (150 mg), 10 was isolated as a yellow oil (54 mg,
32%); dH (300 MHz, CDCl3) 1.52 (3H, d, J = 6.6 Hz, CH3), 5.13
(1H, q, J = 6.6 Hz, CHOH), 7.08 (1H, dd, J = 8.0 Hz, J = 4.5 Hz,
5-H), 7.18 (1H, d, J = 8.0 Hz, 4-H), 7.66 (2H, br s, 2 × OH), 7.99
(1H, d, J = 4.5 Hz, 6-H); dC (75 MHz, CDCl3) 22.6 (CH3), 70.4
(CH), 123.5 (CH), 124.5 (C), 138.6 (CH), 148.9 (CH), 152.1 (C);
m/z (EI) 139 (M+, 72%), 124 (M+ − CH3, 97%), 120 (95%), 39
(100%); HRMS (EI) calcd. for C7H9NO2 (M+): 139.063329, found
139.063240.
3-Hydroxypyridine (4f). From substrate 1f (100 mg), 4f was
isolated as a yellow oil (3 mg, 3%). Spectroscopic data were in
accordance with those published in the literature.29
4-Chloro-3-hydroxypyridine (7d). From substrate 3d (400 mg),
7d was isolated as a white solid (46 mg, 10%); mp 126–127 ◦C. Spec-
troscopic data were in accordance with those published in the
literature.30
The racemic substrate, ( )-5a, yielded (S)-10 with 53% ee, [a]D
−15.7 (c 0.8, CHCl3); (S)-5a, yielded enantiopure (S)-10, [a]D
−28.8 (c 0.8, CHCl3); and (R)-5a yielded (R)-10 with 37% ee,
[a]D +10.1 (c 0.8, CHCl3).
2-Ethyl-3-hydroxypyridine (4a). From substrate 1a (500 mg),
4a was isolated◦as a white solid (62 mg, 11%); mp 135–136 ◦C,
(lit.,22 134–136 C). Spectroscopic data were in accordance with
those published in the literature.23
4-Bromo-3-hydroxypyridine (7e). From substrate 1e (100 mg),
7e was isolated as a pale yellow resin (11 mg, 10%). Spectroscopic
data were in accordance with those published in the literature.31
5-Chloro-3-hydroxypyridine (8). From substrate 2d (300 mg),
8 was isolated as a white solid (10 mg, 9%). Spectroscopic data
were in accordance with those published in the literature.32
Acknowledgements
3-Hydroxy-2-propylpyridine (4b). From substrate 1b (◦200 mg),
4b was isolated as a white solid (24 mg, 10%); mp 134–135 C (lit.,22
133–135 ◦C); dH (500 MHz, CDCl3) 0.99 (3H, t, J = 7.4 Hz, CH3),
1.71 (2H, m, CH2CH3), 2.68 (2H, t, J = 7.3 Hz, CH2CH2), 6.15
(1H, br s, OH), 6.94 (1H, dd, J = 7.8 Hz, J = 4.9 Hz, 5-H),
7.09 (1H, d, J = 7.8 Hz, 4-H), 8.02 (1H, d, J = 4.9 Hz, 6-H);
dC (125 MHz, CDCl3) 13.0 (CH3), 20.8 (CH2), 30.5 (CH2), 124.3
(CH), 134.2 (CH), 137.8 (CH), 150.3 (C), 153.0 (C); m/z (EI)
[silylated with BSTFA] 209 (M+, 93%), 194 (M+ − CH3, 100%),
180 (M+ − CH2CH3, 65%), 164 (80%), 73 (94%).
We thank Queen’s University, Belfast (to M.D.G.), the BBSRC
(to P.G.) and the European Social Fund (to R.S.) for financial
support. We also thank Dr C. C. R. Allen, QUESTOR Centre,
Queen’s University, Belfast, for invaluable assistance in growth
and maintenance of the P. putida UV4 strain.
References
1 D. R. Boyd and G. N. Sheldrake, Nat. Prod. Rep., 1998, 15, 309.
2 (a) D. R. Boyd, N. D. Sharma, I. N. Brannigan, S. A. Haughey, J. F.
Malone, D. A. Clarke and H. Dalton, Chem. Commun., 1996, 2361;
(b) S. C. Kelly, C. A. McDonnell, R. A. M. O’Ferrall, S. N. Rao, D. R.
Boyd, N. D. Sharma and I. N. Brannigan, Gazz. Chim. Ital., 1996, 126,
747; (c) D. R. Boyd, N. D. Sharma, R. Boyle, J. F. Malone, J. Chima
and H. Dalton, Tetrahedron: Asymmetry, 1993, 4, 1307; (d) D. R. Boyd,
N. D. Sharma, R. Boyle, B. T. McMurray, T. A. Evans, J. F. Malone, H.
Dalton, J. Chima and G. N. Sheldrake, J. Chem. Soc, Chem. Commun.,
1993, 49.
3-Hydroxy-2-methylpyridine (4c). From substrate 1c (100 mg),
4c was isolated as a white solid (12 mg, 10%); mp 165–168 ◦C
(lit.,24a 168.5–169.5 ◦C). Spectroscopic data were in accordance
with those published in the literature.24b
4-Ethyl-3-hydroxypyridine (7a). From substrate 3a (100 mg),
7a was isolated as a white solid (17 mg, 15%); mp 94–95 ◦C (lit.,25a
93.5–95 ◦C). Spectroscopic data were in accordance with those
published in the literature.25b
3 D. R. Boyd, N. D. Sharma, M. R. J. Dorrity, M. V. Hand, R. A. S.
McMordie, J. F. Malone, H. P. Porter, H. Dalton and G. N. Sheldrake,
J. Chem. Soc., Perkin Trans. 1, 1993, 1065.
4 D. R. Boyd, N. D. Sharma, J. G. Carroll, J. F. Malone, D. G.
Mackerracher and C. C. R. Allen, Chem. Commun., 1998, 683.
5 (a) L. Modyanova and R. Azerad, Tetrahedron Lett., 2000, 41, 3865;
(b) D. R. Boyd, N. D. Sharma, L. V. Modyanova, J. G. Carroll, J. F.
Malone, C. C. R. Allen, J. T. G. Harrison, D. T. Gibson, R. E. Parales
and H. Dalton, Can. J. Chem., 2002, 80, 589.
6 (a) C.-E. Kuo and S.-M. Liu; (b) S.-M. Liu and C.-L. Kuo, Chemo-
sphere, 1997, 35, 2255; (c) S.-M. Liu, C.-H. Wu and H.-J. Huang,
Chemosphere, 1998, 36, 2345; (d) A. Tinschert, A. Tschech, K.
Heinzmann and A. Kiener, Appl. Microbiol. Biotechnol., 2000, 53, 185;
(e) J. G. Bundy, A. W. J. Morriss, D. G. Durham, C. D. Campbell and
G. I. Paton, Chemosphere, 2001, 42, 885; (f) S. N. Wang, P. Xu, H. Z.
Tang, J. Meng, X. L. Liu and C. Q. Ma, Environ. Sci. Technol., 2005,
39, 6877.
3-Hydroxy-4-propylpyridine (7b). From substrate 3b (300 mg),
7b was isolated as a white solid (24 mg, 7%); mp 94–97 ◦C; dH
(500 MHz, CDCl3) 0.99 (3H, dt, J = 7.4 Hz, J = 2.2 Hz, CH3),
1.71 (2H, m, CH2CH3), 2.66 (2H, q, J = 7.4 Hz, CH2CH2), 7.08
(1H, d, J = 4.9 Hz, 5-H), 7.93 (1H, d, J = 4.8 Hz, 6-H), 8.18
(1H, s, 2-H); dC (125 MHz, CDCl3) 11.3 (CH3), 22.0 (CH2), 30.6
(CH2) 124.8 (CH), 134.1 (C), 136.3 (CH), 145.8 (CH), 152.6 (C);
m/z (EI) [silylated with BSTFA] 209 (M+, 93%), 194 (M+ − CH3,
100%), 180 (M+ − CH2CH3, 65%), 164 (80%), 73 (94%), HRMS
(EI) calcd. for C8H11NO (M+): 137.084064, found 137.083839.
3-Hydroxy-4-methylpyridine (7c). From substrate 3c (100 mg),
7c was isolated◦as a white solid (20 mg, 17%); mp 117–120 ◦C
(lit.,26 120–121 C). Spectroscopic data were in accordance with
those published in the literature.25a
7 D. R. Boyd, N. D. Sharma, N. I. Bowers, H. Dalton, M. D. Garrett,
J. S. Harrison and G. N. Sheldrake, submitted for publication.
8 (a) D. R. Boyd, N. D. Sharma, N. I. Bowers, R. Boyle, J. S. Harrison,
T. Bugg, K. Lee and D. T. Gibson, Org. Biomol. Chem., 2003, 1, 1298;
(b) D. R. Boyd, N. D. Sharma, P. J. Stevenson, J. Chima, D. J. Gray and
H. Dalton, Tetrahedron Lett., 1991, 32, 3887; (c) J. M. Brand, D. L.
Cruden, G. J. Zylstra and D. T. Gibson, Appl. Environ. Microbiol., 1992,
58, 3407; (d) D. R. Boyd, N. D. Sharma, N. I. Bowers, P. A. Goodrich,
2-Chloro-3-hydroxypyridine (4d). From substrate 1d (150 mg),
4d was isolated as a white solid (30 mg, 12%); mp 164–165 ◦C
2714 | Org. Biomol. Chem., 2006, 4, 2710–2715
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