Application of chromium-arene complexes in the organic synthesis. Efficient synthesis of stilbene phytoalexins

Article abstract of DOI:10.1023/B:RUCO.0000022800.70211.7d

Planar chiral η⁶-arene-Cr(CO)₃ complexes represent highly valuable building blocks for the diastereo- and enantioselective synthesis. Their employment as synthons offer new and unique opportunities for the stereoselective multistep synthesis of complex natural products. The strategy of novel efficient synthesis of stilbene phytoalexins was based on arene chromium chemistry and the chemical and stereochemical effects of the metal unit on the reactivity of complexed arene ligand and stereochemical features of such compounds. Two variants for the construction of the trans-stilbene and diarylethanol framework via facilitated benzylic deprotonation of an η⁶benzene-Cr(CO)₃ complex and subsequent coupling with para-anisaldehyde in an aldol-type or a Wittig-Horner reaction were suggested.

Full text of DOI:10.1023/B:RUCO.0000022800.70211.7d

Russian Journal of Coordination Chemistry, Vol. 30, No. 4, 2004, pp. 252–261. From Koordinatsionnaya Khimiya, Vol. 30, No. 4, 2004, pp. 271–280.
Original English Text Copyright © 2004 by Polunin, Schmalz.
Application of Chromium-Arene Complexes in the Organic
Synthesis. Efficient Synthesis of Stilbene Phytoalexins1
K. E. Polunin* and H.-G. Schmalz**
*
Institute of Physical Chemistry, Russian Academy of Sciences, Moscow, Russia
*
*Institute of Organic Chemistry, University of Cologne, D-50939, Koeln, Germany
e-mail: polunina@phyche.ac.ru, schmalz@uni-koeln.de
Received September 1, 2003
6
Abstract—Planar chiral η -arene-Cr(CO) complexes represent highly valuable building blocks for the dias-
3
tereo- and enantioselective synthesis. Their employment as synthons offer new and unique opportunities for the
stereoselective multistep synthesis of complex natural products. The strategy of novel efficient synthesis of stil-
bene phytoalexins was based on arene chromium chemistry and the chemical and stereochemical effects of the
metal unit on the reactivity of complexed arene ligand and stereochemical features of such compounds. Two
variants for the construction of the trans-stilbene and diarylethanol framework via facilitated benzylic depro-
6
tonation of an η -benzene-Cr(CO) complex and subsequent coupling with para-anisaldehyde in an aldol-type
3
or a Wittig–Horner reaction were suggested.
π-Complexes of transition metals with unsaturated boiling solvent [2]. The complexation can also be
and aromatic ligands are characterized by high lability. accomplished under much milder conditions using pyr-
Among the numerous types of transition metal arene role- or naphthalene-Cr(CO) for the transfer of the
3
6
complexes, only η -benzene-Cr(CO) derivatives have Cr(CO) fragment [3–5]. Solutions of chromium arene
3
3
received broad recognition by synthetic chemists. complexes are usually sensitive toward oxidation, par-
Chromium-arene complexes have frequently proven ticularly, in light. This sensitivity can be utilized for
their value for organic synthesis; they are not expen- decomplexation reactions under mild oxidative condi-
4
+
sive, easy to produce, and are convenient for synthetic
work. The chemistry of these compounds has been the
subject of intense investigations for many years. Since
tions (e.g., air/sunlight, I or Ce ) allowing an efficient
2
release of the metal-free organic ligand.
6
the first report in 1957 [1], a large number of η -ben-
From the point of view of organic synthesis, it is
zene-Cr(CO)3 derivatives have been prepared and most beneficial that the electrophilic Cr(CO) group
3
plenty of information has been collected about their activates the arene ligand in a characteristic fashion.
6
physical properties and chemical reactivity. Most η - This offers a variety of transformations, which cannot
arene-Cr(CO) complexes are air-stable, yellow or red be achieved with the free arenes. The chemical effects
3
crystalline compounds and can be easily prepared from of Cr(CO) group on the reactivity of the complexed
3
the free arenes by thermolysis with Cr(CO) in a high- arene ligand can be shown in the following scheme:
6
Facilated oxidative addition Facilated attack of
of the Pd(0)
nucleophiles and radicals
X
Facilated solvolysis
X
H
Enhanced acidity
H
Configurational stability
Enhanced acidity
OC Cr
OC
CO
Shielding of the complexed ligand
X = Cl, Br, I
These effects are associated with pronounced stere- tive shielding of the complexed π-face of the ligand by
ochemical effects, which mainly result from the effec- the bulky Cr(CO) tripod and from the remarkable con-
3
figurational stability of reactive intermediates in benzyl
position [6–9].
1This article was submitted by the authors in English.
1
070-3284/04/3004-0252 © 2004 åÄIä “Nauka /Interperiodica”

APPLICATION OF CHROMIUM-ARENE COMPLEXES IN THE ORGANIC SYNTHESIS
253
Another important stereochemical aspect is that
achiral) arene ligands bearing two nonidentical sub-
–
CH
(
2
CH2
stituents in ortho- or meta-position give rise to substi-
tuted chromium arene complex A and its enantiomer
ent-A:
–
Cr(CO)3
Cr(CO)
3
+
CH
Y
Y
CH2
2
X
X
OC Cr
OC
Cr CO
CO
+
Cr(CO)3
Cr(CO)
3
CO
OC
A
ent-A
.
CH
CH2
2
X, Y are different nonidentical substituents
.
These chiral complexes can be viewed as structures
possessing a planar chirality [6]. While such architec-
tures offer interesting opportunities for the design of
new chiral ligands and materials, the main application
Cr(CO)3
Cr(CO)
3
The stabilization of negative charge in the benzyl
position by the Cr(CO) fragment allows deprotonation
under mild conditions [15, 16]. If a silyl group is intro-
duced first, the second deprotonation occurs at the silyl-
ated position to give the 1,1-disubstituted product,
which can efficiently be further converted to trans-1,3-
alkylated products [17]:
3
of arene-Cr(CO) complexes is in the field of total syn-
3
thesis.
One of the most useful chemical effects caused by
the electron-withdrawing metal fragment is the
enhanced reactivity of the arene ring towards nucleo-
philes. The treatment of chloro- or fluorobenzene-
Me Si
3
Cr(CO) derivatives with a wide range of heteroatom or
1) t-BuLi (2 eq.)
3
TMSCl
carbon nucleophiles (ROH, RSH, R NH, esters,
2
O
O
2
) MeI
nitriles, sulfones, and others) results in aromatic substi-
tution (S Ar). Even alkoxides can act as a leaving
Cr(CO)3
Cr(CO)3
N
group [8, 9].
TMSCl = trimethylchlorosilane; Me = CH3
In general, the addition of nucleophiles to arenes
The regioselectivity of the benzyl deprotonation is
usually controlled by stereoelectronic effects [18]. The
combination of aromatic and benzyl lithiation/alkylation
offers efficient strategies for the regio- and stereoselective
bearing a donor substituent (OR, NR ) proceeds regi-
2
oselectively in the meta-position giving access to meta-
substituted arylethers and anilines. Of particular syn-
thetic value are stereoselective transformations of are- functionalization of relevant ring systems such as tetrahy-
nes to yield dearomatized products [7–9].
droisochinolins [19] or 1-epi-helioporin D [20, 21].
Another consequence of the electronic nature of the
Due to the coordination of the metal fragment, the
benzyl carbocations have a remarkable configurational
Cr(CO) is an enhanced acidity of aromatic protons
3
stability [13], and S 1-type reactions proceed in a
which enables the ring deprotonation with several lith-
ium-based reagents n-butyllithium (n-BuLi) or lithium
dimethylamide (LDA). As in the case of uncomplexed
systems, polar substituents exhibit ortho-directing
N
highly stereocontrolled fashion [22, 23].
The configurational stability of benzyl radicals
caused by Cr(CO) fragment can also be used for highly
3
effects allowing the regioselective preparation of alkyl- stereoselective transformations [24–26]. The samar-
ated complexes under mild conditions [10, 11]. Meta- ium(II) iodide mediated reaction of complexed ortho-
substituted benzaldehydes and arylketones with acry-
lates leads to γ-butyrolactons with virtually complete
diastereoselectivity [27]:
lithiations are also possible, if sterically hindered bases
such as lithium tetramethylpiperidine (LiTMP) are
used [12].
O
Cr(CO) fragment is able to stabilize either nega-
3
tive or positive charge as well as a radical in the benzyl
position. The resonance structures for such intermedi-
ates with structural and energetical details calculated
by DFT methods can be given as follows [13, 14]:
Cr(CO)3
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

2
54
POLUNIN, SCHMALZ
matic ligand can be released by oxidative decomplex-
ation.
O
CO2Me
O
The planar-chiral architecture of ortho-disubstituted
SmI , t-BuOH
arene-Cr(CO) complexes has been exploited for the
2
3
THF
construction of chiral ligands for asymmetric catalysis
36]. Catalysts with these ligands were successfully
[
used in hydrogenation of ketones, allylic alkylations,
Diels–Alder cycloadditions, and other reactions [37–
42] as shown below:
Cr(CO)3
2% (yield), 100% de (diastereoselectivity)
8
Due to its electron-withdrawing character, the Cr(CO)3
unit strongly activates haloarenes towards the oxidative
addition of Pd(0) into the C–X bonds. Chloro- and even
Ethylene,
cat. LPd(Allyl)BF4
fluoroarene-Cr(CO) complexes readily undergo Pd-cata-
3
lyzed coupling reactions such as Suzuki-, Sonogashira-,
Stille-, and Heck-type reactions [28–31]. Chloroarene
complexes with unsaturated side chains undergo intramo-
lecular Heck reactions as presented in reaction [31]:
PPh2
L =
SiMe3
CO Me
2
Cr(CO)3
Cl
CO, MeOH, NEt3
cat. Pd(PPh )
The above-mentioned chemical properties of arene-
chromium complexes have been used in the highly
spectacular enantioselective total syntheses of complex
natural products and their analogs:
3
4
Cr(CO)3
Cr(CO)3
9
8% de
A very important feature of cross-coupling reactions
OMe
OMe
H
between haloarene-Cr(CO) complexes and arylmetals
OH
OH
3
is that the planar chirality of the complex can be trans-
ferred into axial chirality of the resulting biaryl system
in the highly efficient and controlled manner [32]. This
fact has been used in the enantioselective synthesis of
OMe
(
–)-steganone, in which the biaryl system was diastere-
oselectively assembled starting from a planar-chiral
arene-Cr(CO) complex [33]:
3
Seco-pseudopterosin aglycone
Serrulatane diterpene
O
OMe
O
O
O
MeO
MeO
Br
+
O
OH OHC
Cr(CO)3
B(OH)2
O
MeO
O
OHC
OMe
O
MeO
OMe
cat. Pd(PPh )
3
4
MeO
MeO
O
Na CO
2
3
MeO, H O
2
Cr(CO)3
(–)-Steganone
7
2% (yield), >99% de
In these syntheses, the chemical and stereochemical
Chromium arene complexes have also been used as effects of Cr(CO) unit were exploited in several subse-
3
traceless linkers in solid phase chemistry [34, 35]. By quent transformations. As true highlights, the synthesis
photolysis of an arene-Cr(CO) complex in the presence of terpenes (pseudopterosins [42, 43], helioporins [44,
3
of a phosphane-functionalized polymer, one of the car- 45], serrulatane [46], dihydroxyserrulatic acid [47, 48])
bonyl ligands of the Cr(CO) unit is substituted and the or alkoloids (clavicipitic alcohol [49], (+)-ptilocaulin
3
complex attached to the polymer bead. After required [50], and (–)-lasubin [51]) can be considered. Also,
transformation on the immobilized substrate, the aro- syntheses of compounds with axial chirality such as
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

APPLICATION OF CHROMIUM-ARENE COMPLEXES IN THE ORGANIC SYNTHESIS
255
(
−)-steganone [33] or vancomycin [52] must be men- studied and technological procedures for their isolation
tioned.
from plants in the pure state are difficult. In this work,
we have disclosed a new strategy for the synthesis of
trans-isomers of hydroxy- and methoxystilbenes.
The list of such successful syntheses, where chro-
mium chemistry played a significant role, can also be
extended with further examples, where temporary com-
A known method for the synthesis of trans-polyhy-
plexation and application of arene-Cr(CO) complexes droxystilbene (e.g., resveratrol—3,5,4'-trihydroxystil-
3
in the preparation of simple synthetic building blocks bene (I)) proceeds through trans-3,5,4'-trimethoxystil-
has been used [53, 54].
bene (II), which may be synthesized using a Wittig–Hor-
ner reaction from 3,5-dimethoxybenzylbromide and p-
anisaldehyde via the corresponding phosphonate [60].
Another synthesis of resveratrol uses 3,5-dimethoxy-1-
As an example of this approach, the synthesis of stil-
bene phytoalexins can be considered. Phytoalexins are
plant antibiotics that are produced by plants in response
to fungal infection or abiotic stresses such as heavy
metal ions or UV light. The phytoalexins which were
found in grapes, ground nuts, eucalyptus, and pine bark
(
trimethylsilyloxymethyl)benzene, which is condensed
with p-anisaldehyde with the help of lithium powder in
the presence of naphthalene [61]. Dehydration of the
resulting alcohol afforded the trimethoxystilbene, which
was converted into resveratrol by established methodol-
ogy. Recently, a Heck reaction has been employed for the
synthesis of resveratrol [62–64].
(e.g., resveratrol, piceatannol, pterostilbene, pinostil-
bene, tunalbene, etc.) were identified as trans-stil-
benoids with a very high level of biological activities.
They have powerful antifungal, antioxidant, and antivi-
ral activity, as well as cancer chemopreventive and anti-
We developed the method for synthesis of plant stil-
mutagenic properties. Stilbenoid compounds attracted benoids, e.g., trans-resveratrol I, via compound II from
the great attention because they can serve as phy- inexpensive and preparatively convenient tricarbonyl-
toestrogens and polyfunctional drugs without noxious 1,3-dimethoxybenzenechromium (III-1), whereby this
side effect [55–59]. However, stilbene phytoalexins are complex can be converted into stilbenes through a
not virtually used in official pharmacology because the sequence of deprotonation reactions of initial chro-
biochemical properties of cis–trans isomers are poorly mium-arene building block as shown below:
Cr(CO)3
5
9%
85%
e
a
O
O
TMS
III-3
O
O Cr(CO)3
O
O
P(OEt)2
Cr(CO)3
TMS
TMS
VI
O
O
O
H O
IV
8
0%
f
b, c 98%
O
O
O
O
Cr(CO)3
9
8%
61%
TMS
b, f
d
O
VII
H O
V
O
O
II
O
H O
H O
H O
g
h
5
6%
98%
O
O
I
VIII
H
O
H
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

2
56
POLUNIN, SCHMALZ
a: n-BuLi, THF, TMSCl, –78°C; b: LiTMP, THF, MeI, –50°C; c: n-BuLi, THF, –40°C, p-anisaldehyde, –40–0°C, 1.5 h;
d: n-Bu NF, THF, one drop of H O, 2 h; e: hν, AcOH–Et O (1 : 10), 2 days; f: p-TsOH (toluene sulfonic acid), PhH, 80°C,
4
2
2
1
3 h; g: n-BuLi, THF, –40°C, 15 min, ClP(O)(OEt) , –30–0°C, 1.5 h; h: n-BuLi, THF, –30°C, p-anisaldehyde, –30–0°C, 1.5 h.
2
For the synthesis of the key complex tricarbonyl- been described in arene chromium chemistry [28–31],
6
[
η -1,3-dimethoxy-5-methyl-2-trimethylsilylbenzene]- it has never been reported that the required phospho-
chromium(0) (III-3), we used the fact that the regiose- nates (such as VI) can be directly prepared from the
lectivity of deprotonation of chromium-arene com- benzylic deprotonated intermediates by reaction with
plexes may greatly depend on the reaction conditions. diethylchlorophosphate. Interestingly, phosphonate VI
For instance, the ortho-directing influence of a meth- could be synthesized through the deprotonation of
oxy substituent can be overcompensated by the use of a complex III-3 with n-BuLi in dry THF at –40°C in a
sterically demanding base allowing a (contra-thermo- nitrogen atmosphere and the subsequent addition of
dynamic) selective functionalization in position 5. diethylchlorophosphate to the deep red solution of the
Thus, selective methylation of compound III-1 is pos- deprotonated intermediate at –30°C to 0°C. The Wit-
sible in α-position through sterically hindered LiTMP
tig–Horner reaction between phosphonate VI and p-
anisaldehyde was then achieved through deprotonation
of VI with n-BuLi followed by addition of the reaction
partner at a low temperature (–30°C) and warming up
to 0°C. By this way, the complexed stilbene VII was
obtained as red needles in 80% yield.
[
12]. The ortho-position has been protected via depro-
tonation by n-BuLi and silylation by TMSCl in THF.
The benzylic deprotonation/alkylation of 5-methyl-1,3-
dimethoxybenzene-Cr(CO) derivatives occurs with a
3
surprising ease in excellent yield:
Cr(CO)3
Cr(CO)3
It should be noted that the first method described for
the conversion of III-3 into stilbene II (via IV and V)
proceeded in four steps with 51% yield, the same over-
all transformation was achieved (via VI and VII) in
46% overall yield using a Wittig–Horner reaction as a
key step. In the latter case, both the desilylation and
decomplexation steps proceeded cleanly with almost
quantitative yields.
a
9
9%
O
O
O
O
TMS
(III-2)
(
III-1)
Cr(CO)3
b
As a final step for the synthesis of resveratrol I, the
triple demethylation of trimethoxystilbene II had to be
performed. The described methods for this transforma-
tion (using BBr , MeMgI, or LiPPh as a reagent)
7
5%
O
O
TMS
III-3)
3
2
(
afforded the product in 30–60% yield. As a conse-
The synthesis of key complex III-3 from 1,3-dimethoxy- quence of our positive experience employing lithium
benzene has been conducted in three steps in 61% over- thioethylate (LiSEt) for the double demethylation of
all yield.
1,2-dimethoxybenzene derivatives [20, 21], we treated
Two variants for the construction of the stilbene II (a DMF solution of II) with an excess of LiSEt at
were suggested. The first method utilizes the facile ben- 160°C for 2 h. We were surprised and delighted to find
zyl deprotonation of complex III-3 and subsequent that monomethoxystilbene VIII was formed under
(
aldol-type) addition of the resulting intermediate with these conditions in 98% yield. Actually, compound
p-anisaldehyde. This reaction was conducted under a VIII is a well-known natural product called pinostil-
nitrogen atmosphere by first adding n-BuLi at –40°C to bene (trans-3,4'-dihydroxy-5-methoxystilbene) [55,
a solution of complex III-3 in dry THF. After stirring 65–67], that is found in the bark of Pinus sibericahas
for 45 min at the same temperature, the yellow solution and exhibits interesting biological properties as an
was allowed to slowly warm to –10°C. A color change inhibitor of cyclooxygenase (COX-1). It has never been
to deep red indicated the formation of the benzylic synthesized before. Thus, the selective conversion of II
deprotonated intermediate. After cooling to –40°C, p- to VIII with LiSEt opens an efficient synthetic access
anisaldehyde was added and the solution was allowed to pinostilbene and its derivatives [68, 69]. When the
to warm to 0°C for 1.5 h. After workup, the product IV reaction time of the treatment of VIII with LiSEt was
was obtained as a yellow oil in 85% yield. Desilylation extended to 12 h, resveratrol I was formed in 30%
with tetrabutylammonium fluoride and oxidative yield. Note that all reaction products were fully charac-
1
13
decomplexation afforded alcohol V, which was con- terized by H, C NMR, and IR spectroscopy and mass
verted into stilbene II following an established proce- spectrometry. The described route could also be
dure [61].
extended for the preparation of other plant hydroxystil-
In the second set of experiments, we prepared stil- benes [68, 69], for instance, piceatannol (3,5,4',5'-tet-
bene VII from phosphonate VI by means of a Wittig– rahydroxystilbene) and tunalbene (3,3'-dihydroxy-5-
Horner olefination. While some related reactions have methoxystilbene).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

APPLICATION OF CHROMIUM-ARENE COMPLEXES IN THE ORGANIC SYNTHESIS
257
Arene chromium chemistry proved able to be uti- yield (78 mg), m.p. 158°C (in [12]: m.p. 158°C), R 0.27
f
lized as a highly efficient synthetic method and offers (hexane : AcOEt = 5 : 1).
often a unique and effective synthesis strategy. It can be
expected that arene metal chemistry will find many
other applications in natural product synthesis in the
future.
–1
IR spectrum, ν, cm : 2950, 2901, 1937, 1863
1
(
C=O, Cr(CO) ), 1849, 1320, 1229, 1112, 839. H
3
NMR (270 MHz, CDCl ), δ, ppm: 0.33 (s, 9H,CH –Si),
3
3
2
.35 (s, 3H, CH ), 3.68 (s, 6H, OCH ), 4.65 (s, 2H,
3 3
1
3
C(4)H/C(6)H). C NMR (67.7 MHz, CDCl ), δ, ppm:
3
1
(
.5 (q, CH –Si), 21.3 (q, CH ), 55.3 (q, C–OCH ), 72.6
3 3 3
EXPERIMENTAL
d, C(4)/C(6)), 77.2 (s), 108.4 (s), 148.2 (s), 234.6 (s).
+
6
Mass spectrum (EI, 70 eV), m/z (I , %): 360 [M] (18),
rel
Tricarbonyl-[h -1,3-dimethoxy-2-trimethylsilyl-
3
04 (15), 276 (100), 261 (8), 201 (5), 149 (12), 52 (10).
benzene]chromium(0) (III-2).A solution of tricarbon-
yl-1,3-dimethoxybenzenechromium complex (III-1)
6
Tricarbonyl-[2-(h -3,5-dimethoxy-4-trimethylsil-
ylphenyl)-1-(4'-methoxyphenyl)ethanol]chromi-
(2.00 g, 1.4 mmol) in anhydrous THF (50 ml) was
um(0) (IV). A solution of complex III-3 (500 mg,
placed in a 100-ml Schlenk flask and cooled to –78°C.
A 1.6 M solution of n-BuLi (4.78 ml, 7.65 mmol) in
hexane was added with stirring. After stirring for 0.5 h,
TMSCl (2.3 ml, 18.3 mmol) was added. The solution
was stirred for 15 min at –78°C, after which the temper-
ature was raised to 0°C for 1 h. AcOEt (50 ml) was
added to the mixture, and the solution was washed with
1
5
.38 ml) in anhydrous THF (10 ml) was placed in a
0-ml Schlenk flask and cooled to –40°C, and a 1.6 M
solution of n-BuLi (0.95 ml, 1.53 mmol) in hexane was
added with stirring. The mixture was stirred for 15 min
at –40°C and 30 min at 0°C until the solution became
dark red, after which it was cooled to –40°C. Anisalde-
hyde (0.25 mg, 2.08 mmol) was added to the cooled
solution, and the mixture was stirred for 30 min at
a saturated solution of NaHCO (2 × 60 ml) and a satu-
3
rated solution of NaCl (50 ml), dried over MgSO , and
4
−
(
20°C and for 1 h at 0°C. Methyl tert-butyl ether
evaporated in vacuo. Yellow crystals of III-2 were
obtained in 99% yield (2.50 g) with m.p. 150°C (in
MTBE) (40 ml) was added to the reaction mixture. The
organic layer was washed with water (2 × 40 ml) and a
[
12]: m.p. 150°C) and R 0.3 (hexane : AcOEt = 5 : 1).
f
saturated solution of NaCl (30 ml), dried with MgSO4,
–
1
IR spectrum, ν, cm : 2975, 2957, 2903, 1943, 1871,
and concentrated in vacuo. The crude product was puri-
1
8
9
843, 1524, 1505, 1453, 1442, 1415, 1285, 1238, 1096,
fied on a chromatotron eluting with a hexane–AcOEt
1
47, 669. H NMR (270 MHz, CDCl ), δ, ppm: 0.34 (s,
3
(
10 : 1) mixture. Compound IV was obtained in 85%
H, CH –TMS), 3.68 (s, 6H, OCH ), 4.71 (d, 2H,
3
3
yield (584 mg) as yellow oil with R 0.06 (hexane :
f
C(4)H/C(6)H, J = 7.0 Hz), 5.72 (t, 1H, C(5')H, J =
AcOEt = 5 : 1), m.p. 120°C.
1
3
7
.0 Hz). C NMR (67.7 MHz, CDCl ), δ, ppm: 1.6 (q,
3
–1
IR spectrum, ν, cm : 3586 (OH), 2954, 1950, 1865
C=O, Cr(CO) ), 1513, 1496, 1248, 1227. H NMR
400 MHz, CDCl ), δ, ppm: 0.34 (s, 9H, CH –Si), 2.04
CH –Si), 55.4 (q, OCH ), 73.2, 69.7 (d, C(4)/C(6)),
3
3
1
(
(
8
0.9 (s), 93.2 (d, C(5)), 148.4 (s), 234.2 (s, Cr(CO)3).
3
Mass spectrum (electron impact (EI), 70 eV), m/z (I ,
3
3
rel
+
%
(
): 346 [M] (15), 334 (57), 290 (10), 262 (100), 217 (d, 1H, OH, J = 3.0 Hz), 2.85 (dd, 1H, CH
, J = 14.0 Hz,
2
9), 190 (11), 135 (9), 52 (26).
J = 5.0 Hz), 2.93 (dd, 1H, CH , J = 14.0 Hz, J = 8.0 Hz),
2
6
3.61, 3.64 (both s, 3H, OCH ), 3.82 (s, 3H, OCH ),
3
3
Tricarbonyl-[h -1,3-dimethoxy-5-methyl-2-tri-
methylsilylbenzene]chromium(0) (III-3). A 1.5 M
4
.58, 4.65 (both s, 1H, C(2)H/C(6)H), 4.93 (m, 1H,
solution of n-BuLi (0.2 ml, 0.32 mmol) in hexane was CH –OH), 6.91 (d, 2H, C(2')H/C(6')H, J = 9.0 Hz), 7.29
13
added at –78°C to a solution of 2,2,6,6-tetramethylpip- (d, 2H, C(3')H/C(5')H, J = 9.0 Hz). C NMR (67.7 MHz,
eridine (0.055 ml, 0.32 mmol) in anhydrous THF (1 ml)
CDCl ), δ, ppm: 1.5 (q, CH –Si), 26.9 (d, CH –OH),
3
3
placed in a 25-ml Schlenk flask. The mixture was
stirred for 40 min at –40°C and cooled to –78°C. Com-
plex III-2 (100 mg, 0.288 mmol) was added, and the
mixture was stirred for 0.5 h at –78°C. A solution of
4
7
5.4 (t, CH ), 55.4, 55.29, 55.27 (all q, OCH ), 73.2,
4.6 (both d, C(2)/C(6)), 108.3 (s), 114.0 (d,
C(3')/C(5')), 127.2 (d, C(2')/C(6')), 135.3 (s), 148.1 (s),
2
3
1
59.5 (s), 234.5 (s, Cr(CO) ). Mass spectrum (EI, 70
3
NH I (90 µl, 1.4 mmol) in anhydrous THF (4 ml) was
3
+
eV), m/z (I , %): 496 [M] (8), 412 (100), 394 (20),
placed into the second 25-ml Schlenk flask and cooled
to –50°C. A solution of the anion of complex III-3 from
the first flask was rapidly added through a pumping
rel
2
24 (48), 137 (52), 52 (7).
2-(3,5-Dimethoxyphenyl)-1-(4'-methoxyphen-
pipe to a solution in the second flask. The mixture was yl)ethanol (V). Desilylation. One water droplet and
stirred for 0.5 h at –50°C and 1 h at 25°C, then heptane 5.75 ml (5.75 mmol) of n-Bu NF (1 M solution in THF)
4
(
20 ml) was added, and 50% solvent were evaporated in were added with stirring to complex IV (517 mg,
vacuo, AcOEt (20 ml) was added to the residue, and the 1.04 mmol) in THF (20 ml). After stirring for 2 h at
resulting solution was washed with 2 N HCl (2 × 20°C, AcOEt (30 ml) was added. The solution was
2
0 ml), a saturated solution of NaHCO (20 ml), and a washed with water (40 ml) and a saturated solution of
3
saturated solution of NaCl (20 ml). The organic layer NaCl (40 ml), dried with MgSO , and concentrated.
4
was dried with MgSO and concentrated in vacuo. Complex IV was obtained in 99% yield (437 mg) with
4
Complex III-3 was obtained as yellow crystals in 75% Rf 0.55 (hexane : MTBE = 1 : 1).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

2
58
POLUNIN, SCHMALZ
Decomposition of chromium arene complex IV. 0°C, AcOEt (20 ml) was added. The solution was
Desilylated complex IV (450 mg, 0.9 mmol) was dis- washed with a saturated solution of NaCl (2 × 30 ml),
solved in an AcOH–Et O (1 : 10) mixture (60 ml), and water (30 ml), and a saturated solution of NaCl (30 ml),
2
the resulting solution was stored for 2 days in sunlight. dried with MgSO , and concentrated in vacuo. Purifica-
4
Then, the green residue was filtered off on a zeolite tion on a column packed with silica gel (10 g) yielded
layer 1 cm thick, and the colorless filtrate was concen- phosphonate VI (162 mg, 59% yield) as yellow crystals
trated in vacuo. Alcohol V was obtained as yellow vis- with m.p. 130°C and initial compound III (75 mg, 37%
cous oil in 99% yield (285 mg), R 0.27 (hexane : yield) with R 0.18 (hexane : AcOEt = 1 : 1).
f
f
MTBE = 1 : 1).
–1
IR spectrum, ν, cm : 2903, 1951, 1866 (C=O,
–
1
1
IR spectrum, ν, cm : 3450 (OH), 2927, 1596, 1512, Cr(CO) ), 1230, 1104, 1054, 1026. H NMR (400 MHz,
3
1
1
246, 1149, 1066. H NMR (400 MHz, CDCl ), δ, CDCl
3
), δ, ppm: 0.32 (s, 9H, CH
3
–Si), 1.34 (t, 6H, CH
P, H
,
3
3
3
J = 7.0 Hz), 2.96 (d, 2H, CH , J = 20.5 Hz), 3.69 (s,
ppm: 1.94 (d, 1H, OH, J = 3.0 Hz), 2.91 (dd, 1H, CH2,
J = 14.0 Hz, J = 8.0 Hz), 2.96 (dd, 1H, CH , J = 14.0 Hz,
J = 5.0 Hz), 3.77 (s, 6H, OCH ), 3.81 (s, 3H, OCH ),
2
6
H, OCH ), 4.13 (m, 4H, OCH ), 4.74 (s, 2H,
3
2
2
1
3
C(2)H/C(6)H). C NMR (67.7 MHz, CDCl ), δ, ppm:
3
3
3
1
(
.5 (q, CH –Si), 16.4, 16.5 (both q, CH ), 32.7, 34.9
3
3
4
.85 (m, 1H, CH –OH), 6.36 (br. s, 3H,
both t, OCH ), 62.5 (t, CH P), 72.27, 72.31 (both d,
2 2
C(2)H/C(6)H/C(4)H), 6.89 (d, 2H, C(2')H/C(6')H, J =
C(2)/C(6)), 79.3 (s, C(1)), 102.3 (s, C(4)), 148.0 (s,
1
3
9
.0 Hz), 7.3 (d, 2H, C(3')H/C(5')H, J = 9.0 Hz).
C
C(3)/C(5')), 234.2 (s, Cr(CO) ). Mass spectrum (EI,
3
+
NMR (67.7 MHz, CDCl ), δ, ppm: 46.4 (t, CH ), 55.2, 70 eV), m/z (I , %): 496 [M] (2), 412 (100), 360 (30),
3
2
rel
3
45 (61), 315 (10), 285 (68), 52 (40).
5
5.3 (both q, OCH ), 74.7 (q, OCH ), 98.6 (d, CH –
3 3
6
OH), 107.4 (d, C(2)/C(6)), 113.7 (d, C(3')/C(5')), 127.1
(
Tricarbonyl-[1-(h -3,5-dimethoxy-4-trimethylsilyl-
d, C(2')/C(6')), 135.9 (s), 143.5 (s), 140.4 (s), 159.0 (s), phenyl)-2-(4'-methoxyphenyl)ethylene]chromium(0)
1
60.8 (s). Mass spectrum (EI, 70 eV), m/z (I , %): 288 (VII). Phosphonate VI (265 mg, 0.735 mmol) in anhy-
rel
+
drous THF (10 ml) was placed in a 25-ml Schlenk flask,
and a 1.5 M solution of n-BuLi (0.5 ml, 0.81 mmol) in
hexane was added at –40°C. The mixture was stirred
for 15 min at –40°C and 30 min at −10°C (the red color
appeared). Then, anisaldehyde (0.25 ml, 2.08 mmol)
was added. The mixture was heated during 1 h to boil-
ing and cooled to 20°C, and AcOEt (30 ml) was added.
The solution was washed with water (2 × 40 ml), a sat-
[M] (1), 270 (4), 152 (100), 137 (98), 109 (18).
(E)-2-(3,5-Dimethoxy)-1-(4'-methoxyphenyl)ethe-
ne(II). TsOH (20 mg, 0.012 mmol) in benzene (10 ml)
was added to a solution of alcohol V (250 ml,
0
.59 mmol), and the mixture was refluxed for 13 h.
Then, AcOEt (20 ml) was added, and the solution was
washed with a 10% solution of NaHCO (3 × 30 ml)
3
and a saturated solution of NaCl (30 ml), dried with
urated solution of NaHCO (30 ml), and a saturated
solution of NaCl (30 ml), dried with MgSO , and con-
3
MgSO , and concentrated in vacuo. After purification
4
4
on a chromatotron (hexane : AcOEt = 8 : 1), stilbene II
centrated in vacuo. The crude product was purified on a
column packed with kiesel gel (10 g) (hexane : AcOEt =
(
94 mg, 61% yield) was obtained with m.p. 47°C and Rf
0
.16 (hexane : AcOEt = 10 : 1).
5
0 : 1). Stilbene VII was obtained in 80% yield
–
1
IR spectrum, ν, cm : 3027, 2935, 1590, 1511, 1251,
(
280 mg) as red needles with m.p. 202°C and R 0.57
f
1
1
150, 1066. H NMR (400 MHz, CDCl ), δ, ppm: 2.83
3
(
hexane : AcOEt = 1 : 1).
(
s, 9H, OCH ), 6.37 (t, 1H, C(2)H, J = 2.0 Hz), 6.65 (d,
3
–1
IR spectrum, ν, cm : 2978, 2956, 1935, 1843
2
H, C(2)H/C(4)H, J = 2.0 Hz), 6.99 (d, 2H,
C(2')H/C(6')H, J = 9.0 Hz), 7.01 (d, 1H, olefin, J =
7.0 Hz), 7.03 (d, 2H, C(3')H/C(5')H, J = 9.0 Hz), 7.45
1
(
(
C=O, Cr(CO) ), 1605, 1535, 1228, 839. H NMR
3
400 MHz, CDCl ), δ, ppm: 0.45 (s, 9H, CH –TMS),
3
3
1
(
1
3
3.76 (s, 6H, OCH ), 3.83 (s, 3H, OCH ), 4.93 (s, 2H,
3 3
d, 1H, olefin, J = 17.0 Hz). C NMR (67.7 MHz,
CDCl ), δ, ppm: 55.2, 55.3, 55.32 (all q, OCH ), 99.6
C(2)H/C(6)H), 6.72 (d, 1H, olefin, J = 17.0 Hz), 6.91
d, 2H, C(2')H/C(6')H, J = 9.0 Hz), 6.98 (d, 1H, olefin,
J = 17.0 Hz), 7.44 (d, 2H, C(3')H/C(5')H, J = 9.0 Hz).
3
3
(
(
q, C(4)), 104.3 (d, C(2)/C(6)), 114.1 (d,
C(3')H/C(5')H), 126.5 (d, olefin), 127.8 (d, C(2')/C(6')),
1
3
C NMR (67.7 MHz, CDCl ), δ, ppm: 1.5 (q, CH –
3
3
1
28.7 (d, olefin), 139.9 (s), 139.6 (s), 159.4 (s), 160.9
+
TMS), 55.2, 55.3, 55.4 (all q, OCH ), 68.9 (d,
3
(
s). Mass spectrum (EI, 70 eV), m/z (I , %): 270 [M]
rel
C(2)/C(6)), 79.4 (s), 106.5 (s), 114.4 (d, C(3')/C(5')),
(
100), 239 (8), 196 (7), 115 (3).
1
(
23.9 (d, olefin), 128.3 (d, C(2')/C(6')), 128.4 (s), 131.8
6
Tricarbonyl-[1-(h -3,5-dimethoxy-4-trimethylsil-
d, olefin), 148.3 (s), 160.2 (s), 234.0 (s, Cr(CO) ).
3
ylphenyl)methyldiethylphosphonate]chromium(0) (VI).
+
Mass spectrum (EI, 70 eV), m/z (I , %): 478 [M] (1),
rel
Complex III (200 mg, 0.554 mmol) in anhydrous THF
+
+
3
2
94 [M–3CO] (8), 342 [M–3CO–Cr] (92), 327 (21),
67 (100), 223 (45).
(
6 ml) was placed in a 25-ml Schlenk flask, and n-BuLi
(
0.38 ml, 0.71 mmol) as a 1.6 M solution in hexane was
Desilylation of stilbene VII was similar to desilyla-
tion in synthesis of alcohol V. The yield was 99%.
added at –40°C. The mixture was stirred for 15 min at
–
40°C and 30 min at –10°C (the dark red color
appeared). Then, the mixture was cooled to –30°C, and
Synthesis of trimethoxystilbene II was carried out
diethyl chlorophosphate (104 µl, 0.72 mmol) was by the decomposition of its chromium complex. Desil-
added. After stirring for 30 min at –10°C and for 1 h at ylated complex VII (115 mg) was dissolved in an
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

APPLICATION OF CHROMIUM-ARENE COMPLEXES IN THE ORGANIC SYNTHESIS
259
AcOEt–Et O (1 : 10) mixture (50 ml), and diiodine 2H, C(2)H/C(6)H, J = 2.0 Hz), 6.83 (d, 2H,
2
(
300 mg) was added. The mixture was stirred for 12 h C(2')H/C(6')H, J = 9.0 Hz), 6.85 (d, 1H, olefin, J =
at 20°C, and Et O (50 ml) was added. The solution was 17.0 Hz), 7.00 (d, 1H, olefin, J = 17.0 Hz), 7.39 (d, 2H,
2
1
3
washed with a saturated solution of NaCl (50 ml), dried C(3')H/C(5')H, J = 9.0 Hz). C NMR (100.64 MHz,
with MgSO , and concentrated in vacuo. Stilbene II CD Cl ), δ, ppm: 55.6 (q, OCH ), 101.4 (d, C(4)),
was obtained in 99% yield (76 mg) and exhibited char- 104.4, 106.6 (both d, C(2)/C(6)), 116.5 (d, C(3')/C(5')),
4
3
3
3
acteristics described above.
E)-2-(3,5-Dihydroxyphenyl)-1-(4'-hydroxyphen-
yl)ethylene (resveratrol) (I). Trimethoxystilbene II
129.9 (d, olefin), 128.9 (d, C(2')/C(6')), 129.8 (d, ole-
fin), 130.3 (s), 141.3 (s), 158.4 (s), 159.7 (s), 162.5 (s).
(
+
Mass spectrum (EI, 70 eV), m/z (I , %): 228 [M] (56),
rel
1
65 (18), 107 (10), 85 (100), 57 (8). According to the
(
70 mg, 0.26 mmol) in Et O (2 ml) was added to a solu-
2
1
H NMR data, the product contains cis-isomer (3%).
tion of MeMgI, prepared from Mg (148 mg, 6.08 mmol)
1H NMR spectra were recorded on Bruker AM-400
and MeI (1.43 ml, 22.8 mmol) in Et O (10 ml). The
2
ether was distilled off in an argon flow, and the residue (400 MHz) and Bruker AM-270 (270 MHz) spectro-
was heated in vacuo for 30 min at 100°C and then in an meters in CDCl , using CHCl for CDCl and CH OD
3
3
3
3
1
3
argon flow for 15 min while increasing the temperature for CD OD as internal standards. C NMR spectra
3
to 160°C. After the solution was cooled to 20°C, 10% were obtained using Bruker AM-400 (100.64 MHz)
NH Cl (15 ml) andAcOEt (20 ml) were carefully added and Bruker AM-270 (67.7 MHz) instruments. Mass
4
to the contents of the flask. The aqueous layer was spectra were obtained on Varian MAT 711 and Varian
extracted with AcOEt (3 × 30 ml), and the combined MAT 44 mass spectrometers (electron impact, 70 eV,
extracts were washed with a saturated solution of NaCl direct injection into an ion source). IR spectra were
(
30 ml), dried with MgSO , and concentrated in vacuo. recorded on a Magna FT-IR 750 spectrometer (Nicolet)
4
The crude product was purified on a chromatotron with KBr windows. Melting points were measured with
hexane : AcOEt = 1 : 1). Resveratrol I (32 mg, 54%) a Buchi 510 instrument without correction. The reac-
(
was obtained as solid white needles with m.p. 247°C (in tion courses and purity of isolated products were mon-
[60]: m.p. 247°C) and R 0.24 (hexane : AcOEt = 1 : 1).
itored by TLC on the Kieselgel 60F254 plates (Merck) in
f
–
1
an AcOEt–hexane system.
IR spectrum, ν, cm : 3329, 3029, 1604, 1238, 1147,
36. H NMR (400 MHz, CDCl ), δ, ppm: 6.13 (t, 1H,
1
8
Compounds were detected by UV absorption after
3
C(4)H, J = 2.0 Hz), 6.42 (d, 2H, C(2)H/C(6)H, J = irradiation with a Fluotest lamp (λ = 254 or 365 nm).
2
.0 Hz), 6.74 (d, 2H, C(2')H/C(6')H, J = 9.0 Hz), 6.78 Individual compounds were isolated from reaction
(
d, 1H, olefin, J = 17.0 Hz), 6.93 (d, 1H, olefin, J = products by preparative TLC on a Harrison Research
1
3
1
7.0 Hz), 7.33 (d, 2H, C(3')H/C(5')H, J = 9.0 Hz). C 7924 T chromatotron using glass circular plates cov-
NMR (100.64 MHz, CD OD), δ, ppm: 102.6 (d, C(4)), ered with Kieselgel PF–60F254 (Merck) (hexane–
3
1
05.8 (d, C(2)/C(6)), 116.5 (d, C(3')/C(5')), 127 (d, ole- AcOEt as eluent) and by column chromatography (Kie-
fin), 128.8 (d, C(2')/C(6')), 129.4 (d, olefin), 130.3 (s), selgel 60, Merck, 230–400 mesh) using AcOEt–petro-
1
7
8
41.3 (s), 158.4 (s), 159.7 (s). Mass spectrum (EI, leum ether as eluent. The yields of compounds were not
+
0 eV), m/z (I , %): 228 [M] (56), 165 (18), 107 (10), optimized.
rel
5 (100), 57 (8).
All reagents and solvents (Aldrich, Fluka, Acros,
(
E)-2-(5-Hydroxy-3-methoxyphenyl)-1-(4'-
Merck) had 99% purity and were used as received.
hydroxyphenyl)ethylene (pinostilbene) (VIII). Tri- Hexacarbonylchromium (Fluka) with 99% purity was
methoxystilbene II (30 mg, 0.11 mmol) and lithium used in synthesis of chromium arene complex.
thioethoxide (135 mg, 1.33 mmol) in DMF (4 ml) were
All reactions involving chromium arene complex
placed in a 25-ml Schlenk flask connected with a reflux
were carried out in moisture- and oxygen-free highly
condenser and a paraffinic bubble counter. After this
purified argon under a low pressure in the Schlenk flask
apparatus had been thoroughly degassed by tenfold
using a syringe technique. Reagents and solvents were
evacuation and filled with argon, the mixture was
dried using standard methods. Glassware was calcined
heated for 2 h at 160°C. After cooling, 0.1 M HCl
before use and then cooled in an argon flow.
(
15 ml) and AcOEt (20 ml) were slowly added to the
solution, and the latter was washed with water (6 ×
3
0 ml). The organic layer was washed with a saturated
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