H. Antunes et al. / Tetrahedron: Asymmetry 15 (2004) 2615–2620
2619
(film) 3407, 3075, 3010, 2899, 1610, 1504, 1443, 1245,
1037, 981, 863, 816, 739cmꢀ1 1H NMR (300MHz,
52.1, 78.6, 101.1, 107.3, 108.0, 120.6, 131.5, 147.5,
147.8; MS m/z (rel int. %): 324 (M+, 3), 151 (100), 135
(8), 123 (9), 93 (50), 77 (8), 65 (25), 63 (13).
;
CDCl3): d 2.66 (br s, 1H), 3.58–3.70 (m, 2H), 4.81 (d,
1H, J = 5.5Hz), 5.96 (s, 2H), 6.77–6.89 (m, 3H);
13C NMR (75MHz, CDCl3): d 76.3, 78.5, 101.1, 107.2,
108.0, 120.8, 130.9, 147.8, 147.9; MS m/z (rel int. %):
202–200 (M+, 3–10), 182 (2), 151 (76), 135 (7), 123
(17), 93 (100), 77 (17), 65 (93).
Acknowledgements
We thank FAPESP and CNPq for financial support.
4.4.1. (R)-1-(1,3-Benzodioxol-5-yl)-2-bromo-1-ethanol 5c.
When 4c (0.485g, 2mmol) was subjected to the general
procedure for bioreduction, the isolated product was
References
25
5c (0.280g, 57%) as oil; ½a ¼ ꢀ33:2 (c 1, CHCl3),
1. (a) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev.
1996, 96, 835–875; (b) Kanerva, L. T. Acta Chem. Scand.
1996, 50, 234–242; (c) Armstrong, D. W.; He, L.; Yu, T.;
Lee, J. T.; Liu, Y. Tetrahedron: Asymmetry 1999, 10, 37–
60; (d) Bergmeier, S. C. Tetrahedron 2000, 56, 2561–2576;
(e) Nakamura, Y.; Takeuchi, S.; Okumura, K.; Ohgo, Y.
Tetrahedron 2001, 57, 5565–5571; (f) Xu, D. C.; Du, D.
M.; Ji, N.; Wang, I. V.; Hua, W. T. Synth. Commun. 2003,
33, 2563–2574; (g) Gomez, M.; Philipport, K.; Colliere, V.;
Lecante, P.; Muller, G.; Chaudret, B. New J. Chem. 2003,
27, 114–120.
D
ee >99% determined by GC using a chiral column; IR
(film) 3421, 3074, 2961, 2896, 1503, 1487, 1247, 1055,
1
929, 814cmꢀ1; H NMR (300MHz, CDCl3): d 2.78 (br
s, 1H), 3.44–3.58 (m, 2H), 4.80 (dd, 1H, J = 8.8Hz,
J = 3.0Hz), 5.95 (s, 2H), 6.76–6.86 (m, 3H); 13C NMR
(75MHz, CDCl3): d 40.0, 73.5, 101.0, 106.2, 108.1,
119.4, 134.1, 147.3, 147.6; MS m/z (rel int. %): 246–
244 (M+, 7–7), 151 (100), 135 (8), 123 (13), 93 (82), 77
(14), 65 (51).
2. (a) Carvalho, M.; Okamoto, M. T.; Moran, P. J. S.;
Rodrigues, J. A. R. Tetrahedron 1991, 47, 2073–2080; (b)
Fardelone, L. C.; Rodrigues, J. A. R.; Moran, P. J. S.
Arkivoc 2003, X, 404–410.
3. (a) Moran, P. J. S.; Rodrigues, J. A. R.; Joekes, I.;
Brenelli, E. C. S.; Leite, R. A. Biocatalysis 1994, 9, 321; (b)
Siqueira Filho, E. P.; Rodrigues, J. A. R.; Moran, P. J. S.
J. Mol. Catal. B: Enzym. 2001, 15, 23–28.
4. Brenelli, E. C. S.; Carvalho, M.; Okubo, M. T.; Marques,
M.; Moran, P. J. S.; Rodrigues, J. A. R.; Sorrilha, E. P. M.
Indian J. Chem. 1992, 31B, 821–823.
5. Barbieri, C.; Bossi, L.; DÔArrigo, P.; Fantoni, G. P.; Servi,
S. J. Mol. Catal. B: Enzym. 2000, 11, 415–421.
4.4.2. (R)-2-Azido-1-(1,3-benzodioxol-5-yl)-1-ethanol 5d.
When 4d (0.410g, 2mmol) was subjected to the general
procedure for bioreduction, the product isolated was
25
5d (0.410g, 99%) as oil; ½a ¼ ꢀ70:0 (c 1, CHCl3);
D
ee >99% determined by GC using a chiral column; IR
(film) 3406, 2973, 2905, 2102, 1503, 1488, 1443, 1248,
1036, 930, 812cmꢀ1 1H NMR (300MHz, CDCl3): d
;
2.40 (br s, 1H), 3.41 (dd, 2H, J = 4.2Hz, J = 12.4Hz),
3.45 (dd, 2H, J = 8.0Hz, J = 12.4Hz), 4.77 (q, 1H,
J = 4.2Hz, J = 8.0Hz), 5.95 (s, 2H), 6,77 (m, 2H), 6.86
(m, 1H); 13C NMR (75MHz, CDCl3): d 57.9, 73.1,
100.9, 106.1, 108.1, 119.2, 134.2, 147.2, 147.6; MS m/z
(rel int. %): 207 (M+, 3), 179 (6), 151 (51), 150 (43),
149 (100), 135 (2), 121 (33), 93 (45), 65 (41), 63 (27).
6. Romero, M. C.; Hammer, E.; Cazau, M. C.; Arambarri,
A. M. Environ. Pollut. 2002, 118, 379–382.
7. (a) Smit, M. S. Trends Biotechnol. 2004, 22, 123–129; (b)
Yeates, C. A.; van Dyk, M. S.; Botes, A. L.; Breytenbach,
J. C.; Krieg, H. M. Biotechnol. Lett. 2003, 25, 675–680; (c)
Kronenburg, N. A. E.; Bont, J. A. M. Enzyme Microb.
Technol. 2001, 28, 210–217; (d) Cagnon, J. R.; Porto, A. L.
M.; Marsaioli, A. J.; Manfio, G. P.; Eguchi, S. Y.
Chemosphere 1999, 38, 2237–2242.
4.4.3. (R)-1-(1,3-Benzodioxol-5-yl)-2,2-dichloro-1-ethanol
5e. When 4e (0.465g, 2mmol) was subjected to the gen-
eral procedure for bioreduction, the isolated product
25
was 5e (0.415g, 88%) as oil; ½a ¼ ꢀ19:0 (c 1, CHCl3);
D
8. Rubio, M. C.; Runco, R.; Navarro, A. R. Phytochemistry
2002, 61, 605–609.
ee = 76% determined by GC using a chiral column; IR
(film) 3470, 2994, 2899, 1610, 1504, 1490, 1446, 1250,
ˆ
9. Cabon, O.; Larcheveque, M.; Buisson, D.; Azerad, R.
Tetrahedron Lett. 1992, 33, 7337–7340.
1039, 927, 864, 782, 746, 716cmꢀ1
;
1H NMR
(300MHz, CDCl3): d 3.17 (br s, 1H), 4.84 (d, 1H,
J = 5.5Hz), 5.72(d, 1H, J = 5.5Hz), 5.95 (s, 2H),
6.77–6.90 (m, 3H); 13C NMR (75MHz, CDCl3): d
76.2, 78.4, 101.1, 107.2, 107.9, 120.8, 131.0, 147.5,
147.7; MS m/z (rel int. %): 236–234 (M+, 4–6), 151
(100), 135 (5), 123 (19), 93 (91), 77 (14), 65 (70), 63 (23).
10. Brzezinska-Rodak, M.; Zymanczyk-Duda, E.; Kafarski,
P.; Lejczak, B. Biotechnol. Prog. 2002, 18, 1287–1291.
11. Goswami, A.; Mirfakhrae, K. D.; Totleben, M. J.;
Swaminathan, S.; Patel, R. N. J. Ind. Microbiol. Biotech.
2001, 26, 259–261.
12. Patel, R. N.; Goswami, A.; Chu, L.; Donovan, M. J.;
Nanduri, V.; Golberg, S.; Johnston, R.; Siva, P. J.;
Nielsen, B.; Fan, J.; He, W.; Shi, Z.; Wang, K. Y.; Eiring,
R.; Cazzulino, D.; Singh, A.; Mueller, R. Tetrahedron:
Asymmetry 2004, 15, 1247–1258.
13. Homann, J. M.; Vail, R. B.; Previde, E.; Tamarez, M.;
Morgan, B.; Dodds, D. R.; Zaks, A. Tetrahedron 2004, 60,
789–797.
14. Conceic¸a˜o, G. J. A.; Moran, P. J. S.; Rodrigues, J. A. R.
Arkivoc 2003, X, 500–506.
4.4.4. (R)-1-(1,3-Benzodioxol-5-yl)-2,2-dibromo-1-etha-
nol 5f. When 4f (0.64g, 2mmol) was subjected to the
general procedure for bioreduction, the isolated product
25
was 5f (0.60g, 92%) as oil; ½a ¼ ꢀ11:7 (c 1, CHCl3);
D
ee = 72% determined by GC using a chiral column; IR
(film) 3421, 3074, 2961, 2896, 1607, 1503, 1487, 1444,
1247, 1010, 929, 814, 796, 762, 719cmꢀ1 1H NMR
;
15. (a) Hayashi, T.; Katsumura, A.; Konishi, M.; Kumada,
M. Tetrahedron Lett. 1979, 20, 425–428; (b) Corey, E. J.;
Link, J. O. Tetrahedron Lett. 1990, 31, 601–604; (c) Hong,
Y.; Gao, Y.; Nie, X.; Zepp, C. M. Tetrahedron Lett. 1994,
(300MHz, CDCl3): d 2.94 (br s, 1H), 4.94 (d, 1H,
J = 5.5Hz), 5.80 (d, 1H, J = 5.5Hz), 5.98 (s, 2H),
6.78–6.93 (m, 3H); 13C NMR (75MHz, CDCl3): d