Synthesis, characterization, and some reactions of the tricarbonylchromium complexes of 1,3-indandione and ninhydrin

Article abstract of DOI:10.1002/(SICI)1099-0690(199901)1999:1<167::AID-EJOC167>3.0.CO;2-Z

The syntheses and characterization of the tricarbonylchromium complexes of 1,3-indandione and ninhydrin are described. As the direct complexation proved unsuccessful, the acetal route was tried. Although some complexes were obtained, complex deacetalization did not work in the case of ninhydrin. Finally, the oxidation of tricarbonyl(η⁶-1,3-indandione)chromium(0) with dimethyldioxirane gave the ninhydrin complex in 75% yield in equilibrium with the indantrione complex. The latter reacts in hetero Diels-Alder reactions with dienes with diastereoselective formation of spiro anellated pyran derivatives.

Full text of DOI:10.1002/(SICI)1099-0690(199901)1999:1<167::AID-EJOC167>3.0.CO;2-Z

FULL PAPER
Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium
Complexes of 1,3-Indandione and Ninhydrin
[a]
[b]
[a]
Dirk Leinweber, Rudolf Wartchow, and Holger Butenschön*
Keywords: 1,3-Indandione / Ninhydrin / Chromium complexes / Acetals / Oxidation / Hetero Diels-Alder reaction
The syntheses and characterization of the tricarbonyl-
chromium complexes of 1,3-indandione and ninhydrin are
described. As the direct complexation proved unsuccessful,
the acetal route was tried. Although some complexes were
obtained, complex deacetalization did not work in the case
indandione)chromium(0) with dimethyldioxirane gave the
ninhydrin complex in 75% yield in equilibrium with the
indantrione complex. The latter reacts in hetero Diels-Alder
reactions with dienes with diastereoselective formation of
spiro anellated pyran derivatives.
6
of ninhydrin. Finally, the oxidation of tricarbonyl(η -1,3-
(
η6-Arene)tricarbonylchromium complexes with func- cases. Dianionic oxy-Cope rearrangements starting from 2
tionalized anellated rings deserve interest under a variety of are possible with a number of alkenylmetal reagents. In
aspects. Often their chemistry considerably differs from that many cases a subsequent intramolecular aldol addition re-
of the uncoordinated arene for at least two reasons. First, sults in the formation of a highly functionalized benz-anel-
the electron withdrawal of the tricarbonylchromium groups lated diquinane, e.g. 4 from 2 and 1-lithio-1-methoxyal-
renders the anellated ring electron poor. This is especially lene.[
3Ϫ5]
2
the case when sp hybridization of the benzylic carbon
atoms facilitates the transfer of the tricarbonylchromium
electron withdrawal to the anellated ring via resonance in-
teractions. Second, the facial discrimination caused by com-
plexation at only one side of the aromatic system decreases
symmetry and as a consequence can induce changes to the
stereoselectivity of chemical reactions at the anellated ring.
Usually one observes attack of reagents from the face op-
posite to the tricarbonylchromium group. This point is of
special importance when more than one reaction of this
kind takes place at the anellated ring. As a consequence,
the stereodirecting effect of tricarbonylchromium should be
more clearly visible in the reactions of multifunctional anel-
lated rings.
In our work this type of diastereoselectivity became obvi-
ous when (η -benzocyclobutenedione)tricarbonylchromium
2) was treated with nucleophiles: In contrast to the reac-
As 2 proved to be a starting material for diastereoselec-
tive reactions leading to highly functionalized anellated ring
6
(
systems, we became interested in the next higher analogues,
which are the tricarbonylchromium complexes 5 and 7 or 8
of 1,2-indandione and indantrione or ninhydrin, respec-
tively. If similar chemistry were possible with these com-
plexes, this would pave a way to benz-anellated cyclonon-
anedione and hydrindane systems. The keto functionalities
in complexes 5Ϫ8 should be rather electrophilic, because,
tions of the uncoordinated ligand, only cis diaddition was
observed with a number of nucleophiles. 2 can be obtained
by hydrolysis of the diacetal 1 in high yield, which is now
[1]
available by an improved synthesis. The most striking ob-
servation in this context was the dianionic oxy-Cope re-
arrangement upon diaddition of vinyllithium to 2, which
resulted in the formation of benzocyclooctenedione com-
plex 3 in high yield under mild reaction conditions.[
This reaction involves both functionalities and is possible
only because the diaddition to the keto functionalities takes
2
as in 2, the sp hybridization of the benzylic carbon atoms
2Ϫ4]
should facilitate the electron withdrawal to the Cr(CO)3
fragment. In 7 the central keto group at C-2 should be more
electrophilic than the other two. A consequence is that the
first nucleophilic addition will usually take place at C-2,
which means that next in any case a neighbouring keto
group is attacked, which is a precondition of oxy-Cope
chemistry to happen. Here, we report on the synthesis of
the tricarbonylchromium complexes 7 and 8. On the way
place from the face opposite to the Cr(CO) group in both
3
[a]
Institut für Organische Chemie, Universität Hannover,
Schneiderberg 1B, D-30167 Hannover, Germany
Fax: (internat.) ϩ49(0)511/762-4616
E-mail: holger.butenschoen@mbox.oci.uni-hannover.de
Institut für Anorganische Chemie, Universität Hannover,
Callinstraße 9, D-30167 Hannover, Germany
[b]
6
to these complexes it became clear that tricarbonyl(η -1,3-
Eur. J. Org. Chem. 1999, 167Ϫ179

WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ193X/99/0101Ϫ0167 $ 17.50ϩ.50/0
167

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
indandione)chromium(0) (6) plays a key role in the finally
In a first attempt to prepare 16, indantrione (19) or
successful synthesis. The synthesis of 5 will be reported else- ninhydrin (17) were subjected to standard acetalization con-
where.
ditions [1,2-ethanediol, cat. p-toluenesulfonic acid (PTSA),
aceotropic water removal with benzene]. Unexpected and in
contrast to SchönbergЈs work,[ bisacetal 18 was obtained
in 85% yield. Although complexation of 18 was unsuccess-
ful, the compound came out to be a valuable starting mate-
rial for a new synthesis of benzocyclobutenedione by pho-
todecarbonylation and subsequent deacetalization.[
10]
1]
While the acetalization under standard conditions took
place only at the keto groups adjacent to the aromatic ring,
selective acetalization was possible at C-2 using 2-bromo-
ethanol/potassium carbonate.[ Starting from ninhydrin
As with benzocyclobutenedione, all attempts to directly
coordinate the ligands by treatment of indantrione (19) or
ninhydrin (17) with hexacarbonylchromium or triammine-
tricarbonylchromium were not successful and resulted in
decomposed material only. A retrosynthetic analysis of the
problem led to five different possible ways to 7 or 8 starting
from 9Ϫ12 and 6.
9]
(17) or indantrione (19) the sequence of acetalization reac-
tions is interchangeable, so that either 18 or 20 are inter-
9
might be a precursor of 7 and 8 in an acetalizationϪ
complexationϪdeacetalization sequence, which had proven
successful in the case of 2. Similar to an earlier synthesis of
[6]
ninhydrin (17) from diethyl phthalate, 10 could undergo
a Pummerer rearrangement upon treatment with dimethyl
sulfoxide/sodium methanolate. 11 could be obtained from 6
2
and already contains all three sp hybridized carbon atoms
in the anellated ring. A change of the functional group X
mediates leading to 16, the route via 20 giving higher yield.
Next, complexation of 16 was achieved by treatment with
hexacarbonylchromium in dibutyl ether/THF (10:1) at
(diazo, oxime, enamine) by hydrolysis or oxidation to O
would give 7 or 8. Alternatively, 12 (Y ϭ halogen) could be
formed from 6 by halogenation, hydrolysis should give 7 or
1
17°C in 82% yield. 21, which is the first chromium com-
plex of an indantrione acetal, was obtained as a yellow
powder which was crystallized from diethyl ether/petroleum
ether. In contrast to many similar compounds the crystal-
line material is air sensitive and decomposes within 24 h in
the air. From ethyl acetate/petroleum ether (1:1) crystals of
8
. Finally, a direct oxidation of 6 to 7 or 8 must be con-
sidered. However, one would have to use an oxidation
method which must not cause an oxidative decomplexation
of the low valent chromium atom.
2
1 suitable for an X-ray crystal structure analysis were
The Acetal Route
grown at Ϫ30°C (Figure 1).
Indantrione (19) was obtained by treatment of commer-
cially available ninhydrin (17) with boiling thionyl chloride
[
7]
in almost quantitative yield.
Because known acetals
[
8Ϫ10]
1
3؊15
did not give satisfactory complexation results,
new, thermally more stable indantrione acetals were envis-
aged as ligands for chromium complexes. The most promis-
ing acetal in this context is, of course, tris(ethylenedioxy)in-
dane (16).
The structure shows that the central ethylenedioxy group
is bent towards the tricarbonylchromium group whereas the
ethylenedioxy groups at C-1 und C-3 are bent away from
the tricarbonylchromium group. This conformation mini-
mizes steric interactions between the adjacent ethylenedioxy
groups as well as the steric interaction between ethylen-
edioxy groups and the tricarbonylchromium fragment.
168
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
drolysis of rac-24 was only partly successful and gave com-
plex rac-26 in 76% yield upon treatment with 50% sulfuric
acid in acetone, whereas attempts to hydrolyze 25 resulted
in decomposed material only.
As the ethylenedioxy group at C-2 proved to be unexpec-
tedly stable, we envisaged using an open-chain acetal in-
stead. In this case, hydrolysis should be favored for entropic
reasons. 2,2-Diethoxy derivative 27 was obtained from 18
Figure 1. Structure in the crystal and numbering scheme of 21.[
11]
˚
Selected bond lengths [A]: C1ϪC2 1.557(3), C2ϪC3 1.565(4),
C3ϪC3a 1.506(3), C3aϪC4 1.408(3), C4ϪC5 1.395(4), C5ϪC6
.400(4), C6ϪC7 1.392(4), C7ϪC7a 1.412(3), C7aϪC3a 1.387(3),
1
C7aϪC1 1.502(3), C1ϪO1 1.403(3), C1ϪO2 1.423(3), C2ϪO3 by treatment with triethyl orthoformiate in the presence of
1.408(3), C2ϪO4 1.400(3), CrϪCArene 2.209(2) Ϫ 2.218(2).
PTSA in 65% yield and coordinated to tricarbonylchrom-
ium in 79% yield under standard conditions (dibutyl ether/
THF, 10:1, 117°C, 20 h) to give complex 28. Single depro-
tection of 28 to monoacetal 29 was achieved in 85%,
whereas stronger reaction conditions resulted in deprotec-
tion at C-1 and C-3 only in moderate yield (48%) of 30,
After the successful complexation of ligand 16 deprotec-
tion of the keto groups was attempted similar to the depro-
tection of 1. Treatment of 21 with conc. hydrochloric acid
at 20°C for 2 h resulted in the hydrolysis of only one ethyl-
enedioxy group. Racemic 22 was isolated in 85% yield.
However, the reaction had to be traced by TLC in order to
avoid further hydrolysis. Pure 22 was obtained in 93% yield
upon treatment of 21 with 50% sulfuric acid for 3 h at 20°C.
Stronger reaction conditions (conc. HCl, 50°C, 4 h) pro-
vided 1,3-indandione complex 23 in 92% yield.
1
which was characterized by H-NMR and IR spec-
troscopy only.
2
2 and 23 were characterized spectroscopically. The elec-
tron withdrawing effect of the benzylic keto group can
nicely be observed by comparison of the carbonyl ligand
absorptions in the IR spectra: Whereas these bands are ob-
Ϫ1
served at 1972 and at 1903 cm for trisacetal 21, the keto
group in 22 reduces the carbonyl ligand backbonding as
Ϫ1
indicated by values of 1988 and 1922 cm for this com-
pound. This effect is even stronger for diketone 23, the ab-
Although the acetal route so far resulted in the synthesis
of a number of interesting, highly functionalized indanone
and indandione complexes, it did so far not pave a way
to the desired complexes 7 and 8. Experiments directed to
Pummerer rearrangements starting from phthalate complex
Ϫ1
sorption bands appear at 1996 and 1925 cm . A similar
1
3
trend is seen for the C NMR chemical shifts of the car-
bonyl ligand carbon atoms (21: δ ϭ 231.1, 22: δ ϭ 228.9,
2
3: δ ϭ 226.7). In the mass spectra, all three compounds
show a significant peak at m/z ϭ 128, which has to be attri-
1
0 also gave only unsatisfactory results, usually only hy-
6
[12]
buted to the η coordinated benzynechromium cation.
[13]
drolysis to the diacid complex is observed.
Therefore
In order to deprotect all three keto functionalities a vari-
ety of reaction conditions for acetal hydrolysis were tried.
Unfortunately all attempts failed: either the acetal group at
C-2 could not be hydrolyzed or oxidative decomplexation
and decomposition occurred. We concluded that the unpro-
tected keto groups in 22 and 23 were incompatible with the
routes via 1,3-indandione complex 6 were tried next.
The 1,3-Indandione Route
The synthesis of 1,3-indandione complex 6 deserves some
desired hydrolysis. Therefore, 22 and 23 were reduced with interest because a number of syntheses of ninhydrin start
sodium borohydride to give rac-24 and 25 with complete from 1,3-indandione (31).[ Usually the activated methyl-
diastereoselectivity in 96% and 89% yield, respectively. Hy- ene group is functionalized and transformed into a (hy-
14]
Eur. J. Org. Chem. 1999, 167Ϫ179
169

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
drated) keto group by hydrolytic or oxidative processes. We cis diol as a diastereomerically pure product; according to
felt that such reaction sequences might eventually lead to 7 the usual attack of the nucleophile from the face opposite
and 8.
to the tricarbonylchromium group we assign formula 34 to
As the direct complexation of 1,3-indandione using hexa- this product.[2,4,15Ϫ18] Knoevenagel condensation product
carbonylchromium failed, we resorted to the acetal route to 35 was obtained as a side product of the acetal hydrolysis
prepare the complex. 31 was transformed to the new diace- in 5% yield beside 90% of 6, when the reaction was carried
tal 32 under standard reaction conditions in 81% yield. It out in a 1:1 mixture of 50% sulfuric acid/acetone. 35 is the
2
should be mentioned that benzene apparently is neccessary first complex in this series with three sp hybridized carbon
for aceotropic water removal; use of toluene instead re- atoms in the anellated ring.
sulted in a reduced yield of only 38% of 32. The long reac-
tion time is neccessary because shorter ones lead to signifi-
cant amounts of monoacetal. Diacetal 32 can be coordi-
nated to chromium by treatment with hexacarbonylchro-
mium under standard reaction conditions to give 33 in 82%
yield as an air sensitive yellow solid. Crystals of 33 suitable
for an X-ray crystal structure analysis (Figure 2) were
grown from ethyl acetate/petroleum ether (1:1).
Functionalization of 6 at C-2
As there are some published syntheses of ninhydrin start-
ing from 1,3-indandione (29) via functionalization at C-2
some experiments along these line were undertaken. First,
introduction of an oxime function at C-2 was attempted by
treatment of 6 with sodium nitrite in diluted sulfuric acid.
Treatment of the desired oxime with formalin solution and
sulfuric acid should lead to 8.[ However, in contrast to
the uncoordinated 1,3-indandione (31), no reaction oc-
curred with chromium complex 6.
19]
Next, 6 was treated with dimethylformamide dimeth-
ylacetal [dimethoxy(dimethylamino)methane] resulting in
the formation of enamine 36 in 94% yield. It is known that
Figure 2. Structure in the crystal and numbering scheme of 33.[
11]
hydrated 1,2,3-tricarbonyl compounds can be obtained
˚
Selected bond lengths [A]: C1ϪC2 1.538(4), C2ϪC3 1.531(4), from such enamines by oxidation with singulett oxygen or
C3ϪC3a 1.514(4), C3aϪC4 1.415(4), C4ϪC5 1.401(4), C5ϪC6
.417(4), C6ϪC7 1.395(4), C7ϪC7a 1.413(4), C7aϪC1 1.512(4),
[20]
ozone.
Most recently a synthesis of thianinhydrin has
1
been published in which the oxidation was performed with
dimethyldioxirane (DDO),[ which is an oxidant far more
compatible with a low valent tricarbonylchromium complex
than singulett oxygen or ozone.[
C3aϪC7a 1.400(4), C1ϪO1 1.404(4), C1ϪO2 1.433(3), C3ϪO3
21]
1.417(3), C3ϪO4 1.423(4), CrϪCArene 2.204(3) Ϫ 2.218(3).
The crystal structure shows that C-2 is slightly bent
22Ϫ26]
towards the tricarbonylchromium group, presumably as a
result of the steric bulk of the adjacent ethylenedioxy sub-
stituents. However, this effect is much smaller than in 21.
Due to the smaller steric loading the bond lengths C1ϪC2
˚
and C2ϪC3 in 33 [1.538(4), 1.531(4) A] are significantly
shorter than the corresponding bond lengths in 21
˚
[
1.557(3), 1.565(4) A]. As in 21, no CO ligand is located
below the anellated ring.
Another 1,3-indandione derivative which was trans-
Hydrolysis of the acetal functionalities in 33 was easily formed into ninhydrin by oxidation with DDO in high
achieved by treatment with 50% sulfuric acid/THF (1:2) yield, is 2-diazo-1,3-indandione.[ To test in how far simi-
27]
6
and gave tricarbonyl(η -1,3-indandione)chromium(0) (6) in lar chemistry would be possible with the corresponding
9
4% yield. Reduction of 6 with sodium borohydride gave a chromium complex, 6 was treated with tosyl azide at 20°C
170
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
under basic reaction conditions to give 2-diazo-1,3-indan- enium dioxide.[30] The oxidation of 1,3-diphenyl-1,3-pro-
dione complex 37 in 85% yield as an air stable solid. 36 and panedione to 1,3-diphenyl-1,2,3-propanetrione with Dess-
3
7 were fully characterized by their spectroscopic data. The Martin periodane has been reported by Golec et al. more
IR absorptions of the carbonyl ligands (36: ν˜ ϭ 1916, 1964 recently.[ However, both reagents led to oxidative decom-
31]
Ϫ1
Ϫ1
cm , 37: ν˜ ϭ 1944, 1996 cm ) as well as the chemical plexation or decomposition when applied to 6. The oxi-
shifts of the 13C-NMR signals of their carbon atoms (36: dation of 1,3-diphenyl-1,3-propanedione to 1,3-diphenyl-
δ ϭ 232.0, 37: δ ϭ 229.4) and their different colours (36: 1,2,3-propanetrione and its hydrate has also been per-
orange, 37: brown) indicate that the ligands in 36 and 35 formed by Adam et al. with 4 equiv. of dimethyldioxirane
are much different from one another, the enamine substi- (DDO) in 98% yield.[ When 1,3-indandione complex 6
tuted ligand of 36 being more electron rich than the diazo was treated with 3 equiv. of DDO in acetone at Ϫ28°C, a
substituted ligand of 37. The formation and stability of fast reaction occurred. An intermediate, presumably 40, was
compounds 35, 36, and 37 show that 1,3-indandione com- observed by TLC, and after hydrolysis and purification by
32]
2
6
plexes with an sp hybridization at C-2 can exist, and we column chromatography, tricarbonyl(η -ninhydrin)chrom-
felt that the synthesis of the indantrione complex should ium(0) (8) was isolated in 75% yield as a red-brown, moder-
also be possible despite its special electronic properties.
ately air sensitive solid. The reaction could be stopped at
Next, oxidation of 36 and 37 with DDO was tried. The the intermediate step, when only 1 equiv. of DDO was used.
reagent was prepared according to the procedure by Adam Unfortunately, attempts to isolate and characterize the in-
[28]
et al.
36 and 37 were carefully treated with DDO at Ϫ78, termediate so far failed, because the compound rapidly de-
Ϫ28, and at 20°C. Use of up to 3 equiv. of DDO caused composed during the column chromatography. The MS and
no reaction. Use of more than 3 equiv. of DDO caused a IR spectra obtained are in accord with 40. To our knowl-
slow oxidative decomplexation of 36 at Ϫ78 and at Ϫ28°C, edge this is the first example of oxidation at a carbon atom
as well as at 20°C the decomplexation occurred immedi- with DDO in a tricarbonylchromium complex. Although
ately. With 37 slow oxidative decomplexation was observed DDO has been used as an oxidative decomplexation re-
at all three temperatures, when 5 equiv. of DDO were used. agent,[ we do not observe any decomposition in the reac-
Longer reaction times did not change these results. There- tion reported here.
fore, in contrast to their uncoordinated ligands, 36 and 37
33]
prove to be unsuitable as precursors for 7 or 8.
Two other experiments were carried out with diazo com-
pound 37. First, 37 was treated with styrene in the presence
of rhodium(II) acetate. This salt causes loss of nitrogen with
formation of a carbene. We were interested in the diastereo-
selectivity of the cycloaddition of the derived carbene with
styrene and observed the formation of a diastereomerically
pure spirocyclopropane derivative in 32% yield. Although
As the final reaction product only 8 was detected by
we did not obtain crystals suitable for an X-ray crystal TLC. However, in addition to the complete set of signals of
structure analysis, we regard the obtained complex as the ninhydrin complex 8 the complete set of signals of indan-
anti diastereoisomer 38 for steric reasons. Next, 37 was trione complex 7 was observed in the 13C-NMR spectrum,
[
34]
treated with phenylethyne in the presence of rhodium(II) indicating an equilibrium between 8 and 7.
8 and 7 were
1
13
acetate. As result of a 1,3-dipolar cycloaddition, the anel- characterized spectroscopically by H- and C-NMR as
lated furan 39 was formed in 70% yield. The formation of well as by their IR and mass spectra. In addition, there is
3
9 corresponds to the reaction of the uncoordinated li- an X-ray structure analysis of 8, which confirms its consti-
[29]
gand,
apparently the electron withdrawal of the tricar- tution. However, the crystal quality was only poor so that
bonylchromium fragment does not influence the regioselec- structural data cannot be discussed here. The chemical shift
tivity of the cycloaddition.
of the carbon atoms of the carbonyl ligands in 7 is δ ϭ
27.4 (in [D ]acetone). This documents that 7 is more elec-
2
6
tron poor than its lower homologue 2 whose carbonyl li-
gand 13C-chemical shift is δ ϭ 228.3 (in [D ]THF).
[35]
Un-
8
fortunately, the IR absorptions of 7 could not yet be deter-
mined, because the complex exists only in equilibrium with
8
, but according to the known correlation between 13C-
NMR shift of carbonyl ligands and the IR absorptions of
these ligands the smaller 13C-NMR chemical shift can be
taken as evidence for a reduced back bonding of the car-
bonyl ligands in 7 as compared to those in 2.[
35,36]
The mass
Direct Oxidation of 6:
Formation of the Ninhydrin Complex
spectrum of ninhydrin complex 8 does not show a molecu-
lar ion peak at m/z ϭ 314. The highest signal is observed
The direct oxidation of 1,3-indandione to ninhydrin was at m/z ϭ 296 corresponding to the dehydrated indantrione
performed by Teeters and Shriner as early as 1933 with sel- complex 7. The base peak is observed at m/z ϭ 128 corre-
Eur. J. Org. Chem. 1999, 167Ϫ179
171

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
6
ϩ
sponding to the η benzyne-Cr ion which was observed from the face opposite to the tricarbonylchromium group
and characterized in the mass spectrum of 2 already.[
12]
to some extent.
One important problem, which we could not solve so far,
In a first experiment ninhydrin complex 8 was treated wih
is the dehydration of ninhydrin complex 8 with formation 2,3-dimethyl-1,3-butadiene (41) in THF for 72 h at 20°C in
˚
of pure indantrione complex 7. This might be possible the presence of some molecular sieves (3 A). Cycloadducts
either by physical or by chemical methods. Attempts to de- 42 and 43 were obtained in 55% yield as a mixture of dia-
Ϫ3
13
1
hydrate 8 by drying at 20°C or at 50°C at 10 bar failed. stereomers (de ϭ 76%, C NMR, H NMR) in addition to
At higher temperatures thermal decomposition was ob- 13% of unreacted 8, which was recovered. 42 and 43 were
served. This is in accord with the behaviour of uncomplexed identified spectroscopically, including comparison of the
ninhydrin (17), which affords heating up to 190°C to loose data with those of the known ligand.[ So far we did not
37]
[7]
part of its hydrate water. Attempts to remove the hydrate succeed in a separation of the diastereomers and were thus
water azeotropically (benzene, 80°C, cat. PTSA) gave only a unable to confirm their relative configurations beyond any
black suspension of decomposed material. As uncomplexed doubt. However, for steric reasons we assume an attack of
ninhydrin (17) can be dehydrated to indantrione (19) by the diene at the face opposite to the tricarbonylchromium
˚
[37]
treatment with molecular sieves (3A),
8 was treated for group to be preferred, and in accord with results of similar
some time in that way. Although a darkening of the colour reactions reported here we suggest 42 to be the major dia-
of the solution from orange-red to dark red was observed, stereomer.
no enrichment of the dehydrated complexes was detected.
More experiments along this line are under way in our lab-
oratory.
Chemical methods to dehydrate 8 cause problems: Usu-
ally, ninhydrin (17) is dehydrated by boiling it in thionyl
[7]
chloride, a prohibitive procedure for low valent metal
complexes. The presumably increased reactivity of 7 as
compared to 8 does not render a reaction with reagents like
Next, 1-trimethylsilyl-1,3-butadiene (44) was tested. The
trimethyl orthoformiate or 2,2-dimethoxypropane promis- reaction resulted in the formation of cycloadduct rac-45 in
1
13
ing, because an immediate addition of the side product 58% yield as a single diastereomer (de > 95%, H NMR, C
methanol to 7 has to be expected. Similar reactions were NMR). In this case, 20% of unreacted starting material 8
observed upon treatment of ninhydrin (17) with acetanhyd- were recovered. To determine the relative configuration of
[38]
ride or acetyl chloride.
One promising way, which is be- the cycloadduct at C-2, rac-45 was reduced with sodium
ing tested in our group is the reaction of ninhydrin (17) borohydride to give rac-46 in 90% yield. Such a reduction
with trimethylsilyl chloride under basic reaction conditions is known to give the endo alcohol as a result of hydride
[39]
followed by elimination of hexamethyldisiloxane.
attack from the face opposite to the tricarbonylchromium
group.[
42,43]
NOE experiments confirmed the assigned rela-
tive configuration: Irradiation at the resonance frequency
of the benzylic protons gave an NOE at the methylene pro-
tons and vice versa. In conclusion, 8 had diastereoselec-
Reactions of Ninhydrin Complex 8
Hetero-DielsϪAlder reactions are an important tool in tively been attacked by the diene from the face opposite to
[40]
[44]
the synthesis of heterocycles.
Aldehydes and electron de- the tricarbonylchromium group.
ficient ketones can serve as heterodienophiles in such re-
ations leading to 5,6-dihydro-2H-pyrans, which are valuable
intermediates in natural product syntheses, especially in
[
41]
carbohydrate chemistry.
few ketones reported to undergo this reaction with the cen-
tral keto group.
Indantrione (19) is one of the
[37]
The regioselectivity of this reaction is a
result of the electron distribution in indantrione (19) with
the central keto group being the most electron deficient one.
With respect to complexes 7 and 8 we were interested to
know in how far the equilibrium mixture of the ninhydrin
and the indantrione complexes would react in a hetero-
DielsϪAlder fashion. Due to the electron withdrawal of the
tricarbonylchromium group the regioselectivity of the reac-
tion did not neccessarily have to be the same as in the reac-
tion of uncomplexed indantrione (19): The benzylic keto
A similar result was obtained upon treatment of ninhy-
groups are more electrophilic than in the ligand, and the drin complex 8 with 1-methoxy-3-trimethylsiloxy-1,3-buta-
difference in electrophilicity between them and C-2 de- diene (47, Danishefsky diene[ ). Complex rac-48 was ob-
45]
1
creases. Finally, we wanted to verify the suggestion that the tained as an orange-red solid in 78% yield (de > 95%, H
diene would diastereoselectively attack the heterodienophile NMR, 13C NMR) as a result of a hetero-DielsϪAlder
172
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
cycloaddition followed by hydrolysis of the intermediate si- ether, dibutyl ether, dioxane, THF, petroleum ether (40Ϫ70°C),
pentane, hexane, heptane, and benzene were distilled from sodium-
lyl enol ether. In addition, 23% unreacted starting material
potassium alloy/benzophenone. Dichloromethane was distilled
8
were recovered. To our surprise we found that rac-48 does
1
from calcium chloride. Ϫ H NMR: Bruker WP 80 (80 MHz), WP
not easily undergo a methanol elimination to 49. Fortu-
nately, crystals suitable for an X-ray crystal structure analy-
sis (Figure 3) were obtained from dichloromethane/petro-
leum ether.
1
3
2
00 SY (200.1 MHz), AM 400 (400.1 MHz). Ϫ C NMR: Bruker
WP 200 SY (50.3 MHz), AM 400 (100.1 MHz). Signal multiplicit-
ies were determined with APT and DEPT techniques. Chemical
[46,47]
shifts refer to δTMS ϭ 0 or to residual solvent signals.
Air
sensitive samples were prepared and sealed in an argon atmosphere.
Ϫ IR: Perkin-Elmer FT-IR 580 and 1710. Ϫ MS: Finnigan MAT
1
12, 312 at 70 eV. Ϫ HRMS: Finnigan MAT 312, VG Autospec,
peak matching with PFK. Ϫ Combustion analyses: Heraeus CHN
Rapid. Ϫ Melting points (uncorr.) were determined in sealed glass
tubes with an apparatus according to Dr. Tottoli. Ϫ Column chro-
matography: Silica gel (J. T. Baker, 40 µm) was degassed by heating
it with a heat gun at reduced pressure followed by setting it under
normal pressure with argon. This sequence was repeated five times.
Separations were performed using flash chromatography.[ Unless
otherwise indicated, chiral compounds were obtained as racemates.
48]
1
,3-Bis(ethylenedioxy)-2-indanone (18): A solution of 5.00 g (28.1
mmol) of ninhydrin (17), 4.00 g (3.6 mL, 64.5 mmol) of 1,2-ethane-
diol, and 150 mg (1.0 mmol) of para-toluenesulfonic acid (PTSA)
in 100 mL of benzene is heated at reflux for 20 h. The solution
changes its colour from yellow to colourless. After solvent removal
at reduced pressure a colourless solid is obtained, which is dis-
solved in 50 mL of ethyl acetate. The solution is washed three times
each with 10 mL of a saturated aqueous solution of sodium bicar-
bonate and water. After filtration of the crude product through a
short silica gel column with diethyl ether as the eluent 5.90 g (23.9
mmol, 85%) of 18 is obtained as a colourless powder (m. p. 105°C,
DSC), which becomes yellow in the light. Ϫ IR (KBr): ν˜ ϭ 2973
Ϫ1
(
w) cm , 2905 (w), 1777 (m, CO), 1471 (w), 1330 (m), 1310 (m),
1
229 (w), 1029 (s, acetal-CϪO), 945 (m), 864 (w), 765 (m), 740 (w).
1
Ϫ H NMR (200.1 MHz, CDCl
H, 8(8Ј)-H, 9(9Ј)-H], 7.57 (s, 4 H, arom. H). Ϫ C NMR (50.3
MHz, CDCl ): δ ϭ 66.5 [ϩ, C-8(8Ј) or C-9(9Ј)], 66.6 [ϩ, C-8(8Ј)
or C-9(9Ј)], 101.4 [ϩ, C-1(3)], 124.8 [Ϫ, C-4(7)], 132.0 [Ϫ, C-5(6)],
3
): δ ϭ 4.28 ϩ 4.39 [2m, 4 H ϩ 4
1
3
3
1
2
38.5 [ϩ, C-3a(7a)], 209.4 (ϩ, C-2). Ϫ MS (70 eV, 20°C): m/z (%) ϭ
Figure 3. Structure in the crystal and numbering scheme of 48.[
11]
ϩ
ϩ
48 (2) [M ], 220 (34) [M Ϫ CO], 188 (7), 176 (10), 162 (7), 148
˚
Selected bond lengths [A]: C1ϪC2 1.546(5), C2ϪC3 1.544(5),
ϩ
(100) [C H O ], 133 (18), 104 (51), 88 (23), 77 (31). Ϫ C H12O5
9 8 2 13
C3ϪC3a 1.462(5), C4ϪC5 1.400(5), C5ϪC6 1.403(5), C6ϪC7
(248.23): calcd. C 62.90, H 4.87; found C 62.52, H 4.88.
1
2
.369(5), C7ϪC7a 1.411(5), C7aϪC1 1.450(5), CrϪCArene
.170(4)Ϫ2.213(3).
-Ethylenedioxy-1,3-indandione (20):[9] A suspension of 1.00 g (6.2
2
mmol) of indantrione (19), 0.51 mL (7.2 mmol) of 2-bromoethanol
and 3 mL of THF is mixed with 1.00 g (7.2 mmol) of potassium
carbonate and 3 mL of DMSO. After 24 h at 40°C the yellow-
brown suspension is added to 20 mL of water, causing formation
of a yellow precipitate. This is filtered off, washed with water until
no more potassium carbonate can be detected (pH). After drying
at 0.001 mbar 1.21 g (5.9 mmol, 95%) of 20 is obtained as a bright
yellow powder (m. p. 138°C), which was identified spectroscopi-
The structure confirms the NOE results and is the proof
that the diene in these reactions attacks from the face of
the ligand opposite to the tricarbonylchromium group. The
spiro-anellated heterocycle shows a chair conformation,
and presumably due to the steric demand of the spiro-anel-
lated ring no carbonyl ligand is located below the five-mem-
bered ring.
The successful hetero-DielsϪAlder reactions starting cally.[9,10]
from ninhydrin complex 8 show that this compound may
be used as a substitute of the dehydrated indantrione com-
plex 7. We currently investigate reactions of 8 and related
complexes in more depth with some emphasis on addition
1
6
,2,3-Tris(ethylenedioxy)indane (16): a) 4.00 g (19.6 mmol) of 20,
.90 g (6.2 mL, 111.1 mmol) of 1,2-ethanediol, and 15 mg (0.1
mmol) of PTSA in 100 mL of benzene is heated at reflux with
azeotropic water removal. The yellow colour of the solution fades
reactions of organometallic substrates to the keto groups in out during this time. After solvent removal a colourless solid re-
the anellated ring.
mains, which is recrystallized from ethyl acetate. 4.60 g (15.8 mmol,
8
1%) of 16 is obtained as colourless, long needles (m. p. 180°C).
b) A suspension of 4.00 g (16.1 mmol) of 18, 1.36 mL (19.2 mmol)
of 2-bromoethanol, and 8 mL of THF is mixed with 2.60 g (19.2
mmol) of potassium carbonate and 8 mL of DMSO. The yellow
mixture is stirred for 24 h at 50°C and becomes white. THF is
Experimental Section
General: All operations were performed in flame-dried reaction ves-
sels in an argon atmosphere using the Schlenk technique. Diethyl
Eur. J. Org. Chem. 1999, 167Ϫ179
173

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
removed at reduced pressure, and DMSO is removed by filtration.
The white residue is washed with water until a pH indicator does
no more show basic reaction. After recrystallization from ethyl dec.). Ϫ IR (KBr): ν˜ ϭ 3079 (w) cm , 2963 (w), 2905 (w), 1986
orange solid obtained is recrystallized from diethyl ether/petroleum
ether. 153 mg (0.4 mmol, 85%) of 22, orange crystals (m. p. 175°C,
Ϫ1
acetate 3.10 g (10.6 mmol, 66%) of 16 is isolated as colourless,
(s, CO), 1929 (s, CO), 1727 (s, CO), 1520 (w), 1471 (w), 1431 (w),
long needles.
1276 (w), 1186 (m), 1076 (w), 1033 (s, acetal-CϪO), 951 (w), 898
1
(w), 804 (w), 720 (w), 649 (m), 615 (m). Ϫ H NMR (200.1 MHz,
1
6: IR (KBr): ν˜ ϭ 2991 (w) cmϪ1, 2955 (w), 2884 (m), 1472 (w),
CDCl
system, 4 H, arom. H). Ϫ 13C NMR (50.3 MHz, CDCl
ϩ, CH ), 66.8 (ϩ, CH ), 67.1 (ϩ, CH ), 67.9 (ϩ, CH
C-5 or C-6), 84.8 (Ϫ, C-5 or C-6), 90.4 (Ϫ, C-3a), 92.1 (ϩ, C-2),
3
): δ ϭ 4.02Ϫ4.53 (m, 8 H, CH
2
), 5.23Ϫ5.92 (ABCD line
): δ ϭ 66.7
), 84.2 (Ϫ,
1321 (w), 1294 (w), 1270 (m), 1206 (w), 1157 (w), 1078 (m), 1042
3
(
(
4
s, acetal-CϪO), 1008 (m), 980 (m), 956 (m), 868 (w), 785 (m), 655
w). Ϫ H NMR (200.1 MHz, CDCl ): δ ϭ 4.15 [s, 4 H, 9(9Ј)-H],
.23 [s, 8 H, 8(8Ј)-H, 10(10Ј)-H], 7.42 (s, 4 H, arom. H). Ϫ 13
(
2
2
2
2
1
3
C
9
1
1
3.1 (Ϫ, C-7), 103.7 (ϩ, C-3 or C-7a), 105.6 (ϩ, C-3 or C-7a),
3
NMR (50.3 MHz, CDCl ): δ ϭ 66.4 [ϩ, C-8(8Ј), C-(10,10Ј)], 66.8
13.8 (ϩ, C-3a), 196.2 (ϩ, C-1), 228.9 (ϩ, CO). Ϫ MS (70 eV,
[ϩ, C-9(9Ј)], 109.1 [ϩ, C-1(3)], 112.2 (ϩ, C-2), 123.1 [Ϫ, C-4(7)],
ϩ
ϩ
00°C): m/z (%) ϭ 386 (2) [M ϩ 2], 385 (4) [M ϩ 1], 384 (8)
130.3 [Ϫ, C-5(6)], 139.9 [ϩ, C-3a(7a)]. Ϫ MS (70 eV, 70°C): m/z
ϩ
ϩ
[M ], 340 (24), 300 (14) [M Ϫ 3 CO], 284 (10), 256 (28), 228 (8),
ϩ
ϩ
ϩ
(
(
(
%) ϭ 294 (4) [M ϩ 2], 293 (12) [M ϩ 1], 292 (70) [M ], 220
89), 176 (13), 148 (100) [C
20). Ϫ HRMS, C15 : calcd. 292.09668, found 292.09494. Ϫ
ϩ
ϩ
2
1
12 (100) [(C
9
H
4
O
3
)Cr ] , 184 (8), 148 (8), 128 (43) [(C
12CrO : calcd. 383.99372,
(383.99): calcd. C 50.01, H 3.15;
6 4
H )Cr ],
ϩ
9 8 2
H O ], 133 (26), 104 (39), 88 (11), 76
04 (10), 91 (16), 80 (24). Ϫ HRMS, C16
H
8
16 6
H O
found 383.99432. Ϫ C16H12CrO
8
C
15
H
16
O
6
(292.09): calcd. C 61.64, H 5.52; found C 61.58, H 5.45.
found C 48.46, H 3.21.
6
Tricarbonyl[η -1,2,3-tris(ethylenedioxy)indane]chromium(0) (21): A
mixture of 2.00 g (6.8 mmol) of 16 and 1.65 g (7.5 mmol) of hexa-
carbonylchromium(0) in 100 mL of dibutyl ether and 10 mL of
THF is heated at reflux for 20 h, the colour changing to dark yel-
low. The solvent is condensed at reduced pressure at 50°C into a
cold trap, and the remaining solid is recrystallized from diethyl
ether/petroleum ether. 2.40 g (5.6 mmol, 82%) of 21, yellow, long
6
Tricarbonyl(η -2-ethylenedioxy-1,3-indandione)chromium(0) (23): A
solution of 1.00 g (2.3 mmol) of 21 in 20 mL of THF is treated
with 50 mL of conc. hydrochloric acid. The initially yellow solution
is stirred at 50°C until no more 22 is detected by TLC (ca. 4 h,
vide supra). 100 mL of water is added to the dark red solution,
which then is extracted five times with 40 mL of diethyl ether each.
The collected organic layers are washed three times each with 40
Ϫ1
needles (m. p. 210°C). Ϫ IR (KBr): ν˜ ϭ 2965 (w) cm , 2896 (w),
4
mL of water, dried with MgSO , and filtered. The solvent is re-
1
1
972 (s, CO), 1903 (s, CO), 1474 (w), 1275 (m), 1227 (w), 1128 (w),
069 (m), 1039 (s, acetal-CϪO), 1011 (w), 980 (w), 955 (w), 916
moved at reduced pressure, and the red solid obtained is recrys-
tallized from diethyl ether/petroleum ether. 0.73 g (2.1 mmol, 92%)
of 23, red crystals (m. p. 170°C, dec.). Ϫ IR (KBr): ν˜ ϭ 3101 (w)
1
(w), 819 (w), 665 (m), 626 (m). Ϫ H NMR (200.1 MHz, CDCl
3
):
δ ϭ 3.98Ϫ4.35 [m, 12 H, 8(8Ј)-H, 9(9Ј)-H, 10-H, 11-H], 5.23 ϩ
Ϫ1
cm , 2904 (w), 1996 (s, CO), 1925 (s, CO), 1746 (s, CO), 1723 (s,
.37 (AAЈBBЈ line system, 2 ϫ 2 H, arom. H). Ϫ 1 C NMR (50.3
MHz, CDCl ): δ ϭ 66.5 (ϩ, C-10 or C-11), 66.6 [ϩ, C-8(8Ј) or C-
(9Ј)], 66.8 (ϩ, C-10 or C-11), 67.4 [ϩ, C-8(8Ј) or C-9(9Ј)], 84.4
Ϫ, C-4(7)], 90.9 [Ϫ, C-5(6)], 107.7 [ϩ, C-1(3) or C-3a(7a)], 108.5
ϩ, C-1(3) or C-3a(7a)], 109.7 (ϩ, C-2), 231.1 (ϩ, CO). Ϫ MS (70
3
5
CO), 1514 (w), 1472 (w), 1192 (s, acetal-CϪO), 1146 (m), 1020 (s),
3
9
51 (m), 905 (w), 838 (w), 739 (w), 666 (w), 647 (s), 607 (s), 516
9
[
[
1
(w). Ϫ H NMR (200.1 MHz, CDCl
3
): δ ϭ 4.41 (AAЈBBЈ line
), 5.69 ϩ 5.88 (AAЈBBЈ line system, 2ϫ 2 H,
): δ ϭ 67.9 (ϩ, CH ),
), 85.8 [Ϫ, C-5(6)], 92.8 [Ϫ, C-4(7)], 95.4 (ϩ, C-2),
6.1 [ϩ, C-3a(7a)], 193.2 [ϩ, C-1(3)], 226.7 (ϩ, CO). Ϫ MS (70 eV,
system, 4 H, CH
arom. H). Ϫ C NMR (50.3 MHz, CDCl
6
9
1
2
1
3
ϩ
ϩ
3
2
eV, 100°C): m/z (%) ϭ 430 (3) [M ϩ 2], 429 (4) [M ϩ 1], 428
8.1 (ϩ, CH
2
ϩ
ϩ
ϩ
(
13) [M ], 372 (23) [M Ϫ 2 CO], 344 (33) [M Ϫ 3 CO], 292 (16),
ϩ
2
(
56 (39), 228 (11), 212 (100) [(C
14). Ϫ HRMS, C18 16CrO : calcd. 428.01994, found 428.02011.
(428.32): calcd. C 50.48, H 3.77; found C 50.45,
9 4 3
H O )Cr ], 148 (21), 128 (27), 104
ϩ
ϩ
00°C): m/z (%) ϭ 340 (28) [M ], 284 (13) [M Ϫ 2 CO], 256 (27)
H
9
ϩ
ϩ
[
M
Ϫ 3 CO], 212 (100) [(C
9
H
4
O
3
)Cr ], 184 (8), 128 (39)
)Cr ], 104 (8), 91 (5), 80 (6), 76 (7). Ϫ HRMS, C14 CrO
calcd. 339.96751, found 339.96847. Ϫ C14 CrO (339.97): calcd.
, yellow, crystal C 49.43, H 2.37; found C 49.44, H 2.66.
size 0.40 ϫ 0.40 ϫ 0.25 mm, a ϭ 8.506(2), b ϭ 17.211(3), c ϭ
Ϫ C18H16CrO
9
H 3.77.
ϩ
[(C
6
H
4
H
8
7
:
H
8
7
Crystal Structure Analysis of 21:[11]
18 9
C H16CrO
6
Tricarbonyl[η -2,3-bis(ethylenedioxy)-endo-1-indanol]chromium(0)
24): 0.20 g (5.7 mmol) of sodium borohydride is added to a solu-
˚
˚
3
1
2.532(2) A, α ϭ 90, β ϭ 94.13(2), γ ϭ 90°, V ϭ 1829.9(6) A ,
(
Ϫ1
Ϫ1
dcalcd. ϭ 1.555 gcm , µ ϭ 6.80 cm , Z ϭ 4, crystal system mono-
tion of 1.75 g (4.6 mmol) of 22 in 60 mL of THF/ethanol (1:1).
Within 1 min the colour changes from red to yellow. The mixture
is stirred for 2 h at 25°C, then 100 mL of water is added. The
mixture is extracted three times with 50 mL of diethyl ether each.
The collected organic layers are washed three times each with 30
mL of water, dried with MgSO , and filtered. After solvent removal
4
at reduced pressure a yellow solid is obtained which is purified by
column chromatography at silica gel (diethyl ether/petroleum ether,
clinic, space group P2
1
/a (Nr. 14), Stoe IPDS diffractometer, λ ϭ
˚
0
.71073 A, 125 exposures, 2Θmax 56.2°, 16285 measured reflections
(
±h, ±k, ±l), 4292 independent (Rint ϭ 0.03) and 2876 observed
reflections [I > 2σ(I)], 255 refined parameters, H atoms included
into the refinement using the riding model, R ϭ 0.0392, wR
.1141 based on F , min., max. residual electron density Ϫ0.30,
1
2
ϭ
2
0
0
1
˚
Ϫ3
.36 eA ; programs used: SHELXS-86, SHELXL-93. CCDC ϭ
01981.
1
:1, length 20 cm, л 3 cm). 1.70 g (4.4 mmol, 96%) of 24 (de >
6
Tricarbonyl[η -2,3-bis(ethylenedioxy)-1-indanone]chromium(0) (22): 95%, NMR), bright yellow solid (m. p. 160°C, dec.). Ϫ IR (KBr):
Ϫ1
200 mg (0.5 mmol) of 21 is treated with 10 mL of conc. hydro-
ν˜ ϭ 3626 (w, OH) cm , 3100 (w), 2962 (w), 2899 (w), 1976 (s,
chloric acid. The green-yellow mixture is stirred at 25°C for 2 h,
the colour changes to orange-yellow. The reaction is traced by TLC
CO), 1898 (s, CO), 1434 (w), 1262 (m), 1203 (w), 1035 (m), 949
1
(w), 663 (w), 629 (m). Ϫ H NMR (200.1 MHz, [D
6
]acetone): δ ϭ
3
[ethyl actate, R
f
(21) ϭ 0.24, R
f
(22) ϭ 0.59, R
f
(23) ϭ 0.69]. When
3.50 (d, 1 H, J1,OH ϭ 10.0 Hz, OH), 3.93Ϫ4.37 (m, 8 H, acetal-
3
no more 21 and only a minimum amount of 23 is detected, 80 mL
of water is added, and the mixture is extracted three times each
H), 4.88 (d, 1 H, J1,OH ϭ 10.0 Hz, 1-H), 5.44Ϫ5.70 (m, 4 H, arom.
H). Ϫ 13C NMR (50.3 MHz, [D
6
]DMSO): δ ϭ 65.4 (ϩ, CH
2
), 65.5
with 40 mL of diethyl ether. The collected organic layers are (ϩ, CH
2
), 66.2 (ϩ, CH
2
), 66.8 (ϩ, CH ), 70.6 (Ϫ, C-1), 86.4 (Ϫ,
2
washed three times each with 20 mL of water, dried with MgSO
and filtered. The solvent is removed at reduced pressure, and the
4
,
C-4 or C-7), 86.9 (Ϫ, C-4 or C-7), 92.6 (Ϫ, C-5 or C-6), 93.1 (Ϫ,
C-5 or C-6), 108.3 (ϩ, C-2 or C-3), 108.5 (ϩ, C-2 or C-3), 112.1
174
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
(
(
(
(
ϩ, C-3a or C-7a), 114.6 (ϩ, C-3a or C-7a), 232.9 (ϩ, CO). Ϫ MS 341.98465. Ϫ C14
70 eV, 140°C): m/z (%) ϭ 387 (3) [M ϩ 1], 386 (9) [M ], 330 C 48.97, H 2.99.
H
6
CrO
7
(341.98): calcd. C 49.14, H 2.95; found
ϩ
ϩ
ϩ
ϩ
36) [M Ϫ 2 CO], 302 (54) [M Ϫ 3 CO], 256 (9), 242 (42), 214
ϩ
2,2-Diethoxy-1,3-bis(ethylenedioxy)indane (27): A mixture of 1.00 g
4.00 mmol) of 18, 0.48 mL (8.00 mmol) of anhydrous ethanol,
.18 mL (8.00 mmol) of triethyl orthoformiate, and 50 mg (0.30
98) [(C
9
H
6
O
3
)Cr ], 198 (8), 186 (55), 173 (100), 158 (13), 133 (11),
14CrO : calcd. 386.00938,
(386.01): calcd. C 49.75, H 3.65;
(
1
1
05 (15), 89 (18), 52 (75). Ϫ HRMS, C16
H
8
found 386.00955. Ϫ C16H14CrO
8
mmol) of PTSA is stirred for 72 h at 25°C. Then 10 mL of a satu-
rated aqueous solution of sodium carbonate is added, and the mix-
ture is extracted three times with 5 mL of ethyl acetate each. The
collected organic layers are washed three times wih 2 mL of water
each and are then dried with potassium carbonate. After solvent
removal at reduced pressure a colourless solid is obtained which is
recrystallized from diethyl ether/petroleum ether, (2:1). 0.84 g (2.6
found C 49.86, H 3.70.
6
Tricarbonyl(η -2-ethylenedioxy-endo-1,endo-3-indandiol)-
chromium(0) (25): 67 mg (1.8 mmol) of sodium borohydride is ad-
ded to an orange solution of 250 mg (0.7 mmol) of 23 in THF/
ethanol (1:1). The mixture is stirred for 2 h at 2°C, and the colour
changes to yellow. 50 mL of water is added, and the mixture is
extracted three times with 20 mL of diethyl ether each. The col-
lected organic layers are washed three times each with 30 mL of
mmol, 65%) of 27, colourless solid (m. p. 109°C). Ϫ IR (KBr): ν˜ ϭ
Ϫ1
2
1
(
974 (m) cm , 2929 (w), 2899 (m), 1479 (w), 1390 (w), 1320 (w),
267 (m), 1229 (m), 1117 (m), 1083 (s), 1050 (s, acetal-CϪO), 1005
m), 964 (m), 776 (m), 645 (w). Ϫ H NMR (200.1 MHz, CDCl
δ ϭ 1.21 (t, 6 H, J ϭ 7.0 Hz, CH
CH CH ), 4.18Ϫ4.30 (m, 8 H, CH
C NMR (100.6 MHz, CDCl
CH ), 65.2 (ϩ,CH CH
4
water, dried with MgSO , and filtered. After solvent removal at
reduced pressure a bright yellow solid is obtained, which is recrys-
tallized from diethyl ether/petroleum ether. 214 mg (0.6 mmol,
1
3
):
), 3.86 (q, 4 H, J ϭ 7.0 Hz,
CHH ), 7.38 (s, 4 H, arom. H).
): δ ϭ 15.6 (Ϫ, CH ), 58.3 (ϩ,
), 105.4 (ϩ, C-2), 111.1 [ϩ, C-1(3)],
3
3
3
2
3
2
2
89%) of 25 (de > 95%, NMR), bright yellow solid (m. p. 175°C,
1
3
Ϫ1
Ϫ
3
3
dec.). Ϫ IR (KBr): ν˜ ϭ 3551 (m, OH) cm , 3110 (w), 2900 (w),
CH
2
3
2
2
1
1
963 (s, CO), 1865 (s, CO), 1475 (w), 1435 (w), 1396 (m), 1263 (w),
278 (m), 1196 (m), 1181 (m), 1123 (w), 1095 (w), 1047 (m), 1015
1
22.8 [Ϫ, C-4(7)], 129.6 [Ϫ, C-5(6)], 140.3 [ϩ, C-3a(7a)]. Ϫ MS (70
ϩ
ϩ
1
eV, 70°C): m/z (%) ϭ 323 (2) [M ϩ 1], 322 (5) [M ], 292 [21], 265
(5), 249 (9), 221 (20), 193 (24), 177 (13), 162 (8), 149 (100) [C
(
m), 955 (w), 672 (m), 634 (m). Ϫ H NMR (200.1 MHz, CDCl
3
):
3
9 9
H O
δ ϭ 2.63 (d, 2 H, J1(3),OH ϭ 12.0 Hz, OH), 4.11Ϫ4.31 (m, 4 H,
), 4.84 [d, 2 H, 3J1(3),OH ϭ 12.0 Hz, 1(3)-H], 5.33 ϩ 5.49
ϩ
2
], 133 (16), 121 (10), 104 (54), 76 (28). Ϫ HRMS, C17
22 6
H O :
CH
AAЈBBЈ line system, 4 H, arom. H). Ϫ C NMR (100.6 MHz,
]DMSO): δ ϭ 65.0 (ϩ, CH ), 66.7 (ϩ, CH ), 72.1 [Ϫ, C-1(3)],
7.4 [Ϫ, C-4(7)], 92.8 [Ϫ, C-5(6)], 114.1 [ϩ, C-3a(7a)], 115.4 (ϩ,
2
13
calcd. 322.14164, found 322.14163. Ϫ C17 (322.14): calcd. C
22 6
H O
(
6
3.34, H 6.88; found C 63.09, H 6.63.
[
D
6
2
2
8
6
Tricarbonyl[η -2,2-diethoxy-1,3-bis(ethylenedioxy)indane]-
chromium(0) (28): A mixture of 460 mg (1.4 mmol) of 27 and 471
mg (2.1 mmol) of hexacarbonylchromium(0) in 50 mL of dibutyl
ether and 5 mL of THF is heated at reflux for 20 h. The solution
changes its colour from colourless to yellow. Upon cooling to room
temperature a yellow solid precipitates. After addition of 20 mL of
petroleum ether the crystallization is completed at Ϫ30°C for 16
h. After decanting the solvent mixture and drying at 0.001 mbar
ϩ
C-2), 233.9 (ϩ, CO). Ϫ MS (70 eV, 100°C): m/z (%) ϭ 345 (3) [M
ϩ
ϩ
ϩ
ϩ 1], 344 (10) [M ], 288 (41) [M Ϫ 2 CO], 260 (100) [M Ϫ 3
CO], 242 (10), 212 (8), 214 (8), 199 (30), 182 (34), 170 (90), 131
(42), 118 (55), 102 (41), 91 (44), 76 (36). Ϫ HRMS, C14
H
12CrO
7
:
calcd. 343.99881, found 343.99894. Ϫ C14H12CrO (344.00): calcd.
C 48.85, H 3.51; found C 49.78, H 3.91.
7
6
Tricarbonyl(η -2-ethylenedioxy-endo-3-hydroxy-1-indanone)-
chromium(0) (26): At 0°C 30 mL of 50% sulfuric acid is added
slowly to a solution of 1.24 g (3.2 mmol) of 24 in 60 mL of acetone.
Within 4 h the colour changes from yellow to deep red. 150 mL of
ice water is added, and the mixture is extracted three times with 40
mL of diethyl ether each. The collected organic layers are washed
5
2
04 mg (1.1 mmol, 79%) of 28 is obtained as a yellow solid (m. p.
15°C, dec.). Ϫ IR (KBr): ν˜ ϭ 2976 (w) cm , 2904 (w), 1976 (s,
Ϫ1
CO), 1912 (s, CO), 1864 (s, CO), 1480 (w), 1440 (w), 1284 (w), 1256
m), 1232 (m), 1116 (w), 1096 (w), 1048 (m), 1000 (w), 660 (m),
(
1
6
24 (m). Ϫ H NMR (400.1 MHz, [D
6
]acetone): δ ϭ 1.18 (t, 3 H,
), 1.21 (t, 3 H, J ϭ 7.2 Hz, CH ), 3.67 (q, 2 H,
CH ), 4.08Ϫ4.31
), 5.46 ϩ 5.62 (AAЈBBЈ line system, 4 H, arom.
H). Ϫ C NMR (100.6 MHz, [D ]acetone): δ ϭ 14.8 (Ϫ, CH ),
4.8 (Ϫ, CH ), 57.6 (ϩ, CH CH ), 57.9 (ϩ, CH CH ), 65.3 (ϩ,
CH CH ), 65.8 (ϩ,CH CH ), 85.4 [Ϫ, C-4(7)], 92.2 [Ϫ, C-5(6)],
04.5 (ϩ, C-2), 110.35 [ϩ, C-3a(7a) or C-1(3)], 110.41 [ϩ, C-3a(7a)
or C-1(3)], 232.1 (ϩ, CO). Ϫ MS (70 eV, 140°C): m/z (%) ϭ 458
3
3
J ϭ 7.2 Hz, CH
J ϭ 7.2, CH
m, 8 H, CH
3
3
three times with 30 mL of water each, dried with MgSO
4
, and
3
3
2
CH
CH
3
), 3.94 (q, 2 H, J ϭ 7.2, CH
2
3
filtered. After solvent removal at reduced pressure an orange solid
is obtained which is purified by column chromatography at silica
gel (diethyl ether/petroleum ether, 1:1, length 50 cm, л 3 cm). 0.83
g (2.4 mmol, 76%) of 26, orange solid (m. p. 160°C). Ϫ IR (KBr):
(
2
2
13
6
3
1
3
2
3
2
3
2
2
2
2
Ϫ1
ν˜ ϭ 3532 (m, OH) cm , 3412 (br), 3096 (w), 2960 (w), 2904 (w),
1
1972 (s, CO), 1892 (s, CO), 1728 (s, CO), 1524 (m), 1432 (w), 1388
(w), 1264 (w), 1200 (m), 1168 (m), 1116 (m), 1036 (m), 1020 (m),
ϩ
ϩ
ϩ
(4) [M ], 402 (66) [M Ϫ 2 CO], 374 (51) [M Ϫ 3 CO], 330 (29),
1
952 (m), 904 (w), 652 (m), 612 (m). Ϫ H NMR (400.1 MHz, [D
6
]-
ϩ
2
86 (26), 258 (79), 242 (61), 226 (34), 212 (94) [(C
85), 173 (28), 157 (88), 148 (51), 128 (33), 104 (37), 52 (100) [ Cr].
Ϫ HRMS, C20 22CrO : calcd. 458.06689, found 458.06690. Ϫ
22CrO
9 4 3
H O )Cr ], 198
acetone): δ ϭ 4.13Ϫ4.36 (m, 4 H, CH ), 4.48 (br, 1 H, OH), 5.20
2
52
(
3
3
3
(
d, 1 H, J3,OH ϭ 6.8 Hz, 3-H), 5.67 (t, 1 H, J5,6 ϭ J6,7 ϭ 6.3 Hz
H
9
or J4,5 ϭ 3J5,6 ϭ 6.3 Hz, 5-H or 6-H), 5.79 (d, 1 H, J6,7 ϭ J4,5
3
3
3
ϭ
C
20
H
9
(458.07): calcd. C 52.41, H 4.83; found C 52.53, H
3
3
6
7
5
.3 Hz, 4-H or 7-H), 5.89 (d, 1 H, J6,7 ϭ J4,5 ϭ 6.3 Hz, 4-H or
4
.86.
3
3
3
3
-H), 6.04 (t, 1 H, J5,6 ϭ J6,7 ϭ 6.3 Hz or J4,5 ϭ J5,6 ϭ 6.3 Hz,
-H or 6-H). Ϫ 13C NMR (100.6 MHz, [D
]acetone): δ ϭ 66.2 (ϩ,
), 66.3 (ϩ, CH ), 69.4 (Ϫ, C-3), 86.0 (Ϫ, C-4 or C-7), 86.2 (Ϫ,
C-4 or C-7), 91.5 (Ϫ, C-6), 92.7 (ϩ, C-2), 95.3 (Ϫ, C-5), 104.6 (ϩ,
6
6
Tricarbonyl(η -2,2-diethoxy-3-ethylenedioxy-1-indanone)-
chromium(0) (29): 30 mL of 50% sulfuric acid is carefully added at
0°C to a solution of 400 mg (0.87 mmol) of 28 in 70 mL of acetone.
CH
2
2
C-3a), 122.6 (ϩ, C-7a), 197.1 (ϩ, C-1), 230.3 (ϩ, CO). Ϫ MS (70 The yellow solution is stirred for 4 h at 20°C, the colour changing
ϩ
ϩ
eV, 130°C): m/z (%) ϭ 344 (3) [M ϩ 2], 343 (5) [M ϩ 1], 342 to dark red. After addition of 100 mL of ice water the mixture is
ϩ
ϩ
ϩ
(
[(C
15) [M ], 286 (36) [M Ϫ 2 CO], 258 (35) [M Ϫ 3 CO], 214 (93)
extracted three times with 30 mL of tert-butylmethyl ether (TBME)
ϩ
9
H
6
O
3
)Cr ], 186 (75), 183 (63), 174 (19), 158 (18), 151 (10), 133 each. The collected organic layers are washed three times each with
(
5
8), 123 (12), 115 (7), 109 (38), 105 (25), 95 (15), 89 (23), 77 (18),
2 (100) [ Cr]. Ϫ HRMS, C14H CrO : calcd. 341.98316, found
6 7
20 mL of a saturated aqueous solution of sodium carbonate and
another three times each with 20 ml of water. After drying with
52
Eur. J. Org. Chem. 1999, 167Ϫ179
175

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
potassium carbonate, filtration, and solvent removal at reduced
pressure a red solid is obtained which is purified by column chro-
matography at silica gel (TBME/petroleum ether, 2:1, length 25 cm,
carbonylchromium(0) in 120 mL of dibutyl ether and 12 mL of
THF is heated at reflux for 20 h. The initially colourless solution
becomes dark yellow. The reaction mixture is filtered through silica
gel (length 10 cm, л 3 cm). Unreacted starting material is eluted
л 3 cm). 306 mg (0.74 mmol, 85%) of 29, orange solid (m. p.
Ϫ1
1
75°C, dec.). Ϫ IR (CHCl
3
): ν˜ ϭ 3047 (w) cm , 2980 (w), 2900 with diethyl ether/petroleum ether (1:1), then the product is eluted
(w), 1992 (s, CO), 1936 (s, CO), 1728 (m, ketone), 1516 (w), 1424
with ethyl acetate. The solvent is removed at reduced pressure, and
(
1
w), 1392 (w), 1260 (w), 1228 (w), 1176 (m), 1072 (m), 1048 (m),
008 (w), 956 (w), 820 (w), 648 (w), 608 (w). Ϫ H NMR (400.1 p. 245°C, dec.). Ϫ IR (KBr): ν˜ ϭ 3084 (w) cm , 2984 (w), 2956
1.70 g (4.6 mmol, 82%) of 33 is obtained as a yellow powder (m.
1
Ϫ1
MHz, CDCl
CH CH ), 4.35Ϫ4.50 (m, 4 H, CH
Hz, 5-H or 6-H), 5.41 (d, 1 H, J ϭ 6.0 Hz, 4-H or 7-H), 5.65 (t,
3
): δ ϭ 1.10Ϫ1.40 (m, 6 H, CH
3
), 3.60Ϫ3.94 (m, 4 H,
(w), 2880 (w), 1956 (s, CO), 1896 (s, CO), 1316 (m), 1280 (m), 1116
(m), 1072 (s, acetal-CϪO), 1036 (m), 948 (m), 820 (m), 656 (s), 632
3
2
3
2
CH ), 5.23 (t, 1 H, J ϭ 6.0,
2
3
1
(m). Ϫ H NMR (200.1 MHz, CDCl
J
3
): δ ϭ 2.33 (d, 1 H,
3
3
2
anti-2,syn-2 ϭ Ϫ14.0 Hz, syn-2-H or anti-2-H), 2.63 (d, 1 H, 2Janti-
2,syn-2 ϭ Ϫ14.0 Hz , syn-2-H or anti-2-H), 4.00Ϫ4.35 (m, 8 H,
CH O), 5.28 ϩ 5.42 (AAЈBBЈ line system, 2ϫ 2 H, arom.
H). Ϫ C NMR (50.3 MHz, [D ]DMSO): δ ϭ 42.2 (ϩ, C-2), 65.0
(ϩ, OCH ), 66.0 (ϩ, OCH ), 88.0 [Ϫ, C-4(7)], 94.1 [Ϫ, C-5(6)],
110.8 [ϩ, C-1(3)], 113.5 [ϩ, C-3a(7a)], 232.5 (ϩ, CO). Ϫ MS (70
1
7
H, J ϭ 6.0, Hz, 5-H or 6-H), 5.79 (d, 1 H, J ϭ 6.0 Hz, 4-H or
-H). Ϫ 13C NMR (100.6 MHz, CDCl
): δ ϭ 15.5 (CH ), 16.2
), 66.4 (CH CH ), 67.6 OCH
), 83.5 (CH, C-4 or C-5 or C-6 or C-7), 86.3 (CH, C-4 or
3
3
(CH
CH
3
2
), 60.2 (CH
CH
2
CH
3
), 60.7 (CH
2
CH
3
2
2
2
2
1
3
(
2
6
C-5 or C-6 or C-7), 90.2 (CH, C-4 or C-5 or C-6 or C-7), 91.6 (C
C-2), 94.8 (CH, C-4 or C-5 or C-6 or C-7), 98.8 (C , C-3), 109.1
, C-3a), 118.1 (C , C-7a), 194.4 (C , C-1), 229.8 (C , CO). Ϫ eV, 90°C): m/z (%) ϭ 371 (1) [M ϩ 1], 370 (2) [M ], 286 (11) [M
MS (70 eV, 25°C): m/z (%) ϭ 416 (2) [M ϩ 2], 415 (6) [M ϩ 1],
q
,
2
2
q
ϩ
ϩ
ϩ
(C
q
q
q
q
ϩ
ϩ
Ϫ 3 CO], 234 (8), 214 (16), 190 (15), 174 (24), 162 (96), 146 (52),
ϩ
ϩ
ϩ
ϩ
4
(
14 (14) [M ], 358 (72), [M Ϫ 2 CO], 330 (69) [M Ϫ 3 CO], 301 135 (40), 119 (35), 105 (100) [C
7
H
5
O ], 90 (39), 76 (84), 52 (44). Ϫ
: calcd. 370.01446, found 370.01437.
(370.01) : calcd. C 51.90, H 3.81; found C 51.91, H
ϩ
18), 186 (57), 272 (26), 258 (74), 212 (100) [(indantrione)Cr ], 185
HRMS,
C
16
H
14CrO
7
Ϫ
(54), 173 (55), 157 (90), 148 (40), 128 (65), 104 (56), 96 (59).
16
C H
14CrO
7
3
.82.
(
η6-2,2-Diethoxy-1,3-indandione)chromium(0) (30): 30 mL of conc.
hydrochloric acid is added at 20°C to a solution of 150 mg (0.33
mmol) of 28 in 30 mL of THF. The solution is stirred for 8 h at
Crystal Structure Analysis of 33:[11]
C
˚
16 7
H14CrO , yellow, a ϭ
8.335(1), b ϭ 10.064(1), c ϭ 18.695(2) A, α ϭ 90, β ϭ 100.84(1),
˚
3
Ϫ1
Ϫ1
45°C, changing its colour from yellow to dark red. After addition
γ ϭ 90°, V ϭ 1540.2 A , dcalcd. ϭ 1.597 gcm , µ ϭ 7.80 cm
,
of 100 mL of ice water the mixture is extracted three times each
with 30 mL of TBME. The collected organic layers are washed
three times each with 20 mL of a saturated aqueous solution of
sodium carbonate and another three times each with 20 mL of
water. After drying with potassium carbonate, filtration, and sol-
T ϭ 200 K, Z ϭ 4, monoclinic, space group P2
1
/c (Nr. 14), Stoe
˚
IPDS diffractometer, λ ϭ 0.71073 A, 133 exposures, 2Θmax 56°,
15000 measured reflections (±h, ±k, ±l), 3516 independent and
1799 observed reflections [I > 2σ(I)], 218 refined parameters, H
atom positions found and included using the riding model, R
1
ϭ
vent removal at reduced pressure a brown oil is obtained which is 0.0443, wR
2
ϭ 0.0673, min., max. residual electron density Ϫ0.54,
˚
Ϫ3
purified by column chromatography at silica gel (TBME/petroleum
0.38 eA ; programs used: SHELXS-86, SHELXL-93. CCDC
102125.
ether, 1:1, length 20 cm, л 3 cm). Fraction I: 59 mg (0.16 mmol,
4
1
8%) of 30, red solid (m. p. 165°C, dec.). II: 25 mg (0.06 mmol,
8%) of 29.
6
6
Tricarbonyl(η -1,3-indandione)chromium(0) (6) and Tricarbonyl[η -
-(2-methylethylene)-1,3-indandione]chromium(0) (35): a) A solution
2
30: IR (CHCl
3
): ν˜ ϭ 3045 (w) cmϪ1, 2980 (w), 2960 (w), 2008 (s,
of 3.00 g (8.2 mmol) of 33 in 100 mL of THF is mixed with 50
CO), 1944 (s, CO), 1744 (m. ketone-CO), 1720 (m, ketone-CO),
mL of 50% sulfuric acid. A red solution is formed, whose colour
1
600 (w), 1260 (w), 1176 (w), 1140 (w), 1100 (w), 1056 (w), 956 continuously deepens. After 4Ϫ5 h no more 33 is detected by TLC,
1
(w), 636 (w), 600 (w). Ϫ H NMR (200.1 MHz, CDCl
(m, 6 H, CH CH ), 3.90Ϫ4.10 (m, 4 H, OCH CH ), 5.65 ϩ 5.88
(AAЈBBЈ line system, 4 H, arom. H).
3
): δ ϭ 1.23 and 100 mL of water is added. The mixture is extracted three times
2
3
2
3
with 50 mL each of diethyl ether, and the collected organic layers
are washed three times with 20 mL each of a saturated aqueous
solution of sodium bicarbonate. After drying with MgSO
tration, and solvent removal at reduced pressure 2.17 g (7.7 mmol,
4%) of 6 is obtained as a red-brown solid (m. p. 125°C).
4
, fil-
1
,3-Bis(ethylenedioxy)indane (32): A solution of 2.00 g (13.7 mmol)
[49]
of 1,3-indandione (31) , 1.83 mL (32.9 mol) of 1,2-ethanediol,
and 0.02 g (0.1 mmol) of PTSA is heated at reflux with azeotropic
water removal for 48 h, the solution becoming deep red. After sol-
vent removal at reduced pressure a red, greasy solid is obtained,
which is crystallized from ethyl acetate/petroleum ether (1:1). 2.60
9
b) 50 mL of 50% sulfuric acid is slowly added to a solution of 4.40
g (11.9 mmol) of 33 in 50 mL of acetone. Immediately a deep red
solution is formed, which is stirred for 4 h at 25°C. 100 mL of ice
water is added, and the mixture is extracted three times each with
30 mL of diethyl ether. The collected organic layers are washed
g (11.1 mmol, 81%) of 32 as a colourless solid (m. p. 144°C). Ϫ IR
Ϫ1
(
KBr): ν˜ ϭ 3052 (w) cm , 2976 (w), 2896 (m), 1460 (w), 1320 (m),
1
268 (m), 1128 (m), 1064 (m), 1036 (s, acetal-C-O), 940 (m), 804 three times each with 50 mL of water, dried with MgSO
4
, filtered,
and the solvent is removed at reduced pressure. A brown solid is
-H), 4.10 ϩ 4.21 [AAЈBBЈ, 2ϫ 2 H, 8(8Ј)-H, 9(9Ј)-H], 7.37Ϫ7.49 obtained which is purified by column chromatography at silica gel
1
3
(m), 772 (m). Ϫ H NMR (400.1 MHz, CDCl ): δ ϭ 2.58 (s, 2 H,
2
(
m, 4 H, arom. H). Ϫ 13C NMR (100.6 MHz, CDCl
3
): δ ϭ 50.0
ϩ, C-2), 66.2 [ϩ, C-8(8Ј), C-(9,9Ј)], 113.4 [ϩ, C-1(3)], 123.6 [Ϫ,
(diethyl ether/petroleum ether, 1:1, then diethyl ether, length 30 cm,
(
л 5 cm). Fraction I: 190 mg (0.6 mmol, 5%) of 35, orange-brown
C-4(7)], 130.9 [Ϫ, C-5(6)], 143.1 [ϩ, C-3a(7a)]. Ϫ MS (70 eV, 25°C): solid (m. p. 151°C). II: 3.00 g (10.7 mmol, 90%) of 6.
ϩ
ϩ
m/z (%) ϭ 235 (2) [M ϩ 1], 234 (7) [M ], 190 (14), 174 (14), 162
6
1
(
3
: IR (KBr): ν˜ ϭ 3100 (w) cmϪ1, 2960 (w), 2920 (w), 1995 (s, CO),
942 (s, CO), 1907 (s, CO), 1740 (m, CO), 1709 (s), 1364 (w), 1252
ϩ
(
93), 146 (22), 135 (19), 118 (13), 105 (100) [C
HRMS, calcd. 234.08920, found 234.08902. Ϫ
7 5
H O ], 76 (30). Ϫ
C
13
H
14
O
4
:
1
m), 650 (m), 604 (m). Ϫ H NMR (400.1 MHz, [D
6
]acetone): δ ϭ
C
13
H
14
O
4
(234.09): calcd. C 66.66, H 6.02; found C 66.61, H 5.89.
2
.29 (d, 1 H, Janti-2,syn-2 ϭ Ϫ21.9 Hz, syn-2-H or anti-2-H), 3.36
(d, 1 H, Janti-2,syn-2 ϭ Ϫ21.9 Hz , anti-2-H or syn-2-H), 6.07 ϩ
6.18 (AAЈBBЈ line system, 2ϫ 2 H, arom. H). Ϫ C NMR (100.6
6
2
Tricarbonyl[η -1,3-bis(ethylenedioxy)indane]chromium(0) (33):
mixture of 1.30 g (5.6 mmol) of 32 and 2.00 g (9.1 mmol) of hexa-
A
1
3
176
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
MHz, [D
6
]acetone): δ ϭ 43.7 (ϩ, C-2), 88.3 [Ϫ, C-4(7)], 95.9 [Ϫ,
(Ϫ, C-5, C-6), 99.7 (ϩ, C-2), 100.7 (ϩ, C-3a, C-7a), 153.7 [ϩ, ϭ
], 185.5 (ϩ, C-1 or C-3), 188.5 (ϩ, C-1 or C-3), 232.0
C-5(6)], 102.8 [ϩ, C-3a(7a)], 195.9 [ϩ, C-1(3)], 230.2 (ϩ, CO). Ϫ CH-N(CH )
MS (70 eV, 80°C): m/z (%) ϭ 284 (5) [M ϩ 2], 283 (16) [M
3 2
ϩ
ϩ
ϩ
ϩ
(ϩ, CO). Ϫ MS (70 eV, 160°C): m/z (%) ϭ 339 (1) [M ϩ 2], 338
ϩ
ϩ
ϩ
ϩ
ϩ
ϩ
ϩ
1
], 282 (44) [M ], 254 (2) [M Ϫ CO], 226 (44) [M Ϫ 2 CO], 198 (5) [M ϩ 1], 337 (20) [M ], 281 (19) [M Ϫ 2 CO], 253 (69) [M
ϩ
ϩ
(52) [M Ϫ 3 CO], 146 (44), 119 (13), 104 (43), 90 (27), 76 (48), 52 Ϫ 3 CO], 238 (100) [(C11
H
8
NO
181 (7), 153 (8), 95 (18), 52 (53). Ϫ HRMS, C15
337.00423, found 337.00293. Ϫ C15 11CrNO (337.00): calcd. C
2
)Cr ], 223 (6), 210 (13), 197 (10),
52
(
100) [ Cr]. Ϫ HRMS, C12
81.96196. Ϫ C12 CrO (281.96): calcd. C 51.08, H 2.14; found
C 51.17, H 2.38.
H
6
CrO
5
: calcd. 281.96203, found
H
11CrNO : calcd.
5
2
H
6
5
H
5
53.42, H 3.29, N 4.15; found C 52.70, H 3.35, N 3.97.
5: IR (KBr): ν˜ ϭ 3075 (w) cmϪ1, 3036 (w), 2906 (w), 1996 (s, CO),
Tricarbonyl(η -2-diazo-1,3-indandione)chromium(0) (37): 0.16 mL
6
3
1
1
940 (s, CO), 1716 (m), 1676 (m), 1612 (m), 1420 (w), 1404 (w),
(1.24 mmol) of triethylamine is added to a solution of 250 mg (0.89
): mmol) of 6 in 5 mL of THF. 250 mg (1.27 mmol) of para-tosyl
azide is added, and after 30 min no more 6 is detected by TLC.
1
372 (w), 1252 (w), 1132 (w). Ϫ H NMR (200.1 MHz, CDCl
3
δ ϭ 2.59 (s, 6 H, CH
arom. H). Ϫ 13C NMR (100.6 MHz, CDCl
7.7 [Ϫ, C-4(7)], 93.2 [Ϫ, C-5(6)], 99.9 [ϩ, C-3a(7a)], 125.2 (ϩ, ϭ
3 2
C(CH ) ), 172.5 (ϩ, C-2), 189.5 [ϩ, C-1(3)], 229.6 (ϩ, CO). Ϫ MS petroleum ether, 1:2, then 1:1, length 20 cm, л 3 cm). 233 mg (0.76
3
), 5.58 ϩ 5.99 (AAЈBBЈ line system, 4 H,
3
): δ ϭ 24.8 (Ϫ, CH ),
3
The solvent is removed at reduced pressure, and the dark brown,
solid residue is purified by column chromtography (diethyl ether/
8
ϩ
ϩ
(
(
(
70 eV, 100°C): m/z (%) ϭ 323 (1) [M ϩ 1], 322 (5) [M ], 321 mmol, 85%) of 37 as a red-brown solid (m. p. 135°C). Ϫ IR
ϩ
ϩ
Ϫ1
16), 266 (17) [M Ϫ 2 CO], 236 (100) [M Ϫ 3 CO], 223 (9), 186
4), 167 (4), 115 (6), 52 (82). Ϫ HRMS, C15 10CrO : calcd.
(CHCl
): ν˜ ϭ 3034 (w) cm , 2360 (w), 2340 (w), 2124 (s, CN
),
3 2
1996 (s, CO), 1944 (s, CO), 1716 (w, CO), 1688 (s, CO), 1600 (w),
1400 (w), 1344 (s), 1196 (w), 1140 (w), 640 (m), 604 (m). Ϫ
NMR (200.1 MHz, CDCl ): δ ϭ 5.58 ϩ 5.99 (AAЈBBЈ - System,
ϫ 2 H, arom. H). Ϫ C NMR (100.6 MHz, CDCl ): δ ϭ 70.4
ϩ, C-2), 87.7 [Ϫ, C-4(7)], 92.1 [Ϫ, C-5(6)], 97.8 [ϩ, C-3a(7a)],
81.2 [ϩ, C-1(3)], 229.4 (ϩ, CO). Ϫ MS (70 eV, 110°C): m/z (%) ϭ
10 (1) [M ϩ 2], 309 (3) [M ϩ 1], 308 (11) [M ], 307 (43) [M
Ϫ 1], 252 (29) [M Ϫ 2 CO], 224 (57) [M Ϫ 3 CO], 196 (52), 168
92), 140 (82), 114 (13), 90 (14), 80 (11), 52 (100) [ Cr]. Ϫ HRMS,
H
5
1
3
21.99333, found 321. 99332.
H
3
6
Tricarbonyl(η -endo-1,endo-3-indanediol)chromium(0) (34): In a 100
mL Schlenk flask a solution of 100 mg (0.35 mmol) of 6 in 20 mL
of THF and 50 mL of ethanol and 50 mg (1.32 mmol) of sodium
borohydride are mixed. Within 4 h at 25°C the colour of the mix-
ture changes from red-brown to yellow-orange. 60 mL of water is
added, and the mixture is extracted three times each with 15 mL
of diethyl ether. The collected organic layers are washed three times
13
2
3
(
1
3
ϩ
ϩ
ϩ
ϩ
ϩ
ϩ
52
(
C
C
12
H
H
4
4
CrN
CrN
2
2
O
O
5
:
calcd. 307.95253, found
(308.16): calcd. C 46.77, H 1.31, N 9.09; found C
307.95224.
Ϫ
each with 10 mL of water, dried with MgSO
solvent removal at reduced pressure 80 mg (0.28 mmol, 80%) of
4 (de > 95%, NMR) is obtained as a yellow powder, which is
4
, and filtered. After
12
5
4
6.80, H 1.42, N 9.02.
3
6
recrystallized from ethyl acetate (m. p. 205°C, dec.). Ϫ IR (KBr): Tricarbonyl{η -2-phenylspiro(cyclopropane-1,2Ј-[2H]inden)-1Ј,3Ј-
ν˜ ϭ 3586 (w, OH) cm , 3430 (w, OH), 3080 (w), 2960 (w), 1960 dione}chromium(0) (38): A solution of 250 mg (0.82 mmol) of 37,
Ϫ1
(
s, CO), 1880 (s, CO), 1450 (w), 1100 (m), 1090 (w), 1040 (m), 802
0.94 mL (854 mg, 8.20 mmol) of phenylethene, and 10 mg (0.02
1
(m), 668 (w), 640 (w). Ϫ H NMR (400.1 MHz, [D
.80 (dq, 1 H, 2
6
]acetone): δ ϭ mmol) of rhodium(II) acetate in 30 mL of anhydrous benzene is
1
3
J
syn-2,anti-2 ϭ Ϫ11.6 Hz, 3
anti-2,1(3) ϭ 9.2 Hz, syn-2-H or anti-2-H), 2.66 (dq, 1 H,
2Jsyn-2,anti-2 ϭ Ϫ11.6 Hz, 3 syn-2,1(3) ϭ 6.6 Hz or 3
J
syn-2,1(3) ϭ 9.2 Hz or
heated at reflux for 2 h. The solvent is removed at reduced pressure,
and the black residue is purified by column chromatography at
J
J
J
anti-2,1(3) ϭ 6.6 silica gel (diethyl ether/petroleum ether, 1:1, length 20 cm, л 3 cm).
Hz, syn-2-H or anti-2-H), 4.75 [m, 2 H, 1(3)-H], 4.95 (m, 2 H, OH),
5
100 mg (0.26 mmol, 32%) of 38 (de > 95%, NMR, presumably the
exo diastereomer) as an orange-red solid (m. p. 152°C). Ϫ IR
(KBr): ν˜ ϭ 3068 (w) cm , 2960 (w), 1988 (s, CO), 1924 (s, CO),
.50 ϩ 5.63 (AAЈBBЈ line system, 2ϫ 2 H, arom. H). Ϫ 1 C NMR
100.6 MHz, [D ]acetone): δ ϭ 41.9 (ϩ, C-2), 70.0 [ϩ, C-1(3)], 89.2
Ϫ, C-4(7)], 93.7 [Ϫ, C-5(6)], 120.9 [ϩ, C-3a(7a)], 235.2 (ϩ, CO).
3
Ϫ1
(
6
[
1744 (w, ketone), 1700 (m, ketone), 1384 (w), 1308 (w), 1260 (w),
ϩ
ϩ
Ϫ MS (70 eV, 120°C): m/z (%) ϭ 288 (2) [M ϩ 2], 287 (9) [M
ϩ 1], 286 (32) [M ], 230 (47) [M Ϫ 2 CO], 202 (50) [M Ϫ 3 608 (w). Ϫ H NMR (400.1 MHz, [D
1220 (w), 1160 (w), 1096 (w), 1040 (w), 812 (w), 704 (w), 644 (w),
ϩ
ϩ
ϩ
1
6
]acetone): δ ϭ 2.23 (dd, 1
ϩ
2
H, J1,1 ϭ Ϫ 4.4 Hz, J1,2 ϭ 9.0 Hz, 1-H), 2.49 (dd, 1 H, 2J1,1
Ϫ 4.4 Hz, J1,2 ϭ 9.0 Hz, 1-H), 3.43 (t, 1 H, 3J1,2 ϭ 9.0 Hz, 2-H),
2
3
CO], 184 (72), 166 (18), 132 (39), 116 (100) [C
9 (47), 69 (49), 52 (60). Ϫ HRMS, C12 10CrO
8
H
4
O
], 103 (42),
: calcd. 285.99333,
ϭ
3
8
H
5
5
found 285.99322. Ϫ C12H10CrO (285.99): calcd. C 50.36, H 3.52; 6.00Ϫ6.30 (ABCD line system, 4 H, arom. H), 7.21Ϫ7.43 (m, 5 H,
1
3
found C 50.43, H 3.60.
6
phenyl-H). Ϫ C NMR (100.6 MHz, [D ]acetone): δ ϭ 22.2 (ϩ,
C-1), 41.0 (ϩ, C-2Ј), 41.8 (Ϫ, C-2), 87.6 (Ϫ, C-5Ј or C-6Ј), 87.7 (Ϫ,
C-5Ј or C-6Ј), 94.5 (Ϫ, C-4Ј or C-7Ј), 94.6 (Ϫ, C-4Ј or C-7Ј), 99.9
6
Tricarbonyl[η -2-(N,N-dimethylaminomethylene)-1,3-indandione]-
chromium(0) (36): A solution of 300 mg (1.06 mmol) of 6 and 0.27
mL (2.12 mmol) of dimethylformamide dimethylacetal [dimethoxy-
(
1
(
(
ϩ, C-3aЈ or C-7aЈ), 101.1 (ϩ, C-3aЈ or C-7aЈ), 127.5 (Ϫ, C-6),
27.8 (Ϫ, C-5 or C-7), 129.4 (Ϫ, C-4 or C-8), 133.5 (ϩ, C-3), 193.2
ϩ, C-1Ј or C-3Ј), 195.2 (ϩ, C-1Ј or C-3Ј), 229.7 (ϩ, CO). Ϫ MS
(
dimethylamino)methane] in 1 mL of anhydrous dichloromethane
is stirred for 16 h at 25°C with formation of an orange suspension.
The solvent is removed at reduced pressure, and the orange-brown
residue is purified by column chromatography at silica gel (ethyl
acetate/diethyl ether, 1:1, length 15 cm, л 3 cm). 337 mg (1.00
mmol, 94%) of 36 as an orange solid (m. p. 190°C, dec.). Ϫ IR
KBr): ν˜ ϭ 3444 (br) cm , 2960 (w), 2936 (w), 1964 (s, CO), 1916
ϩ
ϩ
70 eV, 140°C): m/z (%) ϭ 386 (3) [M ϩ 2], 385 (7) [M ϩ 1],
ϩ
ϩ
ϩ
3
84 (14) [M ], 328 (8) [M Ϫ 2 CO], 300 (100) [M Ϫ 3 CO], 248
(11), 171 (25), 155 (22), 140 (8), 107 (18), 91 (65), 52 (63). Ϫ
HRMS, C20
H
5
12CrO : calcd. 384.00898, found 384.01050.
Ϫ1
6
(
Tricarbonyl{η -3-oxa-2-phenylcyclopenta[a]inden-8(8a)-one}chro-
mium(0) (39): A mixture of 230 mg (0.77 mmol) of 37 and 10 mg
(0.02 mmol) of rhodium(II) acetate in 7.0 mL of phenylethyne is
stirred for 3 h at 50Ϫ60°C. After removal of the phenylethyne at
0.001 mbar a dark brown solid is obtained, which is purified by
column chromatography at silica gel (diethyl ether/petroleum ether,
(
s, CO), 1880 (s, CO), 1696 (m, CO), 1644 (s), 1612 (s), 1536 (w),
484 (w), 1432 (m), 1380 (s), 1136 (w), 1004 (w), 660 (m), 624 (m).
1
1
Ϫ H NMR (400.1 MHz, [D
6
]acetone): δ ϭ 3.52 (s, 1 H, CH
), 5.86 (s, 2 H, arom. H), 6.11 (s, 2 H, arom. H),
.46 [s, 1 H, ϭCH-N(CH ]ace-
]. Ϫ 13C NMR (100.6 MHz, [D
), 47.8 (Ϫ, CH
3
),
3
7
.75 (s, 3 H, CH
3
3
)
2
6
tone): δ ϭ 43.6 (Ϫ, CH
3
3
), 88.7 (Ϫ, C-4, C-7), 94.8 1:1, length 20 cm, л 3 cm). 207 mg (0.54 mmol, 70%) of 39 as a
Eur. J. Org. Chem. 1999, 167Ϫ179
177

D. Leinweber, R. Wartchow, H. Butenschön
FULL PAPER
dark brown solid (m. p. 162°C, dec.). Ϫ IR (KBr): ν˜ ϭ 3100 (w) 6.05Ϫ6.14 (m, 4 H, arom. H). Ϫ 13C NMR (100.6 MHz, [D
]ace-
), 31.1 (ϩ,
), 73.5 (ϩ, C-2), 86.9 [Ϫ, C-4(7)], 94.9 [Ϫ,
C-5(6)], 97.6 [ϩ, C-3a(7a)], 119.1 (ϩ, CCH CCH ), 123.9 (ϩ,
OCH CCH ), 195.6 [ϩ, C-1(3)], 228.6 (ϩ, CO). Ϫ 42/43: MS (70
eV, 140°C): m/z (%) ϭ 378 (32) [M ], 322 (27) [M Ϫ 2 CO], 294
6
Ϫ1
cm , 2960 (w), 2924 (w), 1996 (s, CO), 1976 (s, CO), 1892 (s, CO),
tone): δ ϭ 12.9 (Ϫ, CCH
CCH ), 67.2 (ϩ, OCH
2 3 2 3
CCH ), 17.4 (Ϫ, OCH CCH
1
1
6
700 (s, ketone), 1524 (w), 1476 (w), 1260 (m), 1164 (w), 1136 (w),
2
2
096 (m), 1064 (m), 1020 (m), 872 (m), 800 (m), 764 (m), 652 (m),
2
3
1
00 (m). Ϫ H NMR (400.1 MHz, CDCl
3
): δ ϭ 5.39Ϫ6.16 (ABCD
2
3
ϩ
ϩ
line system, 4 H, arom. H), 6.76 (s, 1 H, 3-H), 7.33Ϫ7.70 (m, 5 H,
phenyl-H). Ϫ 13C NMR (100.6 MHz, CDCl
): δ ϭ 83.1 (CH, C-6Ј (59) [M Ϫ 3 CO], 276 (25), 264 (36), 212 (94) [(indantrione)Cr ],
or C-7Ј or C-8Ј or C-9Ј), 86.7 (CH, C-6Ј or C-7Ј or C-8Ј or C-9Ј),
0.2 (CH, C-6Ј or C-7Ј or C-8Ј or C-9Ј), 91.1 (CH, C-6Ј or C-7Ј or
C-8Ј or C-9Ј), 97.0 (C , C-5aЈ or C-9aЈ), 98.1 (C , C-5aЈ or C-9aЈ),
00.8 (CH, C-3), 124.3 [CH, C-12Ј(16Ј) or C-13Ј(15Ј)], 127.2 (C
C-4), 129.0 [CH, C-12Ј(16Ј) or C-13Ј(15Ј)], 129.1 (CH, C-14Ј),
ϩ
ϩ
3
ϩ
155 (27), 128 (55, C
[ Cr]. Ϫ HRMS, C13
6
H
H
4
Cr ), 112 (24), 99 (100), 76 (23), 52 (94)
Cr: calcd. 378.01955, found 378.01849.
5
2
9
8
O
5
q
q
6
Tricarbonyl[η -(1,3-dioxoindane)-2-spiro-2Ј-(3Ј-trimethylsiloxy-6Ј-
dihydro-2ЈH-pyrane)]chromium(0) (45): 387 mL (2.39 mmol) of 1-
1
q
,
(
(
trimethylsiloxy)butadiene (44) is added to a solution of 150 mg
0.48 mmol) of 8 in anhydrous benzene. After addition of 200 mg
1
29.2 (C
q
, C-11Ј), 162.4 (C
q q q
, C-2), 168.9 (C , C-5), 181.9 (C , C-
ϩ
10Ј), 230.5 (C
q
, CO). Ϫ MS (70 eV, 140°C): m/z (%) ϭ 384 (2) [M
ϩ
of molecular sieves the mixture is allowed to stand for 7 d at 20°C.
The red solution is separated from the molecular sieves, and the
solvent is removed at reduced pressure. The crude product is puri-
fied by column chromatography (TBME/petroleum ether, 1:1,
length 30 cm, л 3 cm). Fraction I: 121 mg (0.28 mmol, 58%) of 45
as an orange-red solid (de > 95%, NMR; m. p. 202°C). II: 30 mg
(0.09 mmol, 20%) of 8.
ϩ
ϩ
ϩ 2], 383 (5) [M ϩ 1], 382 (14) [M ], 326 (13) [M Ϫ 2 CO], 298
ϩ
(
(
3
100) [M Ϫ 3 CO], 270 (8), 246 (14), 189 (20), 140 (4), 105 (5), 77
6), 52 (66). Ϫ HRMS, C20 Cr: calcd. 381.99333, found
81.99063.
10 5
H O
Tricarbonyl(η -indantrione)chromium(0) (7) and Tricarbonyl(η6-
ninhydrin)chromium(0) (8): 300 mg (1.06 mmol) of 6 is mixed with
6
3
2.0 mL (3.2 mmol) of a Ϫ28°C cold 0.1  solution of dimethyldi-
4
1
1
5: IR (KBr): ν˜ ϭ 3084 (w) cmϪ1, 2960 (w), 2924 (w), 2012 (s, CO),
932 (s, CO), 1736 (s, ketone), 1704 (s, ketone), 1508 (w), 1420 (w),
oxirane in acetone. 6 completely reacts within one minute. The ob-
tained dark brown solution is stirred for 5 min at Ϫ28°C. Then
400 (w), 1280 (w), 1252 (w), 1228 (w), 1188 (w), 1168 (w),1084
1
00 mL of water is added, and the mixture is extracted three times
each with 30 mL of diethyl ether. After drying of the collected
organic layers with MgSO the solvent is removed at reduced pres-
1
(
w), 1044 (m), 888 (w), 864 (w), 844 (m), 640 (w), 596 (m). Ϫ H
NMR (400.1 MHz, [D
m, 1 H, CH ), 2.52 (m, 1 H, CH
.90Ϫ5.96 (m, 2 H, OCHOSiMe , CH
AAЈBBЈ line system, 2 ϩ 2 H, arom. H). Ϫ C NMR (100.6
MHz, [D ]acetone): δ ϭ Ϫ 0.4 (Ϫ, OSiMe ), 26.2 (ϩ, CH ), 75.3
ϩ, C-2), 86.9 (Ϫ, C-4 or C-7), 87.5 (Ϫ, C-4 or C-7), 91.0 (Ϫ,
OCHOSiMe ), 94.8 (Ϫ, C-5 or C-6), 95.3 (Ϫ, C-5 or C-6), 97.1 (ϩ,
C-3a or C-7a), 97.2 (ϩ, C-3a or C-7a), 122.5 (Ϫ, CH CH), 129.3
CHCH), 193.7 (ϩ, C-1 or C-3), 196.2 (ϩ, C-1 or C-3),
6
]acetone): δ ϭ 0.15 (s, 9 H, OSiMe
), 5.81 (m, 1 H, CH
CHCH), 6.10 ϩ 6.15
3
), 2.36
4
(
2
2
2
CH),
sure, and the black residue is purified by column chromatography
at silica gel (diethyl ether/petroleum ether, 1:1, length 20 cm, л 3
cm). 249 mg (0.79 mmol, 75%) of 8 as a brown solid (m. p. 105°C,
5
3
2
1
3
(
[50]
6
3
2
dec.). The NMR spectra show the presence of some 7.
: IR (KBr): ν˜ ϭ 3396 (w, OH) cmϪ1, 3092 (w), 1996 (s, CO), 1936
(
8
3
(
(
(
s, CO), 1744 (s, ketone), 1716 (s, ketone), 1260 (w), 1188 (w), 1092
w), 1020 (w), 996 (w), 936 (w), 640 (m), 596 (m). Ϫ H NMR
400.1 MHz, [D
2
1
(
2
Ϫ, CH
2
]acetone): δ ϭ 6.15 (s, 4 H, arom. H), 6.70 (s, 1
ϩ
6
28.7 (ϩ, CO). Ϫ MS (70 eV, 150°C): m/z (%) ϭ 439 (4) [M
ϩ
1
3
H, endo-OH or exo-OH), 6.83 (s, 1 H, endo-OH or exo-OH). Ϫ
NMR (100.6 MHz, [D ]acetone): δ ϭ 86.6 (ϩ, C-2), 87.1 [Ϫ, C-
(7)], 95.1 [Ϫ, C-5(6)], 96.5 [ϩ, C-3a(7a)], 193.7 [ϩ, C-1(3)], 228.5
C
ϩ
ϩ
ϩ
1
CH
], 438 (6) [M ], 354 (20) [M Ϫ 3 CO], 339 (100) [M Ϫ 3 CO Ϫ
], 321 (33), 296 (7), 268 (10), 247 (17), 212 (13), 197 (15), 139
7), 126 (32), 99 (14), 73 (28), 52 (59). Ϫ HRMS, C19 18CrO Si:
6
3
4
(
H
7
ϩ
(ϩ, CO). Ϫ MS (70 eV, 110°C): m/z (%) ϭ 297 (5) [M ϩ 1 Ϫ
calcd. 438.02269, found 438.02249.
ϩ
ϩ
H
1
2
O], 296 (22) [M Ϫ H
2
O], 212 (54) [(indantrione)Cr ], 184 (15),
7
CrO :
6
ϩ
Tricarbonyl[η -(1,3-dioxoindane)-2-spiro-2Ј-(3Ј-methoxy-4Ј,4Ј,6Ј,6Ј-
tetrahydro-2ЈH-pyran-5Ј-one)]chromium(0) (48): 583 mL (3.60
mmol) of 1-methoxy-3-trimethylsiloxy-1,3-butadiene (47) is added
to a solution of 380 mg (1.20 mmol) of 8 in 10 mL of anhydrous
28 (100) [(C
6
H
4
)Cr ], 104 (12), 80 (14). Ϫ HRMS, C12
H
6
calcd. 295.94130, found 295.94122.
1
7
: H NMR (400.1 MHz, [D ]acetone): δ ϭ 6.30 ϩ 6.43 (AAЈBBЈ
6
13
line system, 2 ϩ 2 H, arom. H). Ϫ C NMR (100.6 MHz, [D
tone): δ ϭ 88.1 [Ϫ, C-4(7)], 95.9 [Ϫ, C-5(6)], 100.1 [ϩ, C-3a(7a)],
6
]ace-
˚
THF. After addition of 200 mg of molecular sieves (3 A) the mix-
ture is allowed to stand for 72 h at 20°C. The red solution is sepa-
rated from the molecular sieves, and the solvent is removed at re-
duced pressure. The crude product is purified by column chroma-
tography (TBME/petroleum ether, 1:1, then TBME, length 30 cm,
л 3 cm). Fraction I: 87 mg (0.28 mmol, 23%) of 8. II: 347 mg
(0.88 mmol, 78%) of 48, orange-red solid (de > 95%, NMR; m.
p. 195°C).
178.3 [ϩ, C-1(3)], 187.1 (ϩ, C-2), 227.4 (ϩ, CO).
6
Tricarbonyl[η -(1,3-dioxoindane)-2-spiro-2Ј-(4Ј,5Ј-dimethyl-3Ј,6Ј-
dihydro-2ЈH-pyrane)]chromium(0) (42/43): 157 mg (1.91 mmol) of
2,3-dimethyl-1,3-butadiene (41) is added to a solution of 150 mg
(0.48 mmol) of 8 in 5 mL of THF. After addition of 200 mg of
˚
molecular sieves (3 A) the mixture is allowed to stand for 72 h at
0°C. The red solution is then separated from the molecular sieves,
2
IR (KBr): ν˜ ϭ 3084 (w) cmϪ1, 2972 (w), 2920 (w), 2848 (w), 2000
s, CO), 1940 (s, CO), 1740 (s, ketone), 1712 (s, ketone), 1512 (w),
and the solvent is removed at reduced pressure. The crude product
is purified by column chromatography (TBME/petroleum ether,
1
of 42/43 as an orange-red solid (mixture of diastereomers, de ϭ
7
(
1
448 (w), 1396 (w), 1264 (w), 1204 (w), 1176 (w), 1040 (m), 980
:4, length 30 cm, л 3 cm). Fraction I: 100 mg (0.27 mmol, 55%)
1
(
w), 924 (w), 640 (m), 604 (m). Ϫ H NMR (400.1 MHz, [D
tone): δ ϭ 2.61 [dd, 1 H, J ϭ Ϫ17.1 Hz, J ϭ 3.6 Hz, OCH(O-
Me)CH ], 2.67 [d, 1 H, J ϭ Ϫ16.5 Hz, CCH C(O)], 2.99 [d, 1 H,
2 2
J ϭ Ϫ17.1 Hz, J ϭ 3.6 Hz, OCH(OMe)CH
C(O)], 3.55 (s, 3 H, OCH ), 6.15 ϩ 6.18 (AAЈBBЈ,
4 H, arom. H). Ϫ C NMR (100.6 MHz, [D ]acetone): δ ϭ 38.9
[CH , CH(OMe)CH ], 45.3 [CH , CCH C(O)], 55.0 (CH , OCH ),
75.3 (C , C-2), 87.1 (CH, C-4 or C-7), 87.4 (CH, C-4 or C-7), 94.9
(CH, C-5 or C-6), 95.3 (CH, C-5 or C-6), 96.5 (C , C-3a or C-7a),
6
]ace-
2
3
6%, NMR). II: 20 mg (0.06 mmol, 13%) of 8.
2/43: IR (KBr): ν˜ ϭ 3084 (w) cmϪ1, 2960 (w), 2920 (w), 2860 (w),
2
2
3
2
4
1
2
], 3.08 (d, 1 H, J ϭ
992 (s, CO), 1932 (s, CO), 1736 (s, ketone), 1704 (s, ketone), 1636 Ϫ16.5 Hz, CCH
2
3
1
3
(w), 1616 (w), 1448 (w), 1424 (w), 1284 (w), 1260 (w), 1144 (w),
6
1
1
(
3
092 (m), 1028 (m), 800 (w), 640 (m), 604 (m). Ϫ 42: H NMR
400.1 MHz, [D ]acetone): δ ϭ 1.61 (s, 3 H, OCH CCH ), 1.69 (s,
CCH ), 2.29 (s, 2 H, CCH ), 4.26 (s, 2 H, OCH ),
2
2
2
2
3
3
6
2
3
q
H, CCH
78
2
3
2
2
q
1
Eur. J. Org. Chem. 1999, 167Ϫ179

Synthesis, Characterization, and Some Reactions of the Tricarbonylchromium Complexes
FULL PAPER
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9
7.5 (C
q
, C-3a or C-7a), 100.1 [CH, OCH(OMe)], 193.5 (C
q
, C-1
or C-3), 196.3 (C
CO). Ϫ MS (70 eV, 150°C): m/z (%) ϭ 398 (32) [M ϩ 2], 397 (9)
q
, C-1 or C-3), 200.5 [C , CH C(O)], 228.5 (C
q
2
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[
M
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[19]
52
212 (41), 146 (6), 128 (19), 104 (16), 96 (13), 52 (100) [ Cr].
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size 0.07 ϫ 0.12 ϫ 0.15 mm, a ϭ 8.304(2), b ϭ 21.332(3), c ϭ
C
17
H
12CrO , red, crystal
8
1
989, 111, 371Ϫ372.
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˚
˚
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10.110(2) A, α ϭ 90, β ϭ 110.38(2), γ ϭ 90°, V ϭ 1678.8(6) A ,
Ϫ3
Ϫ1
A. P e´ rez-Encabo, S. Perrio, A. M. Z. Slawin, S. E. Thomas, A.
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d
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.71073, 150 exposures 2Θmax 48°, 9612 measured reflections (±h,
clinic, space group P2
0
1
1
993, 1059Ϫ1062.
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±
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[
2
P. W. N. Christian, R. Gil, K. Muniz-Fern a´ ndez, S. E. Thomas,
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2 0
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˚
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fellowship. We thank Chemetall GmbH, Degussa AG, Hüls AG,
Merck KGaA, and Phenolchemie GmbH for generous donations
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The crystallographic data (without structural factors) of the
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Received July 17, 1998
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[O98328]
Eur. J. Org. Chem. 1999, 167Ϫ179
179