cis-(1S,2R)-3-tert-Butyl-6-methylcyclohexa-3,5-diene-1,2-diol
11C
1%), 164 (41), 146 (28), 49 (100); CD λ 286 nm (∆ε 0.439), 208
nm (∆ε Ϫ3.791); >98% ee (Method B).
From substrate 10C (5%), unstable solid; mp 56–60 ЊC
(decomp.); [α]D ϩ94 (c 0.4, MeOH) (Found: Mϩ, 182.1304.
C11H18O2 requires M, 182.1307); m/z 182 (Mϩ, 10%), 122 (100).
cis-(1S,2R)-3-[(S)-(1Ј-Hydroxy-2Ј-methylallyl]cyclohexa-3,5-
diene-1,2-diol 4FЈ
From substrate 1F (5%), oil; [α]D Ϫ8 (c 0.3, MeOH); MS and
CD data were virtually identical with those found for diastereo-
isomer 4F; >98% ee (Method B).
cis-(1S,2R)-3-(Hydroxymethyl)cyclohexa-3,5-diene-1,2-diol 4A
From substrates 1A (4%), 1J (15%), 3J (18%) and 5 (8%), oil;
[α]D ϩ35 (c 0.1, MeOH) (Found: Mϩ Ϫ 18, 124.0525. C7H8O2
requires m/z, 124.0524); m/z 142 (Mϩ, <1%), 124 (10); >98% ee
(Method B).
Acknowledgements
We thank the BBRSC (N. D. S.), the European Social Fund
(J. S. H.) and DENI (N. I. B., J. D.) for funding. We also wish to
acknowledge the valuable assistance given by Mr David Clarke
and Ms Petra Kirsch (Mannheim) with the biotransformation
studies.
cis-(1S,2R)-3-[(R)-1Ј-Hydroxyethyl]cyclohexa-3,5-diene-1,2-
diol 4B
From substrate 1B (5%), (R)-3B (20%), oil; [α]D ϩ55 (c 0.57,
MeOH) (lit.,18 [α]D ϩ55); m/z 154 (Mϩ, <1%), 95 (100); CD
λ 282 nm (∆ε 0.421), 222 nm (∆ε Ϫ4.233); >98% ee (Method
B).
References
1 L. Que and R. Y. N. Ho, Chem. Rev., 1996, 96, 2607.
2 D. T. Gibson, Crit. Rev. Microbiol., 1971, 199.
3 D. T. Gibson and V. Subramanian, in Microbial Degradation of
Organic Compounds, ed. D. T. Gibson, Marcel Dekker Inc.,
New York, 1984, p. 181.
4 D. T. Gibson, G. J. Zylstra and S. Chauhan, in Pseudomonas:
Biotransformations, Pathenogenesis and Evolving Biochemistry,
ed. S. Silver, A. M. Charkraberthy, B. Iglewski and S. Kaplan,
American Society for Microbiology, 1990, ch. 13, p. 121.
5 S. M. Resnick, K. Lee and D. T. Gibson, J. Ind. Microbiol., 1996, 17,
438.
6 D. R. Boyd and G. N. Sheldrake, Nat. Prod. Rep., 1998, 15, 309.
7 T. Hudlicky, D. Gonzalez and D. T. Gibson, Aldrichim. Acta, 1999,
32, 35.
8 L. P. Wackett, L. D. Kwart and D. T. Gibson, Biochemistry, 1988, 27,
1360.
9 J. M. Brand, D. L. Cruden, G. J. Zylstra and D. T. Gibson, Appl.
Environ. Microbiol., 1992, 58, 3407.
10 D. R. Boyd, N. D. Sharma, P. J. Stevenson, J. Chima, D. J. Gray and
H. Dalton, Tetrahedron Lett., 1991, 32, 3887.
11 D. R. Boyd, N. D. Sharma, N. I. Bowers, P. A. Goodrich, M. R.
Groocock, A. J. Blacker, D. A. Clarke, T. Howard and H. Dalton,
Tetrahedron: Asymmetry, 1996, 7, 1559.
cis-(1S,2R)-3-[(S)-1Ј-Hydroxyethyl]cyclohexa-3,5-diene-1,2-diol
4BЈ
From substrate (S)-3B (8%), unstable oil; [α]D ϩ5 (c 0.81,
MeOH) (lit.,18 [α]D ϩ 6); m/z 154 (Mϩ, <1%), 43 (100);
CD λ 285 nm (∆ε 0.3206), 222 nm (∆ε Ϫ4.030); >98% ee
(Method B).
cis-(1S,2R)-3-[(R)-1Ј-Hydroxypropyl]cyclohexa-3,5-diene-1,2-
diol 4C
From substrate 1C (26%) and (R)-3C (8%), oil; [α]D ϩ52 (c 0.95,
MeOH) (Found: Mϩ, 170.0941. C9H14O3 requires M, 170.0943);
m/z 170 (Mϩ, 10%), 152 (29), 95 (100); CD λ 282 nm (∆ε 0.421),
222 nm (∆ε Ϫ4.233); >98% ee (Method B).
cis-(1S,2R)-3-[(S)-1Ј-Hydroxypropyl]cyclohexa-3,5-diene-1,2-
diol 4CЈ
From substrate (S)-3C (53%), mp 98–104 ЊC (decomp.) (from
CHCl3–Et2O); [α]D ϩ 16 (c 0.41, MeOH) (Found: Mϩ,
170.0944); m/z 170 (Mϩ, 10%), 152 (29), 95 (100); CD λ 284 nm
(∆ε 0.321), 222 nm (∆ε Ϫ4.030); >98% ee (Method B).
12 N. I. Bowers, D. R. Boyd, N. D. Sharma, P. A. Goodrich, M. R.
Groocock, A. J. Blacker, P. Goode and H. Dalton, J. Chem. Soc.,
Perkin Trans. 1, 1999, 1453.
13 K. Lee, J. M. Brand and D. T. Gibson, Biochem. Biophys. Res.
Commun., 1995, 212, 9.
cis-(1S,2R)-3-[(R)-1Ј-Hydroxybutyl]cyclohexa-3,5-diene-1,2-
diol 4D
14 C. C. R. Allen, D. R. Boyd, H. Dalton, N. D. Sharma, S. A.
Haughey, R. A. S. McMordie, B. T. McMurray, K. Sproule and
G. N. Sheldrake, J. Chem. Soc., Chem. Commun., 1995, 119.
15 D. R. Boyd, N. D. Sharma, S. A. Haughey, M. A. Kennedy, B. T.
McMurray, G. N. Sheldrake, C. C. R. Allen, H. Dalton and
K. Sproule, J. Chem. Soc., Perkin Trans. 1, 1998, 1929.
16 D. R. Boyd, N. D. Sharma, M. Groocock, J. F. Malone and H.
Dalton, J. Chem. Soc., Perkin Trans. 1, 1997, 1897.
17 D. R. Boyd, N. D. Sharma, N. A. Kerley, R. A. S. McMordie,
G. N. Sheldrake, P. Williams and H. Dalton, J. Chem. Soc., Perkin
Trans. 1, 1996, 67.
From substrate 1D (9%) and (R)-3D (31%), oil; [α]D ϩ 58 (c
0.49, MeOH) (Found: Mϩ, 184.2343. C10H16O3 requires M,
184.2346); m/z 184 (Mϩ, 15%), 134 (47), 107 (100); CD λ 280
nm (∆ε 0.407), 222 nm (∆ε Ϫ4.462); >98% ee (Method B).
cis-(1S,2R)-3-[(S)-1Ј-Hydroxybutyl]cyclohexa-3,5-diene-1,2-
diol 4DЈ
From substrate (S)-3D (23%), mp 59–63 ЊC (from CHCl3–
Et2O); [α]D ϩ3 (c 0.42, MeOH) (Found: Mϩ, 184.2349; m/z 184
(Mϩ, 15%), 134 (47%), 107 (100); CD λ 283 nm (∆ε 0.333), 222
nm (∆ε Ϫ4.393); >98% ee (Method B).
18 D. T. Gibson, B. Gschwendt, W. K. Yeh and V. M. Kobal,
Biochemistry, 1973, 12, 1520.
19 R. E. Cripps, P. W. Trudgill and J. G. Whatley, Eur. J. Biochem.,
1978, 86, 175.
20 D. R. Boyd, N. D. Sharma, B. Byrne, M. V. Hand, J. F. Malone,
G. N. Sheldrake, J. Blacker and H. Dalton, J. Chem. Soc., Perkin
Trans. 1, 1998, 1935.
21 S. M. Resnick, D. S. Torok and D. T. Gibson, J. Org. Chem., 1995,
60, 3546.
22 M. V. Hand, S. Kelly, R. A. More O’Ferrall, S. N. Rao, N. D.
Sharma, G. N. Sheldrake and H. Dalton, J. Chem. Soc., Chem.
Commun., 1994, 313.
23 D. R. Boyd, N. D. Sharma, I. N. Brannigan, D. A. Clark, H. Dalton,
S. A. Haughey and J. F. Malone, Chem. Commun., 1996, 2361.
24 D. R. Boyd, N. D. Sharma, M. V. Hand, M. R. Groocock,
N. A. Kerley, H. Dalton, J. Chima and G. N. Sheldrake, J. Chem.
Soc., Chem. Commun., 1993, 974.
cis-(1S,2R)-3-[(R)-(1Ј-Hydroxyallyl]cyclohexa-3,5-diene-1,2-
diol 4E
From substrate 1E (15%), oil; [α]D Ϫ9 (c 1.6, MeOH) (Found:
Mϩ, 168.0787. C9H12O3 requires M, 168.0786); m/z 168 (Mϩ,
13%), 150 (57), 133 (74), 94 (100); CD λ 292 nm (∆ε 0.1839), 256
nm (∆ε Ϫ0.7936), 216 nm (∆ε Ϫ6.452); >98% ee (Method B).
cis-(1S,2R)-3-[(R)-(1Ј-Hydroxy-2Ј-methylallyl]cyclohexa-3,5-
diene-1,2-diol 4F
From substrate 1F (18%), oil; [α]D Ϫ13 (c 0.6, CHCl3) (Found:
Mϩ, 182.0940. C10H14O3 requires M, 182.0943); m/z 182 (Mϩ,
25 D. T. Gibson, M. Hensley, H. Yoshioka and T. J. Mabry,
Biochemistry, 1970, 9, 1626.
1350
J. Chem. Soc., Perkin Trans. 1, 2000, 1345–1350