Biphenyl-cis-diol chemistry to access enantiopure aryl-substituted organoiron complexes

Article abstract of DOI:10.1016/j.tetlet.2011.03.088

The endo face selectivity of the complexation of the biologically derived 3-phenyl-1,2-dihydroxycyclohexa-3,5-diene ligand has been proved by an X-ray crystallographic study of the enantiopure (1R,2S,3S) η⁴ tricarbonyliron complex, and the correlation between the absolute configuration of the complex and its circular dichroism curve has been established to provide a basis on which to assign absolute configurations in the synthetically important ['-(Ar)CCH-CHCH-']Fe(CO)₃ series.

Full text of DOI:10.1016/j.tetlet.2011.03.088

Tetrahedron Letters 52 (2011) 3547–3550
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Tetrahedron Letters
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Biphenyl-cis-diol chemistry to access enantiopure aryl-substituted
organoiron complexes
G. Richard Stephenson a, , Christopher E. Anson b, Graham J. Swinson a
⇑
a School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK
b Institut für Anorganische Chemie, Karlsruhe Institute of Technology, Engesserstr. Geb. 30.45, D-76128 Karlsruhe, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
The endo face selectivity of the complexation of the biologically derived 3-phenyl-1,2-dihydroxycyclo-
hexa-3,5-diene ligand has been proved by an X-ray crystallographic study of the enantiopure
(1R,2S,3S) g4 tricarbonyliron complex, and the correlation between the absolute configuration of the
complex and its circular dichroism curve has been established to provide a basis on which to assign abso-
lute configurations in the synthetically important [‘–(Ar)C@CH–CH@CH–’]Fe(CO)3 series.
Ó 2011 Elsevier Ltd. All rights reserved.
Received 27 January 2011
Revised 3 March 2011
Accepted 18 March 2011
Available online 24 March 2011
Keywords:
Organoiron
Biotransformation
Pseudomonas putida
Stereoselective complexation
Circular dichroism
Tricarbonyliron complexes have become well established as
stereocontrolled intermediates in organic synthesis,1 and recent
examples addressing significant target molecules2 exemplify the
power of this methodology with chiral (unsymmetrically substi-
tuted) dienyliron complexes. In the case of aryl substituents, our
syntheses of O-methyljoubertiamine3 and mesembrine,4 and for-
mal total syntheses of lycoramine5,6 and maritidine6,7 have estab-
lished the strategic importance8 of arylcyclohexadiene- and
cyclohexadienyliron complexes as chiral building blocks for alka-
loids. These synthetic routes are examples of 1,1 iterative
research groups to be an outstanding application of biotechnology
in organic synthesis, and the diol products have been adopted as
starting materials for a wide range of total syntheses, including
galanthamine,18 narciclasine,19 Oseltamivir (Tamiflu),20 perico-
sines,21 isoepiepoformin,22 bromoxone,23 nobilisitine A,24 amabi-
line,25 balanol,26 conduramine,27 codeine,28 brunsvigine,29
analogs of the antitumor agent COTC,30 pancratistatin and its ana-
logues,31 nangustine,32 carba-b-l-glucopyranose33 and sulfur-con-
taining cyclitols.34 Very recently, however, complementary
biotransformations using R. eutrophus B9 have provided35 an excel-
lent alternative access to tricarbonyliron complexes, and an inge-
nious rearrangement allows either enantiomer to be produced in
the 1-carboxymethyl series. The ease of handling of the R. eutro-
phus B9 system, which is well established36 as an entry to major
synthetic projects, combined with the successful manipulation of
the derived metal iron complexes will bring renewed attention to
this strategy for the enantioselective access to tricarbonyliron
diene complexes. Similarly for the dioxygenation of biphenyl,
recent (2007) developments37 using Burkholderia xenovarans
modified with the core segment of the Psueudomonas sp. Strain
{[g4]?[g5]+?[g4]?[g5]+?[g
4]} procedures9 which make re-
peated use of the metal control centre to build aryl-substituted
quaternary centres by two key C–C bond formation steps at the
same position on the working ligand.10 As part of this research,
we have addressed the issue of enantioselective access to organo-
iron complexes equipped with suitably placed leaving groups to al-
low repeated use of the tricarbonyliron moiety. The complexation
of biologically-derived11,12 1,2-dihydroxycyclohexa-3,5-diene li-
gands has proved to be a highly successful approach13 and has
been employed with substituted examples,14,15 including the 3-tri-
fluoromethyl-1,2-dihydroxycyclohexa-3,5-diene case,16,17 which
provided novel enantiopure g4 diene starting materials and g5
organoiron electrophiles containing CF3-substituted six-membered
rings. The use of mutant strains of Pseudomonas putida to gain
access to the required dienes is known through the work of many
B4-Magdeburg dioxygenase constitute
a significant advance.
Substituted biaryls have also been the subject of recent work using
Mycobacterium aromaticivorans JS19b1T38 and a hybrid dioxygen-
ase39 showing improved oxidation of polychlorobiphenyls. The
mutant Rhodocococcus sp. MB 72499 has similarly been shown40
to accumulate the 1,2-dihydrodiol from biphenyl.
In view of the growing importance of 1-arycyclohexadienyliron
⇑
Corresponding author. Tel.: +44 1 603 456161; fax: +44 1 603 259396.
E-mail address: g.r.stephenson@uea.ac.uk (G.R. Stephenson).
complexes as stereocontrolled electrophiles in alkaloid synthesis,3–7
0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.03.088

3548
G. R. Stephenson et al. / Tetrahedron Letters 52 (2011) 3547–3550
complexation of aryl-substituted cis-diols is an important objective.
The required biotransformation of biphenyl is known to be possible
with the widely used P. putida mutant strains with which we have
experienceinNorwich,13–16,41 soweturnedtothissystemtoconfirm
the configurational stability42 and chiroptical properties of the de-
rived diene complexes.
We describe here (Scheme 1) direct access to the synthetically
important9 aryl-substituted series, for the parent (aryl = phenyl)
case, establishing the endo stereochemistry by X-ray crystallogra-
phy, and extending our existing43 CD correlations to the enlarged
chromophore in the aryl-substituted structures.
It is well known that the efficiency of the biodioxygenation of
arenes (e.g., toluene44) is highly dependent on the quality of the
microbiological sample used to obtain the biocatalyst, and the pre-
cise conditions used for the biotransformation itself. As with our
work with phenetole,41 for the preparative scale biotransformation
experiments with biphenyl,45 a careful preliminary study of the
P. putida UV4 mutant46 was needed.47 A revised protocol, monitor-
ing at 300 nm instead of the usual 265 nm wavelength (biodioxy-
genation of toluene44) was adopted. The microorganism was
grown on plates as discrete colonies, of which two were chosen.48
After incubation overnight,49 biphenyl and ethanol were added and
the reaction was followed at 300 nm over 5 h (Fig. 1: the trace la-
belled ‘initial colony’ is an example from this experiment). A trial
preparative run was performed in five 2 l flasks each containing
400 ml of the culture medium. After centrifugation to separate cell
debris and unused biphenyl, and solvent extraction, only 40 mg of
product was obtained from a total of 5 g of biphenyl, and this
material was contaminated with 2- and 3-hydroxybiphenyl by-
products from elimination reactions of the cis-diol. To improve
this, a sequential selection procedure was employed, and the best
colony after four cycles (Fig. 1: diamond markers) was selected for
a repeated preparative scale run (20 l; 2 g crude product).
Figure 1. Examples of the changing activity of individual P. putida UV4 colonies
with biphenyl as the substrate, during a series of optimisation cycles where the
best-performing colonies are selected (activity is calculated by dividing OD300 by
the initial OD600 value to correct for variation in the quantity of bacteria present at
the start of the biotransformation).
Table 1
Results from complexation reactions using Fe2(CO)9 at room temperature in degassed
THF
Entry
Reactiona time (days)
Yieldb of the (+)-(1R,2S,3S)-diene
complex 2 (%)
1
2
3
3
5
7
16
44
40
a
0.2 g (1 mmol) of crude diene and 0.6 g (1.65 mmol) of Fe2(CO)9 were used.
Yield after chromatography, based on crude diene 1.
b
The material from the biotransformation experiments was com-
plexed (Table 1) by stirring in THF with an excess of diiron nonac-
arbonyl and purified by chromatography. A five-day reaction time
gave the best results. The product crystallised in the chiral P212121
space group, and the final value of the Flack parameter
[v = 0.02(3)] confirmed that the (1R,2S,3S)-stereoisomer had been
obtained. The relative stereochemistry (Fig. 2) shows the tricarbon-
yliron group to be on the same face of the ligand as the cis diol, and
the aromatic ring is twisted out of the plane of the diene by
51.5(2)°. The g4 bonding to the diene prevents distortion, and
forces the pair of OH groups, O(25) and O(26), into an eclipsed po-
sition. H(25) forms an intramolecular hydrogen bond to O(26),
while H(26) makes a hydrogen bond to O(25) of the molecule at
{x À 1/2, Ày + 3/2, Àz + 1}, resulting in chains of molecules running
parallel to the a-axis. As is normal in g4 tricarbonyliron struc-
tures,50 one of the CO ligands lies below the saturated section of
the ring, in this case adopting a conformation that places it
Figure 2. ORTEP plot (50% ellipsoids) of the structure of (+)-(1R,2S,3S)-tricar-
bonyl[(3,4,5,6- )-3-phenyl-1,2-dihydroxycyclohexa-3,5-diene]iron (2).
g
between the two OH groups. The Fe(CO)3 tripod is displaced
slightly away from the phenyl substituent.
Scheme 1. Biotransformation and complexation of biphenyl.

G. R. Stephenson et al. / Tetrahedron Letters 52 (2011) 3547–3550
3549
on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK,
(fax: +44 (0)1223 336033 or e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgements
We thank Dr. A. Coddington, Mrs. L. Flegg and the School of Bio-
logical Sciences at UEA for assistance with biotransformation
experiments, the Institute of Food Research, Norwich for access
to their CD spectrometer, ICI for a gift of the Pseudomonas putida
culture UV4 (NCIB 11680), the University of East Anglia and the
EPSRC for financial support, and the EPSRC Mass Spectrometry
Centre at the University of Wales, Swansea for high resolution
mass spectrometric measurements.
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3550
G. R. Stephenson et al. / Tetrahedron Letters 52 (2011) 3547–3550
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47. As a starting point, typical growth conditions were based on Eur. Pat. 0 076 60
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described in detail for the biotransformation of chlorobenzene. see Ref. 12).
48. The quality of each colony was assessed using duplicate plates and the ‘indigo
test’ (for a version of this procedure, see Ref. 14; in our case indole was
included in the minimal salt medium).
49. Incubation overnight to an OD600 value of 0.45.
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diene]iron (2) purified by chromatography on silica eluted with petroleum
ether/Et2O (gradient 100/0?50/50): mp 124 °C (decomp); Found: C, 54.79; H,
3.68 (C15H12FeO5 requires C, 54.88; H, 3.66); mmax (CH2Cl2, cmÀ1) 3057, 2054,
1989; dH (CDCl3, 270 MHz) 7.4–7.1 (5H, multiplet, Harom), 5.55 (1H, d, J 4 Hz,
H-4), 5.25 (1H, dd, J 6.5, 4 Hz, H-5), 3.88 (1H, br s, 2-H), 3.65 (1H, t, J 5.5 Hz,
H-1), 3.11 (1H, d, J 7 Hz, HO-2), 3.01 (1H, d, J 5.5 Hz, HO-1), 2.51 (1H, d, J 4.5 Hz,
H-6); dC (CDCl3, 67.5 MHz) 210.8 (CO); 141.7, 130.4, 128.2, 127.4 (Carom), 87.0
(C-4), 86.8 (C-3); 81.2 (C-5), 70.8 (C-6), 68.5 (C-2), 66.6 (C-1); m/z 300 (M+-CO,
0.2%), 272 (M+-2CO, 1) 230 (M+-2CO-2OH, 0.3), 210 (M+-3CO-2OH, 0.9), 170
(3), 154 (M+-Fe(CO)3-2OH, 100), 115 (4), 76 (63). Crystal data 2: C15H12FeO5,
M = 328.10, orthorhombic, P212121, a = 8.965(4), b = 11.283(5), c = 14.204(6) Å,
V = 1436.8(11) Å3, T = 295(2) K, Z = 4, F(0 0 0) = 672,
l ; 3133
= 1.067 mmÀ1
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Commun. 2011, 215–217; For R. eutrophus B9, see: Reiner, A. M.; Hegeman, G.
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data, 3018 unique (Rint = 0.0606), wR2 = 0.1050, S = 1.009 (all data),
R1 = 0.0429 (2642 with I P 2r(I)), Flack parameter v = 0.02(3), final diff.
peak/hole +0.27/À0.49 eÅ-3
.
52. Howard, P. W.; Stephenson, G. R.; Taylor, S. C. Chem. Commun. 1990, 1182–
1184.