Chem. Biodiversity 2016, 13, 1 – 7
7
The products obtained with deoxycholic acid 1b are
shown below:
Pseudomonas prosekii ECS1, after PLC (AcOEt/cy-
clohexane/AcOH 70:30:2) afforded:
2a-Hydroxy-3-oxo-5b-cholan-24-oic Acid (2b) [27].
REFERENCES
[
1] D. Kritchevsky, in ‘Chemistry of Bile Acids. The Bile Acids –
Chemistry, Physiology and Metabolism’, Eds. P. P. Nair and
D. Kritchevsky, Plenum Press, New York-London, 1971, Vol. 1,
Chapt. 1, p. 1.
1
[
[
[
2] L. F. Fieser, S. Rajagopalan, J. Am. Chem. Soc. 1950, 72, 5530.
3] A. F. Hofmann, Acta Chem. Scand. 1963, 14, 17.
4] O. Bortolini, A. Medici, S. Poli, Steroids 1997, 62, 564.
1
Yield: 20%. H-NMR selected data: 0.75 (s, 3 H); 1.01 (d,
J = 7, 3 H); 1.02 (s, 3 H); 4.05 (s, 1 H).
1
Yield: 22%. H-NMR (CDCl ) selected data: 0.75 (s, 3
2a-Hydroxy-3-oxochol-4-en-24-oic Acid (3b) [30].
1
[5] G. Fantin, S. Ferrarini, A. Medici, P. Pedrini, S. Poli, Tetrahe-
dron 1998, 54, 1937.
3
[
6] A. Medici, P. Pedrini, E. Bianchini, G. Fantin, A. Guerrini, B.
Natalini, R. Pellicciari, Steroids 2002, 67, 51.
H); 0.95 (d, J = 7, 3 H); 1.15 (s, 3 H); 4.05 (br. s, 1 H);
5
.78 (s, 1 H).
Pseudomonas mendocina ECS10, after CC (cyclohex-
[
7] M. Dean, C. Cervellati, E. Casanova, M. Squerzanti, V. Lan-
zara, A. Medici, P. Polverino De Laureto, C. M. Bergamini,
Appl. Environ. Microbiol. 2002, 68, 3126.
ane/AcOEt/AcOH 60:40:1), afforded 3b. Yield: 95%.
Rhodococcus erythropolis ECS25, after 24 h biotrans-
formation (0.2 g of 1b), further 24 h biotransformation
[8] P. Pedrini, E. Andreotti, M. Dean, G. Fantin, P. P. Giovannini,
A. Guerrini, Steroids 2006, 71, 189.
[
9] P. P. Giovannini, A. Grandini, D. Perrone, P. Pedrini, G. Fan-
tin, M. Fogagnolo, Steroids 2008, 73, 1385.
(
0.4 g of 1b), and CC (cyclohexane/AcOEt/AcOH
0:40:1), afforded:
6
[
[
10] T. Eggert, D. Bakonyi, W. Hummel, J. Biotech. 2014, 191, 11.
11] S. Hayakawa, Z. Allg. Mikrobiol. 1982, 22, 309.
[12] B. Philipp, Appl. Microbiol. Biotechnol. 2011, 89, 903.
[13] Y. Hu, R. van der Geize, G. S. Besra, S. S. Gurcha, A. Liu,
M. Rohde, M. Singh, A. Coates, Mol. Microbiol. 2010, 75, 107.
2
3
b. Yield: 61%. Overall yield 39%.
,12-Dioxo-5b-cholan-24-oic Acid (7b) [27]. Yield:
1
3
0%. Overall yield: 20%. H-NMR (CDCl ) selected
3
data: 0.82 (d, J = 7, 3 H); 1.05 (s, 3 H); 1.10 (s, 3 H).
Pseudomonas fragi ECS9, after PLC (AcOEt/cyclo-
hexane/AcOH 70:30:2), afforded 12a-hydroxy-3-oxo-
[
14] J. K. Capyk, I. D’Angelo, N. C. Strynadka, L. D. Eltis, J. Biol.
Chem. 2009, 284, 9937.
[
15] M. Petrusma, L. Dijkhuizen, R. van der Geize, Appl. Environ.
Microbiol. 2009, 75, 5300.
[16] R. J. Park, Steroids 1984, 44, 175.
pregna-1,4-diene-20-carboxylic acid (= bendigole A; 8b)
1
18]. Yield: 80%. H-NMR selected data: 0.80 (s, 3 H);
[
1
.23 (d, J = 6, 3 H); 1.25 (s, 3 H); 3.95 (s, 1 H); 6.05 (s, 1
[17] S. Costa, P. P. Giovannini, G. Fantin, A. Medici, P. Pedrini,
Helv. Chim. Acta 2013, 96, 1062.
H); 6.21 (dd, J = 10, 1, 1 H); 7.11 (d, J = 10, 1 H).
The products obtained with hyodeoxycholic acid 1c
are shown below:
[
18] K. Schneider, E. Graf, E. Irran, G. Nicholson, F. M. Stainsby,
M. Goodfellow, S. A. Borden, S. Keller, R. D. S u€ ssmuth, H.-P.
Fiedler, J. Antibiot. 2008, 61, 356.
Pseudomonas mendocina ECS10, after CC (cyclohex-
ane/AcOEt/AcOH 60:40:1), afforded 6a-hydroxy-3-oxo-
5
[
[
[
[
19] F. M. Stainsby, J. Soddell, R. Seviour, J. Upton, M. Goodfellow,
Water Sci. Technol. 2002, 46, 81.
20] L. Simmons, K. Kaufmann, R. Garcia, G. Schw €a r, V. Huch, R.
M u€ ller, Bioorg. Med. Chem. 2011, 19, 6570.
21] K. Kaufmann, L. Simmons, J. Herrmann, G. Schw €a r, N. Luniak,
R. M u€ ller, Biotechnol. Lett. 2013, 35, 11.
22] S. Costa, P. P. Giovannini, G. Fantin, A. Medici, P. Pedrini,
Helv. Chim. Acta 2013, 96, 2124.
[23] ICE (Industria Chimica Emiliana) extracts, and purifies bile acids
1
b-cholan-24-oic acid (2c) [27]. Yield: 50%. H-NMR
(
CDCl ) selected data: 0.68 (s, 3 H); 0.95 (d, J = 6, 3 H);
3
1
.00 (s, 3 H); 4.15 (m, 1 H).
Pseudomonas prosekii ECS1, after PLC (AcOEt/cy-
clohexane/AcOH 70:30:2), afforded:
a-Hydroxy-3-oxochola-1,4-dien-24-oic
6
Acid
= Bendigole G; 5c) [31]. Yield: 13%. H-NMR selected
data: 0.80 (s, 3 H); 0.98 (d, J = 7, 3 H); 1.25 (s, 3 H);
.42 – 4.53 (m, 1 H); 6.22 (dd, J = 10, 2.1, 1 H); 6.42 (s, 1
H); 7.25 (d, J = 10, 1 H).
a-Hydroxy-3-oxopregna-1,4-diene-20-carboxylic Acid
1
from raw materials (ox and pig bile), http://www.iceitaly.com/.
(
[
[
24] U. Edwards, T. Rogall, H. Bl o€ cker, M. Emde, E. C. B o€ ttger,
Nucleic Acids Res. 1989, 17, 7843.
25] A. M. Rodas, S. Ferrer, I. Pardo, Syst. Appl. Microbiol. 2003,
4
2
6, 412.
6
[26] O. S. Kim, Y. J. Cho, K. Lee, S. H. Yoon, M. Kim, H. Na, S.
C. Park, Y. S. Jeon, J. H. Lee, H. Yi, S. Won, J. Chun, Int. J.
Syst. Evol. Microbiol. 2012, 62, 716.
1
(
= Bendigole H; 8c) [22]. Yield: 20%. H-NMR selected
data: 0.81 (s, 3 H); 1.20 (d, J = 6.5, 3 H); 1.25 (s, 3 H);
.4 – 4.5 (m, 1 H); 6.22 (dd, J = 10, 2.1, 1 H); 6.41 (s, 1
[
27] S. Barnes, D. N. Kirk, in ‘Methods and Applications. The Bile
Acids – Chemistry, Phisiology and Metabolism’, Eds. P. P. Nair
and D. Kritchevsky, Plenum Press, New York-London, 1988, Vol.
4
H); 7.25 (d, J = 10, 1 H).
Rhodococcus erythropolis ECS12, after CC (cyclohex-
ane/AcOEt/AcOH 50:50:1), afforded: bendigole H (8c).
Yield: 16%.
4
, Chapt. 3.
[28] E. Mukhrjee, S. Banerjee, S. B. Mahato, Steroids 1993, 58, 484.
[29] K. Tamaki, J. Biochem. 1958, 45, 693.
[
30] R. A. Leppik, Steroids 1983, 41, 475.
[31] R. W. Owen, R. F. Bilton, J. Steroid Biochem. 1983, 19, 1355.
6a-Hydroxy-3-oxo-23,24-dinor-5b-cholan-22-oic Acid
9c) [17]. Yield: 66%. H-NMR (CDCl ) selected data:
1
(
3
0
4
.71 (s, 3 H); 1.02 (s, 3 H); 1.25 (d, J = 6.2, 3 H);
.05 – 4.18 (m, 1 H).
Received September 18, 2015
Accepted January 25, 2016
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