Synthesis of enantiopure tricarbonyl(indan-1,2-dione)chromium

Article abstract of DOI:10.1002/ejoc.200500527

A multistep synthesis of the planar chiral tricarbonyl(η⁶- indan-1,2-dione)chromium, based on acetal protection of the keto groups, is presented. Since common deacetalization procedures failed, an oxidative deprotection with triphenylcarbenium

Full text of DOI:10.1002/ejoc.200500527

FULL PAPER
DOI: 10.1002/ejoc.200500527
Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
Dirk Leinweber,[a] Ingo Weidner,[a] René Wilhelm,[a][‡] Rudolf Wartchow,[b] and
Holger Butenschön*[a]
Keywords: Indan-1,2-dione / Chromium complexes / Planar chirality / Arene ligands / Enantioselectivity
A multistep synthesis of the planar chiral tricarbonyl(η6-in-
dan-1,2-dione)chromium, based on acetal protection of the
keto groups, is presented. Since common deacetalization
procedures failed, an oxidative deprotection with tri-
phenylcarbenium tetrafluoroborate was used. Tricarbon-
yl(η6-indan-1,2-dione)chromium is regarded as a potential
precursor for dianionic oxy-Cope rearrangements upon alk-
enyllithium diaddition. As an unexpected side product in the
lective ketone reduction with two methoxy substituents pres-
ent in the α position. Although enantiomeric excesses of up
to 84.5% were achieved, the chemical yields decreased with
increasing ee. A classical resolution was therefore under-
taken, giving access to the enantiomerically pure title com-
pound (99.4% ee). The absolute configuration was verified
by an X-ray structure analysis of an intermediate. First ex-
periments concerning the alkenyllithium addition showed
that a single addition is possible while a second one does not
occur, presumably due to enolate formation.
synthesis, an indan-1,2-dione complex with
a
tri-
phenylmethyl substituent at C-3 was obtained. Attempts di-
rected towards the formation of enantiomerically pure mate- (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
rial include the first reported investigation into an enantiose-
Germany, 2005)
asymmetric synthesis of 5, as well as a chiral resolution af-
fording enantiomerically pure 5. The synthesis of 5 is of
interest for investigation of the possibility of dianionic oxy-
Cope rearrangements upon diaddition of alkenyllithium
reagents. This should produce benzanellated cyclononane-
diones, which would presumably be prone to transannular
aldol reactions resulting in tricyclic systems consisting of
anellated six- and five-membered rings. The option of start-
ing from enantiomerically pure 5 would allow such tricycles
to be prepared in enantiomerically pure form. Tricarbonyl-
chromium complexes of indan-1-one[39] and of indan-2-
one[40] were previously prepared by Jackson and by Gibson,
respectively.
Introduction
The interest in the investigation of (arene)tricarbonyl-
chromium complexes during the last 30 years is the result
of their availability and stability on one hand and of the
reactivity of the coordinated arene relative to the uncoordi-
nated ligand on the other.[1–13] (Arene)tricarbonylchromium
complexes have been the subjects of a number of review
articles, the most recent of which give an excellent overview
of the state of the art in this field.[14–21] We have contributed
to this development in our investigations in the field of (ar-
ene)tricarbonylchromium complexes with functionalized
anellated rings.[22–24] Key compounds in our research are
complexes 1–4 of benzocyclobutenone,[22,25–31] benzocy-
clobutenedione,[27,29,30,32–37] 1,3-indandione,[38] and 1,2,3-
indantrione.[38] In particular, chemistry relating to 1 and 2
has unveiled important oxy anion-accelerated reactions,
such as anionic ring-opening reactions or dianionic oxy-
Cope rearrangements, which take place under particularly
mild reaction conditions. Here we wish to report the synthe-
sis of the missing link in the series, tricarbonyl(indan-1,2-
dione)chromium(0) (5), which shares with 1 the property of
planar chirality. We include attempts directed towards an
[a] Institut für Organische Chemie, Universität Hannover,
Schneiderberg 1B, 30167 Hannover, Germany
Fax: +49-511-762-4661
E-mail: holger.butenschoen@mbox.oci.uni-hannover.de
[b] Institut für Anorganische Chemie,
Callinstraße 9, 30167 Hannover, Germany
[‡] New address: Institut für Organische Chemie, Technische Uni-
versität Clausthal,
Leibnizstraße 6, 38678 Clausthal-Zellerfeld, Germany
5224
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Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
FULL PAPER
droxyindan-1-one complex, which was not fully charac-
terized. We suggest that the difference in reactivity of the
diacetal of 2 relative to rac-9 is due to the potential for enol
formation in the hydrolysis products from rac-9, which is
not the case for 2. In order to avoid acidic reaction condi-
tions we made recourse to an oxidative deacetalization with
trityl tetrafluoroborate, introduced by Barton in 1971,
which had already proven successful in the oxidative deace-
talization of 1,2-[bis(ethylenedioxy)benzocyclobutene]tri-
carbonylchromium(0) in our group.[41] In the course of this
reaction a hydride abstraction causes opening of the cyclic
acetal with formation of an oxenium ion, which is finally
hydrolyzed to give the deprotected ketone.[42,43] The reac-
tion was only partly successful, however, resulting in the
formation of a complex mixture of products, from which
monoacetal rac-10 was isolated in 31% yield and charac-
terized spectroscopically. The formation of rac-10 indicates
that the oxidation with trityl tetrafluoroborate is compati-
ble with the low-valent tricarbonylchromium group.
Results and Discussion
None of the complexes 1–5 is obtained in acceptable
yield by direct complexation of the ligand with common
complexation reagents. Complex 4 has been prepared, to-
gether with its hydrate tricarbonyl(ninhydrin)chromium(0),
by oxidation of 3 with dimethyldioxirane, whereas com-
plexes 1–3 have been obtained by protection of the keto
groups as acetals, followed by complexation and subsequent
acetal hydrolysis, and this route was therefore also envis-
aged for the synthesis of 5. Indan-1,2-dione (6) was treated
with ethane-1,2-diol in the presence of a catalytic amount
of p-toluenesulfonic acid (PTSA) for 48 h, resulting in a
77% yield of the desired diacetal 7 along with monoacetal
8 (17%). Subsequent treatment of 7 with Cr(CO)6 in Bu2O/
THF (10:1) afforded chromium complex rac-9 in 82% yield
as a bright yellow, air-sensitive material.
To facilitate the acetal cleavage, a new route using noncy-
clic acetals was envisaged. Indan-1,2-dione was treated with
2,2-dimethoxypropane or with triethyl orthoformate, in the
presence of a catalytic amount of PTSA and in the corre-
sponding alcohol as solvent to afford noncyclic monoacet-
als 11 and 12, respectively, in 91% and 56% yield. Subse-
quent reduction of 11 with sodium borohydride gave the
alcohol rac-13 in 90% yield.
The complexation of rac-13 with hexacarbonylchromium
in dibutyl ether/THF (10:1) afforded a diastereomeric mix-
ture of complexes rac-14 and rac-15 (72:28) in 86% overall
Next, rac-9 was treated with acid in order to hydrolyze yield. The assignment of the diastereomers was achieved on
1
the acetal functions and to obtain rac-5. Unlike in the syn- the basis of the H NMR spectra. The chemical shifts of
thesis of 2, however, use of 6  hydrochloric or sulfuric acid the benzylic protons next to the hydroxy substituent are
did not effect the desired reaction. In order to circumvent δ(rac-14) = 4.98 ppm and δ(rac-15) = 4.65 ppm. The assign-
solubility problems associated with water, dilute hydrochlo- ment for rac-14 compares well with the values observed for
ric or sulfuric acid was added to solutions of rac-9 in ace- the benzylic protons of compounds 16 (δ = 4.95 ppm), 17
tone or in THF. TLC monitoring indicated no reaction un- (δ = 4.84 ppm), and rac-18 (δ = 4.88 ppm).[38]
der these conditions; only addition of concentrated hydro-
Complexation from the sterically more shielded endo face
chloric acid to a THF solution of rac-9 caused an immedi- of the ligand system with predominant formation of rac-14
ate reaction, with TLC indicating the formation of a demonstrates an effect first reported by Schmalz with the
number of colorless decomplexation products after only complexation of tetralol derivatives, which has been ex-
1 min. The only chromium complex, isolated by column plained in terms of precomplexation of chromium to a lone
chromatography as a red oil in 10% yield, was a 2-hy- electron pair of the hydroxy substituent.[44] In order to en-
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D. Leinweber, I. Weidner, R. Wilhelm, R. Wartchow, H. Butenschön
FULL PAPER
Presumably for steric reasons, rac-14 adopts a conforma-
tion with no CO ligand below the anellated five-membered
ring. The arene C,C bond lengths alternate slightly as a re-
sult of the trans effect of the opposite CO ligands. As the
next step in the synthesis of rac-5, oxidation of alcohol rac-
14 to the corresponding ketone was envisaged. To achieve
this, an oxidation method compatible with the chromium in
a formal oxidation state of zero was needed. While oxi-
dation with DMSO/SO3/pyridine[45] afforded the desired
ketone in only 15% yield, together with 71% of starting
material,
a Swern oxidation with acetic anhydride/
DMSO[46] was more successful and gave ketone rac-19 in
81% yield. Remarkably, the acidic workup conditions did
not cause acetal hydrolysis. This observation contrasts with
the fact that the uncoordinated ligand 11 undergoes acetal
hydrolysis in the presence of a catalytic amount of sulfuric
acid in boiling ethanol.[47]
The deacetalization of rac-19 turned out to be problem-
atic. Treatment of rac-19 with concentrated hydrochloric
acid unexpectedly gave rac-20 in 53% yield as a single dia-
stereomer. With a number of other Brønsted or Lewis acids,
either no reaction took place or decomplexation and in
some cases decomposition occurred. Treatment with boron-
trifluoride–diethyl ether caused elimination of methanol re-
sulting in a 77% yield of rac-21. Neither rac-21 nor its li-
gand had been known previously.
hance the diastereomeric excess, Schmalz used dibutyl
ether/heptane/THF (30:30:1), which is less prone to occupy
coordination sites at chromium and thus facilitates the pre-
complexation process. When we used a 1:1 mixture of dibu-
tyl ether and heptane with a catalytic amount of THF as
solvent, we were delighted to obtain rac-14 as the only iso-
lated diastereomer, with only traces of rac-15 being detect-
able by TLC. In contrast to the tetralol ligands used by
Schmalz, rac-13 bears two methoxy substituents situated
next to the hydroxy group, one at each face of the ligand.
We regard it as remarkable that the precomplexation obvi-
ously takes place only at the benzylic hydroxy group and
not at the methoxy substituents.
The elimination of methanol from a dimethyl acetal on
treatment with boron trifluoride–diethyl ether has so far
been observed only once.[48] The only comparable reactions
are methanol elimination from 2,2-dimethoxycyclopenta-
none on treatment with FeCl3/SiO2, affording 2-methoxy-2-
cyclopentenone in 71% yield,[49] and an elimination caused
by DMSO at elevated temperature.[50]
The oxidative deacetalization mentioned above was tried
next.[42,43] When rac-19 was treated with 1.3 equivalents of
The final confirmation of the relative configuration of trityl tetrafluoroborate for 18 h, the substituted derivative
rac-14 was achieved when we succeeded in obtaining crys- rac-22 of the target complex was obtained in 48% yield
tals of rac-14 suitable for X-ray structure analysis (see Ex- along with rac-21, which was formed in 10% yield. In ac-
perimental Section) from a diethyl ether/petroleum ether cord with all analytical data we assign the exo configuration
mixture.
to rac-22 for obvious steric reasons.
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Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
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CBS reduction[51,52] in the synthesis of enantiomerically
highly enriched tetralol complexes.[44] The case of 11 is dif-
ferent, however, because the compound bears an acetal
moiety next to the keto function to be enantioselectively
reduced. The methoxy groups would be likely to cause a
reduction in enantiomeric excess, because their lone elec-
tron pairs might coordinate a chiral reduction catalyst at
either one of the enantiotopic faces of the keto group. In
spite of this concern we attempted the CBS reduction of 11.
After some optimization we found that the reaction works
with the borane/dimethyl sulfide complex as the reducing
reagent to give a 93% yield of (+)-(R)-13 with 74% ee. This
value compares to a 90–94% yield and 97.8% ee for the
CBS reduction of unsubstituted indan-1-one[53] and nicely
reflects the influence of the 2,2-dimethoxy substitution. The
absolute configuration was assigned on the basis of the ac-
cepted mechanism of the CBS reduction[54] and was later
confirmed by a structural analysis of the corresponding
chromium complex (vide infra).
The formation of rac-22 cannot be explained easily. The
reaction mechanism does not necessarily have to be the
same as with the cyclic acetals investigated by Barton.[42,43]
Possibly rac-21 is an intermediate, undergoing some type of
electrophilic addition with formation of rac-22. Use of a
larger excess of trityl tetrafluoroborate (1.5 equivalents) and
a shorter reaction time (3 h) gave rac-5 in 43% isolated yield
along with rac-22 (8%). Further investigation of the acetal
hydrolysis finally showed that the dione rac-5 could be ob-
tained in 55% yield as a red-brown solid by treatment of
rac-19 with formic acid. The polarity of rac-5 caused some
difficulties in the chromatographic purification, resulting in
a reduced yield.
An attractive alternative to the CBS reduction is the
asymmetric transfer hydrogenation of ketones catalyzed by
enantiomerically pure chiral ruthenium or rhodium com-
plexes.[55–58] So far there are no reports of enantioselective
reductions of α-keto acetals catalyzed by these complexes.
Ruthenium complex (S,S)-23 has been shown by Noyori to
catalyze the reduction of indan-1-one in Ͼ99% yield and
99% ee.[58] When 11 was treated with a 5:2 mixture of for-
mic acid and triethylamine as the hydrogen source in the
presence of 3 mol% of (S,S)-23, indanol acetal (–)-(S)-13
was obtained in 82% yield and 75% ee as determined by
1H NMR with Eu(hfc)3 as the shift reagent. A reduction in
the amount of catalyst to 0.85 mol% resulted in a chemical
yield of only 34% and an improved ee of 82%.
In order to improve the enantiomeric excess further we
Although the synthesis of rac-5 was finally successful, it decided to use the similar catalyst (R,R)-24, introduced by
appears somewhat redundant as it involves the reduction of Knochel.[59] Here, the chemical yield decreased to only 27%
the keto group in 11 and its later reoxidation. On the other of (+)-(R)-13, but with 84.5% ee.
hand, the high diastereoselectivity of the complexation of
The results show that the methoxy substituents next to
rac-13 indicates the availability of enantiomerically pure 5 the keto group affect the enantioselective reduction of 11 in
if 11 were to be enantioselectively reduced. This strategy such a way that either the chemical yield is good with mod-
has been pursued by Schmalz et al., who used the so-called erate enantiomeric excess or the enantiomeric excess is com-
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D. Leinweber, I. Weidner, R. Wilhelm, R. Wartchow, H. Butenschön
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paratively high with poor chemical yield. For the first time,
however, it has been shown that it is possible to achieve
reasonable enantiomeric excesses in an enantioselective re-
duction of an α-keto acetal. In order to obtain reasonable
amounts of enantiomerically pure material we therefore
made recourse to a classical racemic resolution of rac-13 by
use of (S)-2-acetoxyphenylacetic acid as the chiral auxiliary.
Esterification in the presence of 1.1 equivalents of dicyclo-
hexylcarbodiimide (DCC) and 10 mol% of 4-(dimeth-
ylamino)pyridine (DMAP) afforded an almost quantitative
yield of diastereomeric esters (R,S)-25 and (S,S)-26. Sepa-
ration by column chromatography was variable, giving 98 monoacetal complex (–)-pR-19 in 76% yield, and oxidative
to 99.4% de (GC). deacetalization with triphenylcarbenium tetrafluoroborate
Subsequent quantitative hydrolysis and complexation of finally gave (–)-pR-5 in 36% yield. Note that the deacetali-
(+)-(R)-13 with hexacarbonylchromium in a 1:1 mixture of zation with formic acid, which was carried out with racemic
dibutyl ether and heptane with 2% of added THF resulted material, gives a 55% yield (vide supra). Assuming no rea-
in the formation of a diastereomeric mixture of (–)-(1R)-14 sonable racemization pathway from (+)-(R)-13 we regard
(61%) and (+)-(1R)-15 (5%), which were separated by col- the ee of (–)-pR-5 as 99.4%.
umn chromatography. Complex (–)-endo-(1R)-14 was crys-
One reason for our interest in the indan-1,2-dione chro-
tallized from tert-butyl methyl ether/petroleum ether to af- mium complex was the potential to perform a dianionic
ford crystals suitable for an X-ray crystal structure analysis, oxy-Cope rearrangement upon alkenyllithium diaddition.
which finally confirmed the absolute configuration (Fig- This type of reaction starting from (benzocyclobutene-
ure 1) by refinement of the Flack x parameter.[60] The struc- dione)tricarbonylchromium has been investigated in depth
ture shows that the ligand adopts an envelope conformation by our group. The reaction sequence proved to be highly
with the acetal carbon atom bent towards the tricarbonyl- diastereoselective and makes highly substituted polycyclic
chromium group.
systems available in a very efficient way.[22,23,33–37,61–63] It
Swern oxidation of (–)-(1R)-14 with dimethyl sulfoxide/ was also shown that the vinyllithium diaddition followed by
acetic anhydride afforded the planar chiral indan-1,2-dione a dianionic oxy-Cope rearrangement works with uncoordi-
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Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
FULL PAPER
the hydroxy group. An enantioselective reduction of an α-
keto acetal has been achieved for the first time, giving up
to 84.5% ee, although the chemical yields were unsatisfac-
tory and a classical racemic resolution was therefore per-
formed. Attempts directed towards diaddition of alkenyl-
lithium reagents were unsuccessful, presumably due to
enolate formation. In order to circumvent this difficulty we
investigate nonenolizable indan-1,2-dione complexes.
Figure 1. Structure of (–)-(1R)-14 in the crystal. Selected bond
lengths [pm]: C1–C2 1.555(3), C1–C7A 149.8(3), C1–O1 140.4(3),
C2–C3 152.5(3), C2–O2 141.1(3), C2–O3 139.9(3), C3–C3A
149.6(3), C3A–C4 139.7(3), C3A–C7A 140.7(4), C4–C5 140.1(4),
C5–C6 140.5(5), C6–C7 139.9(4), C7–C7A 141.5(3), Cr1–C3A
225.6(2), Cr1–C4 224.2(2), Cr1–C5 219.1(2), Cr1–C6 220.1(2),
Cr1–C7 220.2(2), Cr1–C7A 223.6(2).
Experimental Section
General: See ref.[36] Melting points were determined with a Büchi
apparatus (Dr. Tottoli) without any correction. tert-Butyl methyl
ether (TBME), diethyl ether (DEE), petroleum ether (PE), and
tetrahydrofuran (THF) were distilled from sodium–potassium alloy
and benzophenone. Reagents were purchased and used without fur-
ther purification. In the 13C NMR spectra, according to APT and
DEPT measurements, “+” indicates signals of methylene or quater-
nary carbon atoms, whereas “–” indicates signals referring to
methyl or methyne carbon atoms.
1,2-Bis(ethylenedioxy)indan (7) and 1-(Ethylenedioxy)indan-2-one
(8): Indan-1,2-dione[66] (3280 mg, 22.5 mmol), ethane-1,2-diol
(4180 mg, 3.75 mL, 67.4 mmol), and p-toluenesulfonic acid (20 mg)
in benzene (125 mL) were heated at reflux with azeotropic water
removal for 48 h. After solvent removal at reduced pressure the
residue was purified by column chromatography (SiO2, DEE/PE,
1:2, 20×3 cm). Fraction I: 750 mg (3.95 mmol, 17%) of 1-(ethylen-
edioxy)indan-2-one (8), colorless solid (m. p. 110 °C). Fraction II:
4050 mg (17.3 mmol, 77%) of 1,2-bis(ethylenedioxy)indane (7), col-
orless solid (m. p. 123 °C).
Compound 7: 1H NMR (400 MHz, CDCl3): δ = 3.12 (s, 2 H, 3-H),
3.63 + 3.73 [m, 2×2 H, 10(11)-H], 4.04–4.16 [m, 4 H, 8(9)-H], 7.25–
7.44 (m, 4 H, arom.) ppm. 13C NMR (100 MHz, CDCl3): δ = 36.9
(+, C-3), 61.1 [+, C-8(9) or C-10(11)], 61.6 [+, C-8(9) or C-10(11)],
122.9 (–, C-5), 125.7 (–, C-6), 127.3 (–, C-4), 129.9 (–, C-7), 138.4
nated indan-1,2-dione, albeit in only moderate yield.[64] We
envisaged the possibility that the electron withdrawal from
the tricarbonylchromium group in 5 might help to improve
the allkenyllithium diaddition yield and thereby allow the
rearrangement to take place with better overall yield. How-
ever, treatment of rac-5 with an excess of vinyllithium or 1-
ethoxyvinyllithium resulted in the formation of the
monoadducts rac-27 and rac-28 in moderate yields. This re-
sult contrasts with that obtained with the uncoordinated
indan-1,2-dione and might be due to enolate formation as
a result of the enhanced acidity of the benzylic protons in
rac-5. This effect also became evident in the attempted syn-
thesis of a spirobenzylisoquinoline[65] through a Pictet–
Spengler reaction between (–)-pR-5 and 2-(3,4-dimeth-
oxyphenyl)ethylamine, which resulted in the formation of
the enamine (–)-(pR)-29 in 26% yield.
(+, C-3a), 139.6 (+, C-7a) ppm. IR (KBr): ν = 3087 (w), 2972 (w),
˜
2944 (w), 2916 (w), 2876 (w), 1460 (w), 1300 (m), 1256 (w), 1140
(m), 1092 (s, acetal-C–O), 1052 (m), 1028 (m), 972 (s), 904 (w), 776
(m), 684 (w), 660 (w) cm–1. MS (70 eV, 25 °C): m/z (%) = 236 (6)
[M + 2]+, 235 (40) [M + 1]+, 234 (66) [M]+, 206 (39), 189 (6), 174
(50), 162 (67), 146 (27), 135 (50), 118 (100) [C8H6O]+, 105 (60), 90
(64), 77 (33). HRMS, C13H14O4: calcd: 234.0892; found 234.0893.
C13H14O4 (234.09): calcd: C 66.66, H 6.02; found C 66.68, H 5.99.
In conclusion, we report a synthesis of the title com-
pound tricarbonyl(indan-1,2-dione)chromium (5) both in
racemic and in enantiomerically pure form. A striking fea-
ture of the synthesis is the diastereoselective complexation
1
Compound 8: H NMR (400 MHz, CDCl3): δ = 3.54 (s, 2 H, 3-H),
4.26–4.49 (m, 4 H, acetal-H), 7.30–7.56 (m, 4 H, arom.) ppm. 13C
NMR (100 MHz, CDCl3): δ = 38.9 (CH2, C-3), 66.0 [CH2, C-8(9)],
104.2 (Cq, C-1), 125.3 (CH, C-4 or C-5 or C-6 or C-7), 125.5 (CH,
of indanol 13 with the acetal methoxy substituents next to C-4 or C-5 or C-6 or C-7), 128.2 (CH, C-4 or C-5 or C-6 or C-7),
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D. Leinweber, I. Weidner, R. Wilhelm, R. Wartchow, H. Butenschön
2,2-Dimethoxyindan-1-one (11): Indan-1,2-dione[66] (5.000 g,
FULL PAPER
131.2 (CH, C-4 or C-5 or C-6 or C-7), 136.8 (Cq, C-3a or C-7a),
137.8 (C , C-3a or C-7a), 212.0 (C , C-2) ppm. IR (KBr): ν = 3063 34.2 mmol) and p-toluenesulfonic acid (0.030 g, 0.2 mmol) were
˜
q
q
(w), 2992 (w), 2952 (w), 2900 (w), 1756 (s, ketone), 1680 (w), 1612
dissolved in methanol (30 mL) and 2,2-dimethoxypropane (10 mL).
(w), 1464 (m), 1396 (m), 1300 (m), 1232 (w), 1152 (w), 1072 (s), The mixture was heated at reflux under argon for 23 h, the color
1020 (m), 948 (m), 916 (m), 764 (s), 648 (w), 596 (w) cm–1. MS becoming dark brown. After solvent removal at reduced pressure,
(70 eV, 25 °C): m/z (%) = 190 (1) [M]+, 162 (84), 135 (16), 105 (100)
[C7H5O]+, 90 (20), 77 (10). HRMS, C11H10O3: calcd: 190.0630;
found 190.0634. C11H10O3 (190.06): calcd: C 69.46, H 5.30; found
C 69.37, H 5.27.
the residual dark oil was purified by column chromatography
(SiO2, DEE/PE, 1:4, deactivation with triethylamine, 20×3 cm).
After crystallization from DEE/PE (1:5), 11 (5.980 g, 31.1 mmol,
91%) was obtained as a colorless solid (m. p. 65 °C). 1H NMR
(400 MHz, CDCl3): δ = 3.26 (s, 2 H, 3-H), 3.48 [s, 6 H, 8(9)-H],
7.35–7.81 (ABCD line system, 4 H, arom.] ppm. 13C NMR
(100 MHz, CDCl3): δ = 39.1 (+, C-3), 51.3 [–, C-8(9)], 102.6 (+, C-
2), 125.7 (–, C-4 or C-5 or C-6), 127.2 (–, C-4 or C-5 or C-6), 128.6
(–, C-4 or C-5 or C-6), 134.5 (+, C-3a), 136.4 (–, C-7), 150.0 (+,
rac-Tricarbonyl[η6-1,2-bis(ethylenedioxy)indane]chromium(0) (rac-
9): Compound 7 (500 mg, 2.1 mmol) and Cr(CO)6 (705 mg,
3.2 mmol) in dibutyl ether (70 mL) and THF (7 mL) were heated
at reflux for 19 h. After the mixture had cooled to 25 °C, the THF
was removed at reduced pressure, and a yellow precipitate was ob-
tained. After decanting of the almost colorless solvent and removal
of residual solvent at 0.01 mbar, rac-9 (640 mg, 1.7 mmol, 82%)
was obtained as a yellow solid (m. p. 195 °C, dec.). 1H NMR
C-7a), 198.0 (+, C-1) ppm. IR (CHCl ): ν = 3080 (w), 3000 (w),
˜
3
2964 (w), 2944 (m), 2836 (w), 1724 (s, ketone), 1608 (m), 1468 (m),
1304 (m), 1236 (m), 1140 (m), 1120 (m), 1048 (s), 852 (m) cm–1.
MS (70 eV, 20 °C): m/z (%) = 193 (3) [M +1]+, 192 (20) [M]+, 161
(24), 149 (5), 132 (6), 118 (14), 104 (32), 91 (100). HRMS,
C11H12O3: calcd: 192.0786; found 192.0791. C11H12O3 (192.21):
calcd: C 68.73, H 6.29; found C 68.88, H 6.29.
2
(400 MHz, [D6]acetone): δ = 3.00 (d, Jexo-3,endo-3 = –16.1 Hz, 1 H,
2
exo-3-H or endo-3-H), 3.11 (d, Jexo-3,endo-3 = –16.1 Hz, 1 H, exo-
3-H or endo-3-H), 3.58–3.70 (m, 2 H, acetal-H), 3.80–3.88 (m, 1
3
3
H, acetal-H), 3.95–4.12 (m, 5 H, acetal-H), 5.27 (t, J4,5 = J5,6
=
=
=
=
3
3
3
5.8 Hz or J5,6 = J6,7 = 5.8 Hz, 1 H, 5-H or 6-H), 5.58 (d, J4,5
2,2-Diethoxyindan-1-one
(12):
Indan-1,2-dione[66]
(376 mg,
3
3
3
5.8 Hz or J6,7 = 5.8 Hz, 1 H, 4-H or 7-H), 5.84 (t, J4,5 = J5,6
2.6 mmol) and p-toluenesulfonic acid (20 mg) were heated at reflux
in anhydrous ethanol (5 mL) and triethyl orthoformate (5 mL) for
18 h, the mixture becoming dark. After hydrolysis with satd. aq.
sodium hydrogen carbonate (20 mL), the mixture was extracted
3
3
3
5.8 Hz or J5,6 = J6,7 = 5.8 Hz, 1 H, 5-H or 6-H), 6.03 (d, J4,5
5.8 Hz or J6,7 = 5.8 Hz, 1 H, 4-H or 7-H) ppm. 13C NMR
3
(100 MHz, [D6]acetone): δ = 37.9 (+, C-3), 62.5 (+, C-8 or C-9 or
C-10 or C-11), 63.0 (+, C-8 or C-9 or C-10 or C-11), 63.2 (+, C-8 three times with DEE (each 3 mL). The collected organic layers
or C-9 or C-10 or C-11), 63.4 (+, C-8 or C-9 or C-10 or C-11), were washed twice with water (5 mL) and dried with potassium
88.6 (–, C-4 or C-5), 89.0 (–, C-4 or C-5), 94.8 (–, C-6 or C-7), 98.0 carbonate. After filtration and solvent removal at reduced pressure
(+, C-2), 99.1 (–, C-6 or C-7), 101.0 (+, C-1), 111.0 (+, C-3a), 116.9
the residual oil was crystallized from PE. Compound 12 (320 mg,
(+, C-7a), 235.1 (+, CO) ppm. IR (KBr): ν = 3076 (w), 2976 (w),
1.5 mmol, 56%) was obtained as a colorless solid (m. p. 62 °C). 1H
˜
3
2940 (w), 2876 (w), 1964 (s, CO), 1868 (s, CO), 1452 (w), 1424 (w),
NMR (400 MHz, CDCl3): δ = 1.22 [t, J8,9 = 7.0 Hz, 6 H, 9(9Ј)-
3
1300 (w), 1264 (w), 1232 (w), 1144 (m), 1096 (s), 1052 (w), 1028 H], 3.30 (s, 2 H, 3-H), 3.75 [q, J8,9 = 7.0 Hz, 4 H, 8(8Ј)-H], 7.35–
(w), 972 (m), 668 (m), 632 (m), 536 (w) cm–1. MS (70 eV, 60 °C):
m/z (%) = 372 (2) [M + 2]+, 371 (4) [M + 1]+, 370 (11) [M]+, 313
7.82 (m, 4 H, arom.) ppm. 13C NMR (100 MHz, CDCl3): δ = 16.0
[–, C-9(9Ј)], 40.0 (+, C-3), 59.2 [+, C-8(8Ј)], 102.4 (+, C-2), 125.6
(15) [M – 2×CO]+, 286 (26) [M – 3×CO]+, 256 (24), 226 (100) (–, C-4 or C-5 or C-6), 127.2 (–, C-4 or C-5 or C-6), 128.4 (–, C-4
[(C11H10O2)Cr]+, 174 (23), 162 (14), 118 (60), 90 (25). HRMS,
C16H14CrO7: calcd: 370.01446; found 370.01226. C16H14CrO7
(370.01): calcd: C 51.90, H 3.81; found C 51.76, H 3.85.
or C-5 or C-6), 134.7 (+, C-7a), 136.3 (–, C-7), 150.2 (+, C-3a),
198.5 (+, C-1) ppm. IR (CHCl ): ν = 3061 (w), 2980 (m), 2928 (w),
˜
3
2896 (w), 1724 (s, ketone), 1608 (m), 1468 (w), 1392 (w), 1304 (m),
1232 (w), 1192 (w), 1164 (m), 1132 (m), 1164 (w), 1132 (m), 1048
(s), 952 (m) cm–1. MS (70 eV, 25 °C): m/z (%) = 221 (2) [M + 1]+,
220 (11) [M]+, 191 (2), 175 (6), 164 (5), 147 (29), 135 (21), 118
(20), 104 (48), 91 (100). HRMS, C13H16O3: calcd: 220.1010; found
220.1010.
rac-Tricarbonyl[η6-2-(ethylenedioxy)indan-1-one]chromium(0) (rac-
10): Compound rac-9 (300 mg, 0.8 mmol) and triphenylcarbenium
tetrafluoroborate (670 mg, 2.0 mmol) were stirred in anhydrous
dichloromethane (10 mL) for 18 h at 20 °C, the color changing
from yellow to deep red. After solvent removal at reduced pressure
the residual dark oil was purified by column chromatography
(SiO2, DEE/PE, 1:1, 25×3 cm). Compound rac-10 (80 mg,
0.24 mmol, 31%) was obtained as an orange solid (m. p. 128 °C).
rac-2,2-Dimethoxyindan-1-ol (rac-13): Sodium tetrahydridoborate
(1.600 g, 42.2 mmol) was added to 11 (5.400 g, 28.1 mmol) in etha-
nol (75 mL). After the mixture had been stirred for 18 h at 20 °C,
water 200 mL was added and the mixture was extracted ten times
2
1H NMR (400 MHz, CDCl3): δ = 3.22 (d, Jendo-3,exo-3 = –17.2 Hz,
2
1 H, endo-3-H or exo-3-H), 3.40 (d, Jendo-3,exo-3 = –17.2 Hz, 1 H, with DEE (50 mL). The collected organic layers were washed three
endo-3-H or exo-3-H), 4.04–4.50 (m, 4 H, acetal-H), 5.15–5.98 times with water (100 mL each) and dried with potassium carbon-
(ABCD line system, 4 H, arom.) ppm. 13C NMR (100 MHz, ate. After solvent removal at reduced pressure the remaining oil
CDCl3): δ = 35.4 (+, C-3), 64.6 (+, C-8 or C-9), 64.8 (+, C-8 or C-
9), 85.1 (–, C-4 or C-5 or C-6), 87.2 (–, C-4 or C-5 or C-6), 87.3
(–, C-4 or C-5 or C-6), 89.7 (+, C-2), 93.9 (–, C-7), 104.4 (+, C-
was crystallized from PE. Compound rac-13 (4.920 g, 25.3 mmol,
90%) was obtained as a colorless solid (m. p. 56 °C). 1H NMR
3
(400 MHz, CDCl3): δ = 2.92 (d, J1,OH = 8.8 Hz, 1 H, OH), 2.94
2
2
3a), 116.4 (+, C-7a), 197.9 (+, C-1), 228.2 (+, CO) ppm. IR (KBr): (d, J3,3 = –16.5 Hz, 1 H, cis-3-H or trans-3-H), 3.26 (d, J3,3
=
ν = 3075 (w), 2904 (w), 1992 (s, CO), 1928 (s, CO), 1720 (s, ketone), –16.5 Hz, 1 H, cis-3-H or trans-3-H), 5.02 (d, 3J1,OH = 8.6 Hz, 1 H,
˜
1596 (w), 1524 (w), 1428 (w), 1316 (w), 1280 (w), 1228 (w), 1156
(m), 1136 (m), 1100 (m), 1016 (w), 648 (m), 612 (m) cm–1. MS (100 MHz, CDCl3): δ = 38.3 (CH2, C-3), 50.0 (CH3, C-8 or C-9),
(70 eV, 100 °C): m/z (%) = 327 (3) [M + 1]+, 326 (5) [M]+, 325 (11),
51.3 (CH3, C-8 or C-9), 78.4 (CH, C-1), 109.8 (Cq, C-2), 125.3
1-H), 7.14–7.43 (ABCD line system, 4 H, arom.) ppm. 13C NMR
270 (13) [M – 2×CO]+, 242 (13) [M – 3×CO]+, 214 (22), 198 (67) (CH, C-4, C-5), 127.8 (CH, C-6 or C-7), 129.1 (CH, C-6 or C-7),
[(C9H6O2)Cr]+, 186 (5), 170 (7), 142 (13), 118 (5), 105 (6), 90 (5),
52 (100) [52Cr]+. HRMS, C14H10CrO6: calcd: 325.9883; found
325.9888.
138.6 (C , C-7a), 143.5 (C , C-3a) ppm. IR (CHCl ): ν = 3552 (m,
˜
q q 3
OH), 3076 (w), 3000 (m), 2964 (m), 2944 (m), 2840 (w), 1608 (w),
1460 (m), 1392 (m), 1324 (w), 1300 (w), 1268 (m), 1228 (m), 1184
5230
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 5224–5235

Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
FULL PAPER
(m), 1140 (s), 1120 (s), 1056 (s), 860 (w) cm–1. MS (70 eV, 20 °C): 20.8 Hz, 1 H, OH), 3.35 (s, 3 H, 8-H or 9-H), 3.40 (s, 3 H, 8-H or
3
3
3
m/z (%) = 196 (1) [M + 2]+, 195 (8) [M + 1]+, 194 (55) [M]+, 163
9-H), 4.98 (d, J1,OH = 10.3 Hz, 1 H, 1-H), 5.41 (t, J4,5 = J5,6
=
=
=
=
3
3
3
(5), 147 (53), 131 (26), 119 (100), 103 (28), 91 (74), 75 (28). HRMS, 6.3 Hz or J5,6 = J6,7 = 6.3 Hz, 1 H, 5-H or 6-H), 5.53 (d, J4,5
3
3
3
C11H14O3: calcd: 194.09429; found 194.09403. C11H14O3 (194.09):
calcd: C 68.02, H 7.26; found C 67.93, H 7.22.
6.6 Hz or J6,7 = 6.6 Hz, 1 H, 4-H or 7-H), 5.65 (t, J4,5 = J5,6
6.4 Hz or J5,6 = J6,7 = 6.4 Hz, 1 H, 5-H or 6-H), 5.75 (d, J4,5
3
3
3
6.3 Hz or J6,7 = 6.3 Hz, 1 H, 4-H or 7-H) ppm. 13C NMR
(100 MHz, [D6]acetone): δ = 37.1 (+, C-3), 49.7 (–, C-8 or C-9),
50.9 (–, C-8 or C-9), 77.7 (–, C-1), 89.1 (–, C-4 or C-5 or C-6 or
C-7), 91.5 (–, C-4 or C-5 or C-6 or C-7), 96.1 (–, C-4 or C-5 or C-
6 or C-7), 107.3 (+, C-2), 111.8 (+, C-7a), 116.0 (+, C-3a), 234.8
3
(+)-(R)-2,2-Dimethoxyindan-1-ol [(+)-(R)-13] by Enantioselective
Reduction: a) Borane–dimethyl sulfide (0.07 mL, 0.7 mmol) was
added dropwise at –15 °C to 11 (200 mg, 1.1 mmol) and (S)-
1-methyl-3,3-diphenyltetrahydro-1H,3H-pyrrolo[1,2-c][1,3,2]oxaza-
borole (oxazaborolidine) (0.04 mL, 0.2 mmol) in THF (5 mL). The
mixture was warmed to 25 °C over 14 h, and after addition of
methanol (1 mL) the solvent was removed at reduced pressure. The
crude product was purified by column chromatography (SiO2,
TBME/PE, 1:2, 20×3 cm) to provide (+)-(R)-13 (1187 mg,
1.0 mmol, 93%, 74% ee) as a colorless oil. The ee was determined
by NMR with europium()-tris[3-(heptafluoropropylhydroxyme-
thylene)camphorate] as the chiral shift reagent and integration of
the signals of the benzylic protons. b) Compound 11 (400 mg,
2.1 mmol), (R,R)-24[59] (39 mg, 0.063 mmol, 3 mol%), and potas-
sium hydroxide (6 mg, 0.1 mmol, 5 mol%) were stirred in propan-
2-ol (10 mL) at 25 °C for 60 h. After addition of water (100 mL)
the mixture was extracted five times with TBME (each 50 mL).
After drying over potassium carbonate, filtration, and solvent re-
moval at reduced pressure, the crude product was purified by col-
umn chromatography (SiO2, TBME/PE, 1:5, 20×3 cm) to provide
(+)-(R)-13 (110 mg, 0.6 mmol, 27%, 84.5% ee), [α]2D0 = +20.8 (c =
1, CHCl3). The enantiomeric excess was determined by gas
chromatography of the (S)-2-acetylphenylacetate.
(+, CO) ppm. IR (KBr): ν = 3500 (s, OH), 3085 (w), 2940 (w), 2908
˜
(w), 2840 (w), 1956 (s, CO), 1856 (s, CO), 1448 (m), 1428 (w), 1388
(w), 1316 (w), 1260 (w), 1216 (m), 1180 (w), 1136 (m), 1052 (s),
1008 (w), 664 (s), 632 (m) cm–1. MS (70 eV, 20 °C): m/z (%) = 331
(4) [M + 1]+, 330 (14) [M]+, 274 (19) [M – 2×CO]+, 246 (60) [M –
3×CO]+, 228 (7), 214 (54), 198 (13), 184 (65), 146 (100)
[C9H6O2]+, 131 (28), 119 (16), 103 (67), 91 (23), 77 (19), 52 (67).
HRMS, C12H14CrO4 [M – 2×CO]+: calcd: 274.02929; found
274.02939. C12H14CrO4 (330.05): calcd: C 50.92, H 4.27; found C
50.78, H 4.34.
1
Compound rac-15: H NMR (400 MHz, [D6]acetone): δ = 2.97 (d,
2Jendo-3,exo-3 = –16.5 Hz, 1 H, endo-3-H or exo-3-H), 3.05 (d,
2Jendo-3,exo-3 = –16.5 Hz, 1 H, endo-3-H or exo-3-H), 3.32 (s, 3 H,
3
8-H or 9-H), 3.35 (s, 3 H, 8-H or 9-H), 4.53 (d, J1,OH = 6.4 Hz, 1
H, OH), 4.65 (d, J1,OH = 7.2 Hz, 1 H, 1-H), 5.47 (t, J4,5 = J5,6
= 6.3 Hz or J5,6 = J6,7 = 6.3 Hz, 1 H, 5-H or 6-H), 5.57 (t, J4,5
= J5,6 = 6.3 Hz or J5,6 = J6,7 = 6.3 Hz, 1 H, 5-H or 6-H), 5.67
3
3
3
3
3
3
3
3
3
3
3
(d, J4,5 = 6.4 Hz or J6,7 = 6.4 Hz, 1 H, 4-H or 7-H), 5.84 (d,
3J4,5 = 6.4 Hz or J6,7 = 6.4 Hz, 1 H, 4-H or 7-H) ppm. 13C NMR
3
(–)-(S)-2,2-Dimethoxyindan-1-ol [(–)-(S)-13] by Enantioselective Re-
duction: a) A suspension of 11 (400 mg, 2.1 mmol) and (S,S)-23
(12 mg, 0.018 mmol, 0.85 mol%) in formic acid/triethylamine (5:2,
1 mL) was stirred at 25 °C for 60 h. After addition of water
(100 mL) the mixture was extracted five times with TBME (each
50 mL). After drying over potassium carbonate, filtration, and sol-
vent removal at reduced pressure the remaining crude product was
purified by column chromatography (SiO2, TBME/PE, 1:5,
20×3 cm) to provide (–)-(S)-13 (139 mg, 0.71 mmol, 34%, 82% ee),
[α]2D0 = –20.1 (c = 1, CHCl3). The ee was determined by NMR with
europium()-tris[3-(heptafluoropropylhydroxymethylene)cam-
phorate] as the chiral shift reagent and integration of the signals of
the benzylic protons. b) As a), with 3.0 mol% of (S,S)-23: Yield
82%, 75% ee.
(100 MHz, [D6]acetone): δ = 37.4 (+, C-3), 50.0 (–, C-8 or C-9),
50.7 (–, C-8 or C-9), 77.7 (–, C-1), 90.8 (–, C-4 or C-5 or C-6 or
C-7), 92.8 (–, C-4 or C-5 or C-6 or C-7), 93.3 (–, C-4 or C-5 or C-
6 or C-7), 94.8 (–, C-4 or C-5 or C-6 or C-7), 108.9 (+, C-2), 112.6
(+, C-7a), 113.1 (+, C-3a), 234.5 (+, CO) ppm. IR (KBr): ν = 3520
˜
(m, OH), 3085 (w), 2976 (w), 2948 (w), 1968 (s, CO), 1876 (s, CO),
1452 (w), 1436 (w), 1356 (w), 1256 (w), 1212 (w), 1120 (m), 1076
(w), 1048 (m), 668 (m), 632 (m) cm–1. MS (70 eV, 80 °C): m/z (%)
= 332 (3) [M + 2]+, 331 (9) [M + 1]+, 330 (32) [M]+, 274 (10) [M –
2×CO]+, 246 (62) [M – 3×CO]+, 228 (9), 214 (65), 198 (18), 184
(66), 171 (7), 147 (100) [C9H7O2]+, 131 (26), 119 (13), 103 (44), 91
(21), 77 (14), 52 (74). HRMS, C12H14CrO4 [M – 2×CO]+: calcd.:
274.02972; found 274.02985. C12H14CrO4 (330.05): calcd: C 50.92,
H 4.27; found C 50.94, H 4.17.
rac-endo-Tricarbonyl(η6-2,2-dimethoxyindan-1-ol)chromium(0) (rac-
Crystal Structure Analysis of rac-14:[67] C14H14CrO6, molecular
weight 330.25, crystal system monoclinic, space group P 21/n, a =
7.234(1), b = 18.707(3), c = 10.512(2) Å, α = 90°, β = 90.01(2)°, γ
= 90.11(2)°, V = 1422.6(4) Å3, Z = 4, dcalcd. = 1.542 Mgm–3, F(000)
= 680, µ = 8.28 mm–1, crystal size 1.37×0.26×0.15 mm, Stoe IPDS
area detector diffractometer, T = 300(2) K, Mo-Kα = 0.71073 Å,
θmin = 2.18, θmax = 24.15°, –8 Յ h Յ 8, –21 Յ k Յ 21, –12 Յ l
Յ 12, no absorption correction, no extinction correction, 10108
collected, 2182 unique reflections, 1638 observed reflections [I Ͼ
2σ(I)], 194 refined parameters, [R(int) = 0.0363], refinement pro-
gram: SHELXL-93, refinement by full-matrix least-squares method
(F2), hydroxy H was found and refined, R indices: [I Ͼ 2σ(I)] R1 =
0.0290, wR2 = 0.0660, largest diff. peak and hole 0.222 and –0.159
eÅ3
14)
and
rac-exo-Tricarbonyl(η6-2,2-dimethoxyindan-1-ol)chro-
mium(0) (rac-15): a) Compound rac-13 (4.200 g, 21.6 mmol) and
hexacarbonylchromium (6.210 g, 28.1 mmol) in dibutyl ether
(200 mL) and THF (20 mL) were heated at reflux for 24 h. The
solvent was removed at reduced pressure, and the remaining green-
yellow solid was purified by column chromatography (SiO2, DEE/
PE, 1:1, then DE, 30×5 cm). Fraction I: 4.340 g (13.2 mmol, 61%)
of rac-14, bright yellow solid (m. p. 149 °C). Fraction II: 1.740 g
(5.3 mmol, 25%) of rac-15, bright yellow solid (m. p. 128 °C).
b) Compound rac-13 (7.000 g, 27.7 mmol) and hexacarbonylchro-
mium (6.700 g, 30.5 mmol) in dibutyl ether (120 mL), heptane
(120 mL), and THF (4 mL) were heated at reflux for 24 h. After
solvent removal at reduced pressure the remaining green-yellow so-
lid was purified by column chromatography (SiO2, TBME/PE, 1:4,
then TBME, 25×5 cm) to provide rac-14 (6.600 g, 19.9 mmol,
72%) as a bright yellow solid [m. p. 149 °C, de Ͼ 95% (NMR)].
rac-Tricarbonyl(η6-2,2-dimethoxyindan-1-one)chromium(0) (rac-19):
Compound rac-14 (1620 mg, 4.90 mmol) was stirred for 10 h at
25 °C in anhydrous DMSO (9.6 mL) and acetic acid anhydride
(7.2 mL). After hydrolysis with water (200 mL) the mixture was
1
Compound rac-14: H NMR (400 MHz, [D6]acetone): δ = 2.84 (d,
2Jendo-3,exo-3 = –16.7 Hz, 1 H, endo-3-H or exo-3-H), 3.16 (d,
2Jendo-3,exo-3 = –16.7 Hz, 1 H, endo-3-H or exo-3-H), 3.34 (d, J = extracted three times with diethyl ether (each 40 mL). The collected
Eur. J. Org. Chem. 2005, 5224–5235
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5231

D. Leinweber, I. Weidner, R. Wilhelm, R. Wartchow, H. Butenschön
FULL PAPER
3
3
organic layers were washed five times with satd. aq. sodium hydro-
gen carbonate and satd. aq. sodium chloride (each 30 mL). After
drying over magnesium sulfate, filtration, and solvent removal, the
crude product was purified by column chromatography (SiO2,
DEE/PE, 1:1, 20×3 cm) to provide rac-19 (1.300 g, 4.0 mmol,
5.70 (d, J4,5 = 6.5 Hz or J6,7 = 6.5 Hz, 1 H, 4-H or 7-H), 6.09 (t,
3
3
3
3J4,5 = J5,6 = 6.5 Hz or J5,6 = J6,7 = 6.5 Hz, 1 H, 5-H or 6-H),
3
3
6.31 (d, J4,5 = 6.5 Hz or J6,7 = 6.5 Hz, 1 H, 4-H or 7-H), 6.43 (s,
1 H, 3-H) ppm. 13C NMR (100 MHz, [D6]acetone): δ = 57.4 (–, C-
8), 87.1 (+, C-3a), 87.1 (–, C-4 or C-5 or C-6 or C-7), 87.8 (–, C-4
or C-5 or C-6 or C-7), 91.6 (–, C-4 or C-5 or C-6 or C-7), 94.6
(–, C-4 or C-5 or C-6 or C-7), 109.7 (–, C-3), 113.8 (+, C-7a), 156.3
1
81%) as a red solid (m. p. 119 °C). H NMR (400 MHz, [D6]ace-
2
tone): δ = 3.19 (d, Jendo-3,exo-3 = –16.7 Hz, 1 H, endo-3-H or exo-
2
3-H), 3.33 (d, Jendo-3,exo-3 = –16.7 Hz, 1 H, endo-3-H or exo-3-H),
(+, C-2), 187.2 (+, C-1), 232.2 (+, CO) ppm. IR (KBr): ν = 3080
˜
3.39 (s, 3 H, 8-H or 9-H), 3.39 (s, 3 H, 8-H or 9-H), 5.59–6.13 (m), 3060 (m), 2980 (m), 2936 (m), 1972 (s, CO), 1904 (s, CO), 1696
(ABCD-system, 4 H, arom.) ppm. 13C NMR (100 MHz, [D6]ace-
(s, ketone), 1600 (m), 1544 (m), 1520 (w), 1452 (w), 1404 (m), 1316
(w), 1260 (w), 1220 (m), 1160 (w), 1096 (w), 1028 (m), 804 (m), 652
tone): δ = 36.9 (+, C-3), 49.5 (–, C-8 or C-9), 49.9 (–, C-8 or C-9),
88.4 (–, C-4 or C-5 or C-6), 89.3 (–, C-4 or C-5 or C-6), 90.4 (–, (m), 620 (m) cm–1. MS (70 eV, 110 °C): m/z (%) = 298 (4) [M + 2],
C-4 or C-5 or C-6), 92.7 (+, C-2), 97.3 (–, C-7), 100.2 (+, C-3a),
297 (10) [M + 1]+, 296 (33) [M]+, 268 (3) [M – CO]+, 240 (23) [M –
2×CO]+, 212 (97) [M – 3×CO]+, 197 (100) [(C9H5O2)Cr]+, 169
(20), 160 (16), 141 (59), 131 (10), 108 (9), 89 (42), 81 (16), 52 (92)
[52Cr]+. HRMS, C13H8CrO5: calcd: 295.9777; found 295.9764.
119.2 (+, C-7a), 194.8 (+, C-1), 230.7 (+, CO) ppm. IR (KBr): ν =
˜
3061 (w), 2948 (w), 2924 (w), 2836 (w), 1996 (s, CO), 1924 (s, CO),
1892 (s, CO), 1716 (s, ketone), 1520 (w), 1276 (w), 1232 (w), 1136
(m), 1052 (w), 1028 (w), 896 (w), 656 (w), 612 (m) cm–1. MS (70eV, C13H8CrO5 (295.98): calcd: C 52.72, H 2.72; found C 53.32, H 2.98.
110 °C): m/z (%) = 330 (1) [M + 2]+, 329 (4) [M + 1]+, 328 (14)
[M]+, 297 (5), 272 (20) [M – 2×CO]+, 244 (29) [M – 3×CO]+, 229
(100), 213 (9), 199 (60), 184 (8), 171 (76), 143 (11), 118 (5), 91 (15).
HRMS, C14H12CrO6: calcd: 328.0039; found 328.0032.
C14H12CrO6 (328.00): calcd: C 51.23, H 3.68; found C 51.11, H
3.70.
Tricarbonyl[η6-3-(triphenylmethyl)indan-1,2-dione]chromium(0)
(rac-22): Compound rac-19 (200 mg, 0.6 mmol) and triphenylmeth-
ylcarbenium tetrafluoroborate (262 mg, 0.8 mmol) were stirred at
20 °C for 18 h in anhydrous dichloromethane (10 mL). After sol-
vent removal at reduced pressure the remaining black residue was
purified by column chromatography (SiO2, TBME/PE, 1:3, then
TBME, 25×3 cm). Fraction I: 125 mg (0.6 mmol, 48%) of rac-22
as a brown solid (m. p. 186 °C). Fraction II: 10 mg (0.03 mmol,
5%) of rac-21 [de Ͼ 95% (NMR)].
Tricarbonyl(η6-2-hydroxyindan-1-one)chromium(0) (rac-20): Conc.
hydrochloric acid (30 mL) was slowly added to rac-19 (240 mg,
0.7 mmol) in THF (30 mL). The solution immediately became dark
red and lighter afterwards. After 5 min no starting material could
be detected by TLC. Water (100 mL) was added, and the mixture
was extracted three times with TBME (each 20 mL). The combined
organic layers were washed three times with satd. aq. sodium hy-
drogen carbonate and three times with water (each 20 mL). After
drying over potassium carbonate, filtration, and solvent removal at
reduced pressure a brown oil was obtained and was purified by
column chromatography (SiO2, TBME/PE, 1:1, then TBME,
30×3 cm) to provide rac-20 (110 mg, 0.39 mmol, 53%) as a red oil
1
Compound rac-22: H NMR (400 MHz, [D6]acetone): δ = 5.45 (d,
3
3J4,5 = 7.0 Hz or J6,7 = 7.0 Hz, 1 H, 4-H or 7-H), 5.63 (s, 1 H, 3-
3
3
3
3
H), 5.69 (t, J4,5 = J5,6 = 7.0 Hz or J5,6 = J6,7 = 7.0 Hz, 1 H, 5-
3
3
H or 6-H), 6.05 (d, J4,5 = 7.0 Hz or J6,7 = 7.0 Hz, 1 H, 4-H or 7-
3
3
3
3
H), 6.08 (t, J4,5 = J5,6 = 7.0 Hz or J5,6 = J6,7 = 7.0 Hz, 1 H, 5-
H
or 6-H), 7.13–7.52 (m, 15 H, trityl-H) ppm. 13C NMR
(100 MHz, [D6]acetone): δ = 49.6 (CH, C-3), 64.1 (Cq, C-8), 89.7
(CH, C-4 or C-5 or C-6), 90.4 (CH, C-4 or C-5 or C-6), 91.0 (CH,
C-4 or C-5 or C-6), 97.1 (CH, C-7), 97.1 (CH, C-7), 97.3 (Cq, C-
3a), 117.7 (Cq, C-7a), 126.7 (CH, C-12), 127.9 [CH, C-10 (11, 13,
14)], 129.8 (Cq, C-9), 179.0 (Cq, C-1), 195.9 (Cq, C-2), 229.7 (Cq,
1
[(de Ͼ 95% (NMR)]. H NMR (400 MHz, [D6]acetone): δ = 2.86
2
(d, Jendo-3,exo-3 = –17.1 Hz, 1 H, endo-3-H or exo-3-H), 3.60 (d,
2Jendo-3,exo-3 = –17.1 Hz, 1 H, endo-3-H or exo-3-H), 4.45 (br., 1
H, 2-H), 5.17 (br., 1 H, OH), 5.48–6.23 (ABCD line system, 4 H,
arom.) ppm. 13C NMR (100 MHz, [D6]acetone): δ = 34.6 (+, C-3),
71.2 (–, C-2), 88.7 (–, C-4 or C-5 or C-6), 89.6 (–, C-4 or C-5 or
C-6), 90.0 (–, C-4 or C-5 or C-6), 95.5 (+, C-3a), 97.2 (–, C-7),
CO) ppm. IR (KBr): ν = 3088 (w), 3056 (w), 3032 (w), 2924 (w),
˜
2852 (w), 1988 (s, CO), 1928 (s, CO), 1756 (m, ketone), 1712 (s,
ketone), 1524 (w), 1492 (w), 1448 (w), 1284 (w), 1252 (w), 1100 (w),
1032 (w), 704 (m), 648 (m), 608 (m) cm–1. MS (70 eV, 150 °C): m/z
(%) = 524 (1) [M]+, 440 (20) [M – 3×CO]+, 243 (100) [Ph3C]+, 228
(10), 215 (9), 197 (9), 165 (84), 141 (8), 115 (6), 91 (7), 77 (4), 52
(11). HRMS, C31H20CrO5: calcd: 524.0716; found 524.0703.
121.2 (+, C-7a), 202.9 (+, C-1), 231.0 (+, CO) ppm. IR (CHCl ): ν
˜
3
= 3555 (w, OH), 3032 (w), 2976 (w), 1988 (s, CO), 1928 (s, CO),
1716 (s, ketone), 1520 (w), 1428 (w), 1260 (w), 1100 (w), 1016
(w) cm–1. MS (70 eV, 140 °C): m/z (%) = 286 (2) [M + 2]+, 285 (4)
[M + 1]+, 284 (12) [M]+, 228 (10) [M – 2×CO]+, 220 (15), 200 (67)
[M – 3×CO]+, 182 (84) [(C9H6O)Cr]+, 172 (19), 148 (17), 131 (6),
115 (4), 91 (9), 52 (42). HRMS, C12H8CrO5: calcd: 283.9772; found
283.9773.
rac-Tricarbonyl(η6-indan-1,2-dione)chromium(0) (rac-5): a) Com-
pound rac-19 (250 mg, 0.8 mmol) and triphenylcarbenium tetra-
fluoroborate (374 mg, 1.1 mmol) were stirred at 20 °C in anhydrous
dichloromethane (10 mL) for 3 h. After addition of water (30 mL)
the layer was extracted three times with dichloromethane (each
10 mL). The combined organic layers were dried with magnesium
sulfate and filtered, and the solvent was removed at reduced pres-
sure. The remaining black residue was purified by column
chromatography (SiO2, TBME/PE, 1:1, then TBME, 30×3 cm).
Fraction I: 30 mg (0.1 mmol, 8%) of rac-22. Fraction II: 20 mg
(0.1 mmol, 8%) of rac-19. Fraction III: 92 mg (0.3 mmol, 43%) of
rac-5 as a brown solid (m. p. 129 °C). b) Compound rac-19
(4.000 g, 12.0 mmol) in formic acid (50 mL) was stirred at 25 °C
for 1.5 h. After addition of water (200 mL) the layer was extracted
three times with dichloromethane (each 20 mL). After drying over
magnesium sulfate, filtration, and solvent removal at reduced pres-
sure, the crude product was purified by column chromatography
(SiO2, TBME/PE, 1:11, then TBME, 25×30 cm) to provide rac-5
(1.860 g, 6.6 mmol, 55%) as a red-brown solid (m. p. 127 °C).
Tricarbonyl(η6-2-methoxyinden-1-one)chromium(0) (rac-21): A solu-
tion of boron trifluoride–diethyl ether in DEE (50%, 10 mL) was
added at 0 °C to rac-19 (500 mg, 1.5 mmol). A blue-purple suspen-
sion formed, and the mixture was stirred at 0 °C for 1 h. After
hydrolysis with ice water (100 mL) the mixture was extracted three
times with TBME (each 30 mL). The collected organic layers were
washed twice with water (50 mL each) and dried with magnesium
sulfate. After solvent removal at reduced pressure the remaining
purple-black crude product was purified by column chromatog-
raphy (SiO2, TBME/PE, 1:1, then TBME, 30×3 cm) to provide
rac-21 (347 mg, 1.2 mmol, 77%) as a purple solid (m. p. 132 °C).
1H NMR (400 MHz, [D6]acetone): δ = 3.81 (s, 3 H, 8-H), 5.59 (t,
3
3
3
3J4,5 = J5,6 = 6.5 Hz or J5,6 = J6,7 = 6.5 Hz, 1 H, 5-H or 6-H),
5232
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 5224–5235

Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
FULL PAPER
Compound rac-5: 1H NMR (400 MHz, [D6]acetone): δ = 3.47 (d,
2Jendo-3,exo-3 = –21.2 Hz, 1 H, endo-3-H or exo-3-H), 3.90 (d,
bright yellow solid {m. p. 161 °C, de Ͼ95% (NMR), 99.4% ee,
[α]2D0 = –6.1 (c = 0.25, THF)}. Fraction II: 167 mg (0.51 mmol, 5%)
2Jendo-3,exo-3 = –21.2 Hz, 1 H, endo-3-H or exo-3-H), 5.77–6.41 of (+)-(1R)-15, bright yellow solid {m. p. 135 °C, de Ͼ 95%
(ABCD line system, 4 H, arom.) ppm. 13C NMR (100 MHz, [D6]-
acetone): δ = 36.3 (+, C-3), 88.8 (–, C-4 or C-5 or C-6), 90.4 (–, C-
4 or C-5 or C-6), 91.2 (–, C-4 or C- 5 or C-6), 97.9 (–, C-7), 97.0
(+, C-3a), 116.5 (+, C-7a), 182.4 (+, C-1), 195.3 (+, C-2), 230.3 (+,
(NMR), 99.4% ee, [α]2D0 = +48.6 (c = 0.25, THF}.
Compound (–)-(1R)-14: C14H14CrO6: calcd: C 50.93 H 4.24; found
C 50.77 H 4.11.
Crystal Structure Analysis of (–)-(1R)-14:[67] C14H14CrO6, molecu-
lar weight 330.25, crystal system monoclinic, space group P 21, a
= 8.815(2) Å, b = 7.140(1) Å, c = 11.595(2) Å, α = 90°, β =
108.02(2)°, γ = 90°, V = 694.0(2) Å3, Z = 2, dcalcd. = 1.580 Mgm–3,
F(000) = 340, µ = 0.849 mm–1, crystal size 0.52×0.24×0.22 mm,
CO) ppm. IR (KBr): ν = 3040 (w), 2960 (w), 2932 (w), 2860 (w),
˜
2000 (s, CO), 1932 (s, CO), 1764 (w, ketone), 1708 (s, ketone), 1600
(w), 1524 (w), 1428 (w), 1280 (w), 1260 (w), 1100 (m), 1016 (m),
644 (m), 604 (m) cm–1. MS (70 eV, 170 °C): m/z (%) = 282 (12)
[M]+, 280 (17), 198 (36) [M – 3×CO]+, 189 (9), 167 (42), 149 (100)
[C9H9O2]+, 146 (8), 142 (12), 128 (17), 118 (11), 96 (21), 90 (12),
52 (59) [52Cr]+.
Stoe IPDS area detector diffractometer, T = 300(2) K, Mo-Kα
=
0.71073 Å, θmin = 2.43, θmax = 26.14°, –10 Յ h Յ 10, –8 Յ k Յ
8, –14 Յ l Յ 14, no absorption correction, no extinction correction,
6155 collected, 2685 unique reflections, [R(int) = 0.0363], refine-
ment program: SHELXL-93, refinement by least-squares method
(F2), F2 = 1.109, R indices: [I Ͼ 2σ(I)] R1 = 0.0257, wR2 = 0.0541,
R indices (all data): R1 = 0.0324, wR2 = 0.0551, residual electron
density: –0.152 Å–3, completeness of data 99.7%, Flack x param-
eter 0.00(2).
(–)-(pR)-Tricarbonyl(η6-2,2-dimethoxyindan-1-one)chromium(0)
[(–)-pR-19]: Dimethyl sulfoxide (12 mL) and acetic anhydride
(9 mL) were added at 25 °C to (–)-(1R)-14 (1.500 g, 4.5 mmol), the
solution becoming dark red. After the mixture had been stirred for
15 h, water (200 mL) was added, and the mixture was extracted
three times with TBME (each 50 mL). The combined organic layers
were washed three times with satd. aq. sodium hydrogen carbonate
and with satd. aq. sodium chloride (30 mL). After drying over mag-
nesium sulfate and filtration through a frit covered with a 1 cm
thick layer of silica gel the remaining material was purified by col-
umn chromatography (TBME/PE, 1:1, 20×3 cm) to provide (–)-
(pR)-19 (1.122 g, 3.4 mmol, 76 %) as a red solid {m. p. 125 °C,
99.4% ee, [α]2D0 = –561.0 (c = 0.05, THF)}.
(–)-(pR)-Tricarbonyl(η6-indan-1,2-dione)chromium(0) [(–)-(pR)-5]:
Compound (–)-(pR)-19 (1.000 g, 3.0 mmol) and triphenylcarben-
ium tetrafluoroborate (1.476 g, 4.5 mmol) were stirred for 3 h at
25 °C in anhydrous dichloromethane (50 mL). After addition of
water (150 mL) the layer was extracted three times with dichloro-
methane (each 20 mL). After drying over magnesium sulfate, fil-
tration through a frit, and solvent removal at reduced pressure, the
remaining crude product was purified by column chromatography
(SiO2, TBME/PE, 1:1, then TBME, 25×3 cm) to provide (–)-(pR)-
5 (305 mg, 1.1 mmol, 36%) as a red brown solid {m. p. 132 °C,
99.4% ee, [α]2D0 = –36.0 (c = 0.017, THF)}.
rac-Tricarbonyl(η6-exo-1-hydroxy-endo-1-vinylindan-2-one)chro-
mium(0) (rac-27): Compound rac-5 (150 mg, 0.5 mmol) in DEE/
THF (1:1, 20 mL) was added dropwise at –78 °C to a solution of
vinyllithium in DEE (1.0 , 3.19 mL, 3.2 mmol) in THF (10 mL).
The mixture was stirred for 4 h at –78 °C and was then allowed to
warm to 25 °C over 14 h. Sat. aq. ammonium chloride (20 mL) was
added at –78 °C and the mixture was allowed to warm to 25 °C.
After addition of water (10 mL) the aqueous layer was extracted
(R,S)-2,2-Dimethoxy-1-indanyl 2-Acetyl-2-phenylacetate [(R,S)-25]
and (S,S)-2,2-Dimethoxy-1-indanyl 2-Acetyl-2-phenylacetate [(S,S)-
26]: A solution of rac-13 (1340 mg, 6.9 mmol), 2-acetyl-2-phen-
ylacetic acid (1340 mg, 6.9 mmol), dicyclohexylcarbodiimide
(1444 mg, 7.0 mmol), and 4-(dimethylamino)pyridine (84 mg,
0.69 mmol) in dichloromethane (50 mL) was stirred for 11 h at 0 °C
and then for 16 h at 25 °C. Formed dicyclohexylurea was filtered
off, and the filtrate was washed with satd. aq. sodium hydrogen
carbonate (100 mL). After drying over magnesium sulfate the crude
product was purified by column chromatography (SiO2, TBME/
PE, 1:10, 50×3 cm). Fraction I: 0.745 g (2.0 mmol, 29%) of (S,S)-
26 [de = 99.3%, GC], colorless solid. Fraction II: 1041 mg
(2.8 mmol, 41%) of (R,S)-25 [de = 99.4%, GC]. Fraction III
741 mg (2.0 mmol, 29%) mixture of (R,S)-25 and (S,S)-26.
Compound (R,S)-25: 1H NMR (400 MHz, CDCl3): δ = 2.09 [s, 3
H, C(O)CH3], 3.08–3.22 (AB line system, 2 H, 3-H), 3.25 (s, 3 H,
OCH3), 3.30 (s, 3 H, OCH3), 5.91(s, 1 H, 1-H), 6.02 (s, 1 H, CHPh),
7.07–7.47 (m, 9 H, arom.) ppm. MS (70 eV, 76 °C): m/z (%) = 373
(3) [M + 3]+, 372 (5) [M + 2]+, 371 (24) [M + 1]+, 370 (100) [M]+,
339 (6), 279 (3), 219 (3), 193 (62), 177 (26), 161 (50), 131 (8), 107
(22), 91 (7), 77 (9).
Compound (S,S)-26: 1HNMR (400 MHz, CDCl3): δ = 2.21 [s, 3 H,
C(O)CH3], 2.86 (s, 3 H, OCH3), 3.06 (AB line system, 2 H, 3-H),
3.15 (s, 3 H, OCH3), 5.93 (s, 1 H, 1-H), 6.06 (s, 1 H, CHPh), 7.18–
7.491 (m, 9 H, arom.) ppm. MS (70 eV, 70 °C): m/z (%) = 373 (3)
[M + 3]+, 372 (5) [M + 2]+, 371 (24) [M + 1]+, 370 (100) [M]+, 339
(6), 279 (3), 219 (3), 193 (62), 177 (26), 161 (50), 131 (8), 107 (22),
91 (7), 77 (9).
(+)-(R)-2,2-Dimethoxyindan-1-ol [(+)-(R)-13] from (R,S)-25: A sus-
pension of (R,S)-25 (4.000 g, 10.8 mmol) and potassium carbonate
(14.900 g, 108.0 mmol) in methanol/water (2:1) was stirred at 25 °C
for 16 h. After addition of water (200 mL), the mixture was ex-
tracted five times with TBME (each 100 mL). After drying over
potassium carbonate, filtration, and solvent removal at reduced
pressure, the crude product was purified by column chromatog-
raphy (SiO2, TBME/PE, 1:5) to provide (+)-(R)-13 (2.070 g,
10.7 mmol, 99%, 99.4% ee), [α]2D0 = +24.5 (c = 1, CHCl3).
(–)-(1R)-endo-Tricarbonyl(η6-2,2-dimethoxyindan-1-ol)chromium(0)
[(–)-(1R)-14] and (+)-(1R)-Tricarbonyl(η6-2,2-dimethoxyindan-1-ol)- three times with TBME (each 30 mL). After drying over magne-
chromium(0) [(+)-(1R)-15]: Compound (+)-(R)-13 (1.950 g,
10.1 mmol, 99.4% ee) and hexacarbonylchromium (3.300 g,
15.0 mmol) in dibutyl ether (50 mL), heptane (50 mL), and THF
(2 mL) were heated at reflux for 20 h under a light flow of argon.
After cooling to 25 °C, the greenish reaction mixture was filtered
through a frit covered with a 1 cm thick layer of silica gel. After
solvent removal at reduced pressure, the crude product was purified
by column chromatography (SiO2, TBME/PE, 1:4, then TBME,
sium sulfate, filtration through a frit, and solvent removal at re-
duced pressure, the crude product was purified by column
chromatography (SiO2, TBME/PE, 1:3, 25×3 cm) to provide rac-
27 (52 mg, 0.2 mmol, 32%) as a yellow solid (m. p. 145 °C). 1H
2
NMR (200 MHz, [D6]acetone): δ = 3.39 (d, Jgem = –20.3 Hz, 1 H,
2
endo-3-H or exo-3-H), 3.83 (d, Jgem = –20.3 Hz, 1 H, endo-3-H or
exo-3-H), 5.05 (s, 1 H, OH), 5.12–5.95 (m, 7 H, 4-H, 5-H, 6-H, 7-
H, 8-H, 9-H) ppm. IR (ATR): ν = 3451 (w, br, OH), 3018 (w), 2986
˜
20×3 cm). Fraction I: 2.033 g (6.2 mmol, 61%) of (–)-(1R)-14, (w), 2921 (w), 1963 (s, CO), 1865 (s, CO), 1765 (s, C=O, ketone),
Eur. J. Org. Chem. 2005, 5224–5235
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5233

D. Leinweber, I. Weidner, R. Wilhelm, R. Wartchow, H. Butenschön
(m), 1259 (s), 1235 (s), 1139 (s), 1082 (s, C–O), 1024 (s, C–O), 801
FULL PAPER
1716 (m, C=O, ketone), 1633 (m), 1532 (m), 1439 (m), 1428 (m),
1382 (m), 1261 (m), 1050 (m, C–O), 819 (s), 667 (s), 633 (s) cm–1. (s), 782 (s), 762 (m) cm–1. MS (EI+): m/z (%) = 361 (5) [M –
MS (70 eV, 90 °C): m/z (%) = 310 (16) [M]+, 282 (20) [M-CO]+, 254
(40) [M-2×CO]+, 226 (30) [M-3×CO]+, 174 (26) [M-Cr(CO)3]+,
149 (100), 132 (17), 115 (29), 91 (28), 77 (17), 53 (14), 52 (51).
3×CO]+, 309 (14) [M – Cr(CO)3=ligand]+, 293 (10), 279 (6), 220
(43), 167 (22), 158 (44), 149 (100), 108 (9), 80 (13), 71 (25), 52 (60)
[52Cr]+. C22H19CrNO6: calcd: C 59.33 H 4.30 N 3.14; found C
59.55 H 4.99 N 2.49.
rac-Tricarbonyl[η6-exo-1-hydroxy-endo-1-(1-ethoxyvinyl)indan-2-
one]chromium(0) (rac-28): A solution of tert-butyllithium in pen-
tane (1.6 , 2.0 mL, 3.2 mmol) was added at –78 °C to 360 mg
(5.0 mmol) of ethoxyethene in THF (10 mL). The mixture was
warmed to –5 °C over 2 h and was then stirred for another 45 min
at this temperature, the color changing from yellow to colorless. A
solution of rac-5 (150 mg, 0.5 mmol) in DEE/THF (1:1, 20 mL)
was then added dropwise at –78 °C. The mixture was stirred for
4 h at –78 °C and then allowed to warm to 25 °C over 14 h. Sat.
aq. ammonium chloride (50 mL) was then added at –78 °C, and
the mixture was allowed to warm to 25 °C. After addition of water
(10 mL) the layer was extracted three times with TBME (each
30 mL). After drying over magnesium sulfate, filtration, and sol-
vent removal at reduced pressure the crude product was purified
by column chromatography (SiO2, TBME/PE, 1:4, 25×3 cm) to
provide rac-28 (79 mg, 0.2 mmol, 42%) as a viscous, yellow oil. 1H
NMR (200 MHz, [D6]acetone): δ = 1.15 (t, 3J = 7.0 Hz, 3 H, CH3),
Acknowledgments
This work was generously supported by the Deutsche Forschungs-
gemeinschaft. We are indebted to Professor T. Ikariya, Tokyo Insti-
tute of Technology, for a gift of catalyst (S,S)-23.
[1] M. F. Semmelhack, J. Organomet. Chem. Library B 1976, 1,
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[2] R. Davis, L. A. Kane-Maguire, in: Comprehensive Organome-
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Sci. Ser. C 1972, 274, 545–548.
[6] G. Jaouen, B. Caro, J.-Y. Le Bihan, C. R. Acad. Sci. Ser. C
1972, 274, 902–904.
[7] A. Meyer, R. Dabard, J. Organomet. Chem. 1972, 36, C38–
C42.
[8] G. A. Moser, M. D. Rausch, Synthesis and Reactivity in Inor-
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[9] M. D. Rausch, J. Org. Chem. 1974, 39, 1787–1788.
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[11] H. des Abbayes, M.-A. Boudeville, Tetrahedron Lett. 1976, 17,
2137–2140.
2
3
3.29 (d, Jgem = –20.5 Hz, 1 H, endo-3-H or exo-3-H) 3.70 (m, J
2
= 7.0 Hz, 2 H, CH2CH3), 3.83 (d, Jgem = –20.5 Hz, 1 H, endo-3-
2
2
H or exo-3-H), 4.20 (d, Jgem = 2.9 Hz, 1 H, =CH2), 4.60 (d, Jgem
= 2.9 Hz, 1 H, =CH2), 5.43 (m, 1 H, 4-H or 5-H or 6-H or 7-H),
5.60 (s, 1 H, OH), 5.67 (m, 1 H, 4-H or 5-H or 6-H or 7-H), 5.75–
5.90 (m, 2 H, 4-H or 5-H or 6-H or 7-H) ppm. IR (ATR): ν = 3416
˜
(w, br, OH), 3015 (w), 2980 (w), 2932 (w), 1959 (s, CrCO), 1857 (s,
CrCO), 1767 (s, C=O, ketone), 1713 (m, C=O, ketone), 1631 (m),
1537 (m), 1444 (m), 1428 (m), 1382 (m), 1261 (m), 1091 (s, C–O),
1050 (s, C–O), 819 (s), 661 (s), 623 (s) cm–1. MS (70 eV, 120 °C):
m/z (%) = 356 (24) [M – 2]+, 354 (43) [M]+, 298 (22) [M –
2×CO]+, 270 (40) [M – 3×CO]+, 252 (14), 226 (30), 218 (30) [M –
Cr(CO)3]+, 208 (100), 191 (26), 172 (17), 149 (25), 132 (17), 115
(29), 91 (28), 77 (17), 53 (16), 51 (55).
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(–)-(pR)-Tricarbonyl{η6-2-[2-(3,4-dimethoxyphenyl)ethylamino]-
inden-1-one}chromium(0) [(–)-(pR)-29]: Hydrochloric acid (10%,
10 mL) was added to (–)-(pR)-5 (150 mg, 0.5 mmol) and 2-(3,4-
dimethoxyphenyl)ethylamine (100 mg, 0.6 mmol) in THF (10 mL).
The mixture was stirred for 16 h, its color slowly changing from
brown to deep purple. Water (100 mL) was added, and the mixture
was extracted three times with TBME (30 mL each). After drying
with magnesium sulfate, filtration, and solvent removal at reduced
pressure, the crude product was purified by column chromatog-
raphy (SiO2, TBME/PE, 1:1, 25×3 cm) to provide (–)-(pR)-29
(61 mg, 0.1 mmol, 26%) as a purple solid (m. p. 155 °C, dec.).
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1
Compound (–)-pR-29: H NMR (200 MHz, CDCl3): δ = 2.81 (t, 2
H, NCH2CH2), 3.31 (m, 2 H, NCH2CH2), 3.87 (2×s, 6 H, OCH3),
4.67 (t, 1 H, NH), 5.05–5.17 (m, 2 H, coord. arom. CH), 5.28 (s, 1
H, 3-H), 5.75 (m, 1 H, coord. arom. CH), 6.08 (d, 1 H, coord.
arom. CH), 6.66–6.76 (m, 2 H, arom. CH), 6.82 (d, 1 H, arom.
CH) ppm. 13C NMR (100 MHz, CDCl3, APT/BB/HMQC): δ =
34.7 (+, NCH2CH2), 45.8 (+, NCH2CH2), 56.3 (–, OCH3), 56.4
(–, OCH3), 84.4 (–, coord. arom. CH), 84.6 (–, coord. arom. CH),
86.5 (+, C-3a), 91.9 (–, coord. arom. CH), 94.3 (–, coord. arom.
CH), 97.9 (–, C-3), 112.1 (–, arom. CH), 112.5 (–, arom. CH), 121.1
(–, arom. CH), 129.3 (+, C-7a), 131.4 (+, quat. arom. C), 144.9 (+,
C-2), 148.4 (+, quat. arom. C), 149.6 (+, quat. arom. C), 190.3 (+,
C-1), 232.7 (+, CrCO) ppm. IR (ATR): ν = 3351 (w-m, br, NH),
˜
3083 (w), 2961 (m), 2929 (m), 2837 (m), 1958 (s, CrCO), 1872 (s,
CrCO), 1695 (s, C=O, ketone), 1615 (s), 1541 (m), 1514 (s), 1418
5234
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Eur. J. Org. Chem. 2005, 5224–5235

Synthesis of Enantiopure Tricarbonyl(indan-1,2-dione)chromium
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Published Online: October 20, 2005
Eur. J. Org. Chem. 2005, 5224–5235
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5235