Preparation of chiral amine carbonyl chromium(0) complexes with [(norbornadiene)Cr(CO)4] as the complexation reagent

Article abstract of DOI:10.1002/1099-0690(200006)2000:12<2273::AID-EJOC2273>3.0.CO;2-M

A number of chiral amines were prepared and used as ligands in carbonylchromium(0) complexes. Included are monoamines chelating diamines and methionine methyl ester. For their complexation (norbornadiene)tetracarbonylchromium(0) was found to allow complex

Full text of DOI:10.1002/1099-0690(200006)2000:12<2273::AID-EJOC2273>3.0.CO;2-M

FULL PAPER
Preparation of Chiral Amine Carbonyl Chromium(0) Complexes with
[(Norbornadiene)Cr(CO)4] as the Complexation Reagent
Markus Strotmann[a] and Holger Butenschön*[a]
Keywords: Chromium / Chirality / Arene complexes / N ligands / Norbornadiene
A number of chiral amines were prepared and used as li-
complexes prepared could be used as complexation reagents
gands in carbonylchromium(0) complexes. Included are for arenes in up to 81% yield in the presence of boron
monoamines, chelating diamines and methionine methyl es-
trifluoride−diethyl ether adduct if THF was used as the solv-
ter. For their complexation (norbornadiene)tetracarbonylch- ent. Significant chirality transfer from the chiral com-
romium(0) was found to allow complexation in high, some-
times quantitative yields in boiling THF (65 °C). The amine
plexation reagents to the chiral arene complexes was, how-
ever, not observed.
Introduction
L3Cr(CO)3. In these reagents L is usually an electroneutral,
two-electron ligand, e.g. ammonia, pyridine, acetonitrile or
propionitrile.
Complexes such as (carbene)pentacarbonylchromium(0),
(alkene)pentacarbonylchromium(0), (diene)tetracarbonyl-
chromium(0), and (arene)tricarbonylchromium(0) are im-
portant classes of carbonyl chromium(0) complexes. Many
of these are used in organometallic and preparative organic
chemistry, as well as in materials science and other fields.
Most prominent for organic chemistry are Fischer-type car-
bene complexes and arene complexes.[1Ϫ20]
Here we describe the syntheses of a number of enantiom-
erically pure chiral amine carbonyl chromium(0) complexes.
We regard such complexes as possible chiral complexation
reagents for the formation of nonracemic (arene)tricarbon-
ylchromium(0) complexes with prochiral arene ligands.[23]
As well as by simple complexation of enantiomerically
pure ligands, enantiomerically pure chiral (arene)tricarbon-
ylchromium(0) complexes have been obtained by diverse
methods of resolution of racemic mixtures,[24] by diastereo-
selective complexation of enantiomerically pure chiral
arenes,[25Ϫ27] and by enantioselective deprotonation and
subsequent electrophilic attack at prochiral arene com-
plexes using a chiral amide base.[28Ϫ37] The idea which in-
spired us in this context is based on the use of complexation
reagents L*3Cr(CO)3 or L*2Cr(CO)4 with enantiomerically
pure chiral ligands L*. The mechanism of their replacement
by an arene is presumably a stepwise one involving interme-
diates like (η2-arene)L*2Cr(CO)3 or (η4-arene)L*Cr(CO)3.
With a prochiral arene, these intermediates should be
formed as mixtures of diastereomers. The face of com-
plexation is defined with the first complexation step and
will not change after this first step. If these diastereomers
are sufficiently different, the transition states of their forma-
tion, as well as those of the following steps, will also be
different in energy. This should lead to the preferred forma-
tion of one of the enantiomers of the final, planar chiral
arene complex. The ligands L*, liberated in the course of
the reaction, could be recycled. In the optimum case, they
could be used only in catalytic amounts and be reintro-
duced into the cycle after their liberation. It should be men-
tioned that related techniques have been used in the syn-
thesis of planar chiral complexes of iron and
ruthenium.[38Ϫ40]
Because of electronic and steric effects due to the highly
electron-withdrawing and sterically bulky tricarbonylchro-
mium(0) fragment, (arene)tricarbonylchromium(0) com-
plexes allow interesting reactions which are not observed
for the uncomplexed arene. Semmelhack has elegantly sum-
marized the key properties of tricarbonylchromium com-
plexes in a figure published in 1976, which can now be
found in many organometallic chemistry textbooks.[20] Im-
portant features are: the enhanced acidity of the protons at
the aromatic ring as well as of those in benzylic positions,
facilitation of nucleophilic attack at the arene ring, and en-
hanced rates of solvolysis in benzylic positions. In addition
to these consequences of the electron-withdrawing nature
of the Cr(CO)3 group, the steric bulk of the tricarbonylch-
romium fragment usually makes reagents attack selectively
at the face of the arene opposite to the Cr(CO)3 group. An
important additional aspect is the decrease in symmetry
upon complexation of an arene to a metal, making com-
plexes of prochiral arenes chiral. In combination with the
selective attack at the face opposite to the metal this allows
for stereoselective syntheses of chiral aromatic com-
pounds.[4,10,11,13,14,21]
There are a number of complexation reagents known for
the formation of (arene)tricarbonylchromium(0) complexes.
In addition to Cr(CO)6, these include tricarbonyl(naph-
thalene)chromium(0)[22] and reagents of the general formula
[a]
Institut für Organische Chemie, Universität Hannover,
To allow the selectivity of complexation reactions to be
tested by NMR, they were performed using chiral arenes
bearing asymmetric carbon atoms at some distance from
Schneiderberg 1B, D-30167 Hannover, Germany
Fax: (internat.) ϩ 49-(0)511/762-4616
E-mail: holger.butenschoen@mbox.oci.uni-hannover.de
Eur. J. Org. Chem. 2000, 2273Ϫ2284
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ193X/00/0612Ϫ2273 $ 17.50ϩ.50/0
2273

M. Strotmann, H. Butenschön
FULL PAPER
Scheme 2
Kündig had obtained 7 (Scheme 2), which is also used as a
complexation reagent under mild reaction conditions, in a
mixture of dibutyl ether and THF (100:1) at 138Ϫ142 °C
in 80% yield.[22]
When 6 was dissolved in an approximately 9-fold excess
of (S)-1-cyclohexylethylamine[44,45] and stirred in the dark
for 18 h at 20 °C, enantiomerically pure monoaminepenta-
carbonylchromium complex (S)-8 was obtained in 43%
yield. The formation of aminepentacarbonylchromium
complexes as side products had been observed by
Werner.[43] Here, however, this reaction has become the
main reaction path. The comparatively high yield indicates
that carbonyl ligand exchange reactions between the parti-
cipating chromium complexes play an important role, in ad-
dition to the desired complexation of the amine ligand.
While attempts to prepare complexes with monoamines
were less successful, some complexes with diamines were
obtained in high yields. In a first test, achiral (N,NЈ-dicyclo-
hexyl)-1,2-ethanediamine[46,47] was coordinated to chro-
mium by heating the diamine and 6 in THF at reflux for
30 min to give complex 9 in almost quantitative yield
(Scheme 3).
Scheme 1
the prochiral arene fragment. Before evaluating the desired
complexation with chiral reagents, it was necessary to check
the diastereoselectivity obtained by using an achiral com-
plexation reagent. Therefore some chiral arenes were coord-
inated to Cr(CO)3 to give arene complexes 1؊5[41] in
43Ϫ54% yield (Scheme 1).
In all cases the determination of the de was possible by
1
inspection of the H and 13C NMR spectra. This makes all
these complexes suitable for the detection of effects of chiral
complexation reagents, where the diastereoselectivity ob-
served with Cr(CO)6 has to be taken into account.
Next, a complexation reagent for the amine ligands, al-
lowing complexation under mild reaction conditions in
good yield, had to be found. In our hands, tetracarbonyl-
(norbornadiene)chromium(0) (6) was found to be particu-
larly useful for this purpose, as this reagent allows com-
plexation of a variety of ligands at comparatively low tem-
perature, namely in boiling THF (65 °C). Tetracarbonyl-
(norbornadiene)chromium(0) was first prepared by Werner
Scheme 3
When, as according to Cotton,[48] a 15-fold excess of a
by treatment of norbornadiene with Cr(CO)6.[42,43] Al- mixture of cis- and racemic trans-1,2-diaminocyclohexane
though the authors showed its feasibility as a complexation (1:3.5) was heated with Cr(CO)6 without solvent at 120 °C
reagent, it has not very often been used as such. To check for 4 h, a 90% yield of rac-trans-(1,2-diaminocyclohexane)-
its quality, we tried the complexation of naphthalene and tetracarbonylchromium(0) (rac-10) was obtained. Presum-
obtained tricarbonyl(naphthalene)chromium(0) (7) in 80% ably for steric reasons, no cis-1,2-diaminocyclohexane com-
yield by heating naphthalene and 6 in THF at 65 °C. plex was observed. However, as this method is unsuitable
2274
Eur. J. Org. Chem. 2000, 2273Ϫ2284

Preparation of Chiral Amine Carbonyl Chromium(0) Complexes
FULL PAPER
economically for enantiomerically pure ligands, (1R,2R)-
1,2-diaminocyclohexane was complexed using tricarbonyl-
(norbornadiene)chromium(0) (6). Heating an equimolar
mixture of enantiomerically pure diamine and 6 in THF for
30 min at 65 °C resulted in an almost quantitative yield of
(1R,2R)-10.
Compounds rac-11[49] and rac-12 (Scheme 3) were each
obtained in 98% yield using the Cotton method.[48] At-
tempts to coordinate (Ϫ)-sparteine met with failure either
with Cr(CO)6 or with 6, presumably for steric reasons.
Enantiomerically pure diamines can be obtained by the
reduction of amino acid amides with LiAlH4.[50] Thus, con-
densation of diethyl glutamate with cyclohexylamine (89%),
followed by reduction with LiAlH4 (66%)[51,52] and com-
plexation with 6 (87%), afforded the enantiomerically pure
tetracarbonylchromium complex (S)-13. In the complex the
amine nitrogen atoms are asymmetric, because their lone
electron pairs are no longer available for an inversion of
their configuration. Remarkably, (S)-13 was formed in dias-
tereomerically pure form.
In a similar way, enantiomerically pure diamine complex
(S)-14 was prepared as a single diastereomer in 95% yield
by reduction of the known[51] (S)-2-[(butylamino)carbonyl]-
5-oxopyrrolidine (66%), followed by complexation with 6.
Another route to chiral diamines is the reduction of the
corresponding diazadienes, which are obtained by con-
densation of amine precursors with glyoxal (Scheme 4).
(ϩ)-(4S,5S)-5-Amino-2,2-dimethyl-4-phenyl-1,3-dioxane[53]
[(S,S)-15], a side product in the synthesis of chloroamphen-
icol, was condensed with glyoxal in methanol in 99% yield
to give diazadiene (S,S,S,S)-16. Quantitative reduction with
sodium borohydride afforded chiral diamine (S,S,S,S)-17,
which was coordinated at chromium by heating with 6 in
THF to give complex (S,S,S,S)-18 in 76% yield.
Scheme 4
Isoquinoline derivative (R)-19 (Scheme 5) is commer-
cially available as its tartrate and has been used by Vedejs
as a chiral proton source for the enantioselective pro-
tonation of prochiral amide enolates.[54] Complexation with
11 over 2 h gave complex (R)-20 in 67% yield, beside minor
amounts of (arene)tricarbonylchromium(0) complexes
which were not identified.
Binaphthyl derivatives, especially BINAP, are successfully
used in many asymmetric catalytic reactions.[55Ϫ59] Here,
(R)-2,2Ј-diamino-1,1Ј-binaphthyl [(R)-DABN] was coordin-
ated to the tetracarbonylchromium fragment using 6 for the
complexation. The [(R)-DABN] complex (R)-21 was ob-
tained in 70% yield as a yellow, highly air-sensitive solid. As
side products, some (arene)tricarbonylchromium complexes
were separated by column chromatography. These were not
completely characterized.
The results show that, with 6 as the complexation re-
agent, complexes of 1,2-, 1,3- and even 1,4-diamines can be
obtained in good yields under comparatively mild reaction
conditions.
Scheme 5
crystalline solid. Remarkably, the corresponding reaction of
As an example of a chiral heterobidendate ligand, -me- -cysteine methyl ester did not work, either with Cr(CO)6
thionine methyl ester[60] was included. Complexation was or with 6. Possibly, steric reasons account for this, as the
achieved in 49% yield with Cr(CO)6. Chromium complex covalent radius of sulfur is much larger than that of nitro-
(S)-22 was obtained as an orange, moderately air-stable, gen. In addition, sulfur is a weaker ligand than nitrogen, so
Eur. J. Org. Chem. 2000, 2273Ϫ2284
2275

M. Strotmann, H. Butenschön
FULL PAPER
that the situation with -cysteine methyl ester is very differ- Table 1. Complexation of chiral arenes with chiral amine carbonyl
ent from that of 1,2-diamine ligands.[61]
After the preparation of a number of chiral amine chro-
chromium complexes (TBME ϭ tert-butyl methyl ether, MCH ϭ
methylcyclohexane)
mium(0) complexes, their suitability as complexation re-
agents had to be tested. When complexes 1؊5 are prepared
by reaction of the chiral ligands with a chiral complexation
reagent, double stereodifferentiation[62] cannot formally be
excluded. However, as the centers of chirality in the ligands
and the aromatic system to be coordinated are rather far
away from each other, double stereodifferentiation would
not be expected to be important in these cases. Any signific-
ant influence of double stereodifferentiation would be unco-
vered by experiments with racemic material.
Entry Reagent
Product Solvent Temp. [°C] Yield [%] de
1
rac-10
rac-11
rac-12
(1R,2R)-10
(1R,2R)-10
(S)-14
(S)-13
rac-12
rac-12
(S)-14
(S)-14
(S)-14
(S)-22
(S)-22
(S)-22
(S)-22
(S)-22
(S)-22
1
1
1
1
3
3
5
3
3
3
3
3
1
1
3
4
3
5
THF
THF
THF
THF
THF
THF
THF
CHCl3 61
TBME 55
MeCN 81
Bu2O
MCH
THF
Et2O
THF
65
65
65
65
65
65
65
50
50
54
53
63
25
0
5
9
6
10
1
6
-
2
3
4
5
6
7
8
0
-
9
8
5
-
10
11
12
13
14
0
70
70
65
34
65
0
-
-
0
Triaminetricarbonylchromium(0) complexes have been
known as complexation reagents for some time. The decom-
plexation of three ligands with complexation of just one 15
35
0
6
-
77
19
29
0
4
6
2
-
16
TBME 55
TBME 55
THF
supports the reaction entropically. While triamminetricar-
17
bonylchromium rather easily releases its ammonia ligands,
which evaporate from the reaction mixture,[63Ϫ65] the cor-
responding reaction with substituted amine ligands, in or-
der to be irreversible, requires the presence of Lewis acids
to bind the liberated amine.[66] When a (diamine)tetracar-
bonylchromium(0) complex is used as a complexation re-
agent those factors should not be as important as with tria-
minetricarbonylchromium(0) complexes. However, the de-
complexation of one of the carbonyl ligands and its evap-
oration out of the reaction mixture should make the
reaction irreversible.
18
65
Table 2. Complexation of chiral arenes with hexacarbonylchrom-
ium
Entry Product Solvent
Temp. [°C] Yield [%] de
1
2
3
4
5
1
2
3
4
5
Bu2O/THF (10:1) 117Ϫ120
Bu2O/THF (10:1) 117Ϫ120
Bu2O/THF (10:1) 117Ϫ120
Bu2O/THF (10:1) 117Ϫ120
Bu2O/THF (10:1) 117Ϫ120
48
43
54
46
46
14
7
0
6
11
Here, it was found that some of the diamine complexes
prepared allow complexation of arenes in the presence of
trifluoroboraneϪdiethyl ether adduct in THF at 65 °C in
good yields (Scheme 6). Results are summarized in Table 1.
For comparison, Table 2 summarizes the results obtained
with Cr(CO)6 as the complexation reagent.
ene. Thus, intermediates lacking chiral information, like
[(THF)2Cr(CO)4] and [(THF)3Cr(CO)3], are likely to be in-
volved. In order to obtain significant des, the use of ligands
other than amines as sources of the chiral information must
therefore be considered.
Experimental Section
General: All operations were performed in flame-dried reaction ves-
sels under an argon atmosphere using standard Schlenk techniques.
Halogen-free solvents were distilled from sodium-potassium alloy/
benzophenone. Dichloromethane was distilled from calcium chlor-
Scheme 6. Complexation of arenes with amine carbonyl chro-
mium complexes
The results clearly demonstrate the importance of the
solvent THF. Only when this coordinating solvent at 65 °C
was used were acceptable yields of complexes achieved. Ent-
ries 16 and 17 show that lower yields can also be obtained
in TBME (tert-butyl methyl ether) at 55 °C. A comparison
ide.
Ϫ
1H NMR: Bruker WP 80 (80 MHz), WP 200 SY
(200.1 MHz), AM 400 (400.1 MHz). 13C NMR: Bruker WP 200
SY (50.3 MHz), AM 400 (100.1 MHz). Signal multiplicities were
determined using APT and DEPT techniques, ϩ or Ϫ indicating
positive or negative signal phase. Chemical shifts refer to δTMS
ϭ
with the results in Table 2 shows that, when THF is used, 0 or to residual solvent signals.[69,70] For clarity, atom numbering
is given in the formulas of the ligands and is used accordingly for
their complexes. 31P NMR: Bruker WP 200 (81.3 MHz) and AM
400 (161.9 MHz), 1H decoupling, external standard 85% H3PO4. Ϫ
IR: Bruker ISS 25, PerkinϪElmer FT-IR 580 and 1710. Ϫ MS:
Finnigan MAT 112, 312 at 70 eV. FAB spectra were obtained using
o-nitrobenzyl alcohol as the matrix and cesium as the ion source
with Fisons VG autospec. Ϫ HRMS: Finnigan MAT 312, Fisons
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
the yields are somewhat higher even at reaction temper-
atures more than 50 °C lower. This indicates that amine
carbonyl chromium(0) complexes are suitable complexation
reagents for arenes. However, the diastereomeric excesses
(de determined by NMR signal integration) achieved are
the same as those obtained with Cr(CO)6 within experi-
mental error. This, and the preference for THF as the solv-
ent,[22,67,68] suggests that the complexations performed
starting from the amine complexes proceed by replacement
of the amine by THF prior to the complexation of the ar- Optical rotation: PerkinϪElmer polarimeter 241. Ϫ Column chro-
2276 Eur. J. Org. Chem. 2000, 2273Ϫ2284

Preparation of Chiral Amine Carbonyl Chromium(0) Complexes
FULL PAPER
matography: Silica gel (J. T. Baker, 40 µm) was degassed by heating
it with a heat gun at reduced pressure followed by putting it under
normal pressure with argon. This sequence was repeated five times.
Separations were performed by flash chromatography.[71]
5.11Ϫ6.44 (ABCD line system, 4 H, 3-H, 4-H, 5-H, 6-H), 5.17 (q,
1 H, 9-H). Double set of signals due to diastereomers. Ϫ 13C NMR
(100.6 MHz, [D6]acetone, APT): δ ϭ 14.3 ϩ 14.4 (Ϫ, C-13), 17.1
ϩ 17.2 (Ϫ, C-10), 56.85 ϩ 56.86 (Ϫ, C-7), 61.7 ϩ 61.8 (ϩ, C-12),
70.3 ϩ 70.4 (Ϫ, C 9), 75.4 ϩ 75.6 (Ϫ, C-3, C-4, C-5 or C-6), 83.2
ϩ 83.5 (ϩ, C-1), 85.6 ϩ 85.7 (Ϫ, C-3, C-4, C-5 or C-6), 97.9 ϩ
98.0 (Ϫ, C-3, C-4, C-5 or C-6), 98.9 ϩ 99.1 (Ϫ, C-3, C-4, C-5 or
C-6), 145.6 ϩ 145.8 (ϩ, C-2), 164.0 ϩ 164.1 (ϩ, C-11), 170.8 ϩ
170.9 (ϩ, C-8), 232.8 ϩ 232.9 (ϩ, CO). Double set of signals due
Procedure for the Synthesis of Chiral Substituted Benzoic Acid Es-
ters (Procedure 1): The acid chloride in diethyl ether was added
dropwise to the enantiomerically pure alcohol (1 equiv.) and pyrid-
ine (1.5 equiv.) in diethyl ether at 0 °C. After the addition the mix-
ture was allowed to warm to 20 °C and was then heated at reflux
for 48 h. Then the mixture was poured into a threefold volume of
ice water and acidified by addition of 1  hydrochloric acid. The
suspension was extracted four times with diethyl ether (50 mL
each). The collected organic layers were dried over MgSO4. After
solvent removal at reduced pressure, some anhydride (side product)
was removed by column chromatography.
to diastereomers. Ϫ MS (70 eV, 160 °C): m/z (%) ϭ 389 (2) [Mϩ
ϩ
1], 388 (4) [Mϩ], 387 (1) [Mϩ Ϫ 1], 331 (1) [Mϩ Ϫ 2CO Ϫ 1], 304
(3) [Mϩ Ϫ 3CO], 303 (7) [Mϩ Ϫ 3CO Ϫ 1], 252 (24) [Mϩ Ϫ 3CO
Ϫ Cr], 207 (8), 160 (35), 136 (50), 135 (100) [Mϩ Ϫ Cr Ϫ 3CO Ϫ
ethyl lactate], 134 (60), 120 (14), 105 (47), 92 (54), 77 (63).
(1S)-1-Ethoxycarbonylethyl 3,4-Dimethoxybenzoate: Procedure 1;
3,4-dimethoxybenzoic acid chloride (4.01 g, 20 mmol) in diethyl
ether (50 mL), ethyl (S)-2-hydroxypropanoate (2.27 mL, 2.36 g,
20 mmol) and pyridine (2.4 mL, 20 mmol) in diethyl ether (20 mL).
Column chromatography (SiO2, diethyl ether/petroleum ether 1:1,
Procedure for the Synthesis of (Arene)tricarbonylchromium(0) Com-
plexes by Complexation with Cr(CO)6 (Procedure 2): A mixture of
the arene (1 equiv.) and hexacarbonylchromium (1.1 equiv.) in di-
butyl ether/THF (10:1) was heated at reflux (117Ϫ120 °C) until no
more uncomplexed arene could be detected (TLC control). After
cooling to 25 °C, the solvent was removed at reduced pressure, and
the product was purified by column chromatography.
length 25 cm,
ø 3.5 cm) and solvent removal gave 5.21 g
(18.5 mmol, 92%) of (1S)-1-ethoxycarbonylethyl 3,4-dimeth-
oxybenzoate as a light brownish solid, m.p. 67 °C. Ϫ IR (CHCl3): ν˜ ϭ
3076 cmϪ1 (m), 2984 (m), 2968 (m), 2940 (m), 2912 (m), 2840 (m,
OCH3), 1748 (s, ester CϭO), 1712 (s, ester CϭO), 1600 (s), 1516
(s), 1464 (s), 1420 (s), 1380 (m), 1352 (m), 1272 (s), 1228 (s), 1176
(s), 1136 (s), 1112 (s), 1024 (s), 948 (m), 876 (m). Ϫ 1H NMR
(1S)-1-Ethoxycarbonylethyl 2-Methoxybenzoate: Procedure 1; 2-
methoxybenzoic acid chloride (17.1 g, 100 mmol) in diethyl ether
(50 mL), ethyl (S)-2-hydroxypropanoate (9.75 mL, 11.8 g,
100 mmol), pyridine (11.6 mL) in diethyl ether (100 mL). Column
chromatography (SiO2, diethyl ether/petroleum ether 1:1, length
20 cm, ø 5 cm) and solvent removal gave 20.5 g (80 mmol, 80%) of
(1S)-1-ethoxycarbonylethyl 2-methoxybenzoate as a colorless oil.
Ϫ IR (cap. film): ν˜ ϭ 3076 cmϪ1 (w), 2984 (m), 2940 (m), 2908
(m), 2840 (m, OCH3), 1732 (s, br, ester CϭO), 1600 (s), 1544 (m),
1492 (s), 1464 (s), 1436 (m), 1380 (m), 1348 (m), 1284 (s), 1252 (s),
1204 (s), 1164 (m), 1128 (s), 1096 (s), 1076 (s), 1048 (s), 1020 (s),
3
(400.1 MHz, CDCl3): δ ϭ 1.28 (t, J14-13 ϭ 7.2 Hz, 3 H, 14-H),
1.62 (d, 3J11-10 ϭ 7 Hz, 3 H, 11-H), 3.92 (s, 3 H, 7-H or 8-H), 3.93
3
(s, 3 H, 8-H or 7-H), 4.2 (q, J13-14 ϭ 7.2 Hz, 2 H, 13-H), 5.3 (q,
3J10-11 ϭ 7 Hz, 1 H, 10-H), 6.9 (d, 3J5-6 ϭ 8.6 Hz, 1 H, 5-H), 7.6 (d,
4J2-6 ϭ 1.8 Hz, 1 H, 2-H), 7.7 (dd, 3J6-5 ϭ 8.6 Hz, 4J2-6 ϭ 1.8 Hz, 1
H, 6-H). Ϫ 13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 14.7 (CH3,
C-14), 17.6 (CH3, C-11), 56.5 (CH3, C-7 or C-8), 56.6 (CH3, C-8
or C-7), 61.9 (CH2, C-13), 69.6 (CH, C-10), 110.8 (CH, C-2, C-5
or C-6), 112.7 (CH, C-2, C-5 or C-6), 122.5 (Cq, C-1), 124.6 (CH,
C-2, C-5 or C-6), 149.2 (Cq, C-3 or C-4), 153.8 (Cq, C-3 or C-4),
166.3 (Cq, C-12), 171.5 (Cq, C-9). Ϫ MS (70 eV, 60 °C): m/z (%) ϭ
283 (5) [Mϩ ϩ 1], 282 (29) [Mϩ], 237 (3), 210 (2), 166 (11), 165
(100) [Mϩ Ϫ ethyl lactate], 149 (2), 137 (5), 122 (3), 107 (3), 91
(5), 79 (5), 77 (5). Ϫ HRMS (C13H16O5): calcd. 281.110339; found
281.110474. Ϫ C14H18O6 (282.29): calcd. C 59.57, H 6.43; found C
59.15, H 6.41. Ϫ [α]2D0 ϭ ϩ22.6 (c ϭ 1, Et2O).
1
856 (m), 756 (s), 708 (m), 660 (m). Ϫ H NMR (200.1 MHz, [D6]-
3
acetone): δ ϭ 1.25 (t, J13-12 ϭ 6.6 Hz, 3 H, 13-H), 1.56 (d,
3J10-9 ϭ 7 Hz, 3 H, 10-H), 3.88 (s, 3 H, 7-H), 4.2 (2q, 2 H, 12-H),
5.2 (q, 1 H, 9-H), 6.98Ϫ7.83 (ABCD line system, 4 H, 3-H, 4-H,
5-H, 6-H). Ϫ 13C NMR (50.3 MHz, [D6]acetone, APT): δ ϭ 14.4
(Ϫ, C-13), 17.2 (Ϫ, C-10), 56.2 (Ϫ, C-7), 61.5 (ϩ, C-12), 69.6 (Ϫ,
C-9), 113.3 (Ϫ, C-3, C-4, C-5 or C-6), 120.7 (ϩ, C-1), 120.8 (Ϫ, C-
3, C-4, C-5 or C-6), 132.1 (Ϫ, C-3, C-4, C-5 or C-6), 134.5 (Ϫ, C-
3, C-4, C-5, C-6), 160.0 (ϩ, C-2), 165.6 (ϩ, C-11), 171.3 (ϩ, C-8).
Ϫ MS (70 eV, 25 °C): m/z (%) ϭ 253 (1) [Mϩ ϩ 1], 252 (6) [Mϩ],
207 (2), 136 (10), 135 (100) [Mϩ Ϫ ethyl lactate], 120 (3), 106 (7),
92 (10), 77 (22). Ϫ HRMS (C13H16O5): calcd. 252.0998; found
252.0998. Ϫ C13H16O5 (252.26): calcd. C 61.90, H 6.39; found C
60.98, H 6.37. Ϫ [α]2D0 ϭ ϩ3.0 (c ϭ 1, Et2O).
Tricarbonyl[η6-(1S)-1-ethoxycarbonylethyl
3,4-dimethoxybenzo-
ate]chromium(0) [(1S)-2]: Procedure 2; (1S)-1-ethoxycarbonylethyl
3,4-dimethoxybenzoate (282 mg, 1.00 mmol) and Cr(CO)6 (300 mg,
1.36 mmol) in dibutyl ether (75 mL) and THF (8 mL). The solution
was heated at reflux for 26 h with formation of a yellow suspension.
Column chromatography (SiO2, diethyl ether/petroleum ether 1:3
Ǟ 1:1, length 40 cm, ø 2 cm) and solvent removal gave 180 mg
[0.43 mmol, 43%, de ഠ 7%, purity ca. 95% (NMR)] of (1S)-2, mix-
Tricarbonyl[η6-(1S)-1-ethoxycarbonylethyl 2-methoxybenzoate]chro-
mium(0) [(S)-1]: Procedure 2; (1S)-1-ethoxycarbonylethyl 2-me-
thoxybenzoate (1.0 g, 3.9 mmol), Cr(CO)6 (1.0 g, 4.5 mmol) in di- ture of diastereomers, as a viscous orange oil. Ϫ IR (CHCl3): ν˜ ϭ
butyl ether (100 mL) and THF (10 mL). The solution was heated 3040 cmϪ1 (w), 2984 (w), 2940 (w), 1976 (s, CO), 1904 (s, br, CO),
at reflux for 36 h with formation of a brown suspension. Column
1724 (m, br, esterϪCϭO), 1540 (w), 1512 (w), 1488 (m), 1384 (w),
chromatography (SiO2, diethyl ether/petroleum ether 1:4 Ǟ 1:1,
1312 (w), 1264 (s), 1222 (m), 1196 (m), 1180 (m), 1108 (m), 1016
1
3
length 30 cm,
ø 2.5 cm) and solvent removal gave 720 mg (w). Ϫ H NMR (400.1 MHz, [D6]acetone): δ ϭ 1.25 (t, J14-13 ϭ
3
[1.86 mmol, 48%, de ഠ 14%, purity ca. 95% (NMR)] of (S)-1 as a
7.1 Hz, 3 H, 14-H), 1.55 (2d, J11-10 ϭ 7 Hz, 3 H, 11-H), 3.88 (4s,
viscous orange-red oil. Ϫ IR (CHCl3): ν˜ ϭ 3098 cmϪ1 (w), 2960 6 H, 7-H, 8-H), 4.2 (2q, J13-14 ϭ 7.1 Hz, 2 H, 13-H), 5.2 (2q,
3
3
(w), 2936 (w), 1980 (s, CO), 1912 (s, br, CO), 1728 (m, br, esterϪCϭ
3J10-11 ϭ 7 Hz, 1 H, 10-H), 5.8 (2d, J5-6 ϭ 6.6 Hz, 1 H, 5-H or 6-
3
O), 1524 (w), 1464 (m), 1416 (w), 1288 (m), 1228 (m), 1180 (m), H), 6.15 (2d, J5-6 ϭ 6.6 Hz, 1 H, 6-H or 5-H), 6.24 (s, br, 1 H, 2-
1096 (m), 1012 (m), 624 (m). Ϫ 1H NMR (200.1 MHz, [D6]ace-
H). Double set of signals due to diastereomers. Ϫ 13C NMR
(100.6 MHz, [D6]acetone, DEPT): δ ϭ 14.29 ϩ 14.30 (CH3, C-14),
tone): δ ϭ 1.22 (2t, 3J13-12 ϭ 6.8 Hz, 3 H, 13-H), 1.53 (2d, 3J10-9
ϭ
7 Hz, 3 H, 10-H), 3.85 (2s, 3 H, 7-H), 4.22 (4q, 2 H, 12-H), 16.05 ϩ 16.08 (CH3, C-11), 56.13 ϩ 56.18 (CH3, C-7 or C-8), 56.98
Eur. J. Org. Chem. 2000, 2273Ϫ2284 2277

M. Strotmann, H. Butenschön
FULL PAPER
ϩ 57.03 (CH3, C-7 or C-8), 60.82 ϩ 60.84 (CH2, C-13), 69.64 ϩ C21H26CrO6 (426.42): calcd. C 59.15, H 6.15; found C 58.28, H
69.76 (CH, C-10), 75.63 ϩ 75.89 (CH, C-2, C-5 or C-6), 80.36 ϩ 6.16.
80.92 (CH, C-2, C-5 or C-6), 83.84 ϩ 83.85 (Cq, C-1), 90.91 ϩ
91.06 (CH, C-2, C-5 or C-6), 130.21 ϩ 130.40 (Cq, C-3 or C-4),
137.18 ϩ 137.24 (Cq, C-3 or C-4), 164.26 ϩ 164.31 (Cq, C-12),
The diastereomers were separated by column chromatography
(SiO2, diethyl ether/petroleum ether 1:4 Ǟ 1:1, length 120 cm, ø
3.5 cm).
169.53 ϩ 169.54 (Cq, C-9), 232.07 ϩ 232.09 (Cq, CO). Ϫ MS
(70 eV, 90 °C): m/z (%) ϭ 418 (1) [Mϩ], 334 (3) [Mϩ Ϫ 3CO], 306
Fraction I: Rf ϭ 0.50 (diethyl ether/petroleum ether 2:1), orange
(2), 283 (4), 282 (27) [Mϩ Ϫ 3CO Ϫ Cr], 278 (4), 237 (3), 219 (4),
solid, m.p. 140 °C (dec.). Ϫ 1H NMR (400.1 MHz, [D6]acetone):
166 (9), 165 (100) [Mϩ Ϫ Cr Ϫ 3CO Ϫ ethyl lactate], 137 (5), 122
3
δ ϭ 0.80 (d, J18-13 ϭ 7 Hz, 3 H, 18-H), 0.89 (m, 1 H), 0.91 (d,
(3), 107 (3), 92 (3), 79 (6), 52 (3) [52Cr]. Ϫ HRMS (C17H18CrO9):
3
3J16/17-15 ϭ 6.4 Hz, 3 H, 16-H or 17-H), 0.93 (d, J17/16-15 ϭ 7 Hz,
calcd. 418.035592; found 418.035126.
3 H, 17-H or 16-H), 1.1 (m, 2 H), 1.51 (m, 2 H), 1.73 (m, 2 H),
2.12 (m, 2 H), 3.87 (s, 3 H, 7-H), 4.85 (m, 1 H), 5.21Ϫ6.35 (ABCD
(1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl
2-Methoxybenzoate:
system, 4 H, 3-H, 4-H, 5-H, 6-H). Ϫ 13C NMR (100.6 MHz, [D6]a-
cetone, DEPT): δ ϭ 15.4 (CH3, C-16 or C-17), 20.2 (CH3, C-16 or
C-17), 21.4 (CH3, C-18), 22.7 (CH2, C-11), 25.5 (CH, C-15), 31.1
(CH, C-13), 33.9 (CH2, C-12), 40.5 (CH2, C-14), 47.1 (CH, C-10),
55.8 (CH3, C-7), 74.5 (CH, C-9), 74.9 (CH, C-3, C-4, C-5 or C-6),
84.66 (Cq, C-1), 84.67 (CH, C-3, C-4, C-5 or C-6), 97.1 (CH, C-3,
C-4, C-5 or C-6), 98.2 (CH, C-3, C-4, C-5 or C-6), 144.7 (Cq, C-
2), 163.7 (Cq, C-8), 232.0 (Cq, CO).
[72,73]
Procedure 1; 2-methoxybenzoic acid chloride (3.41 g,
20 mmol) in diethyl ether (15 mL), (Ϫ)-menthol (3.12 g, 20 mmol)
and pyridine (2.4 mL, 30 mmol) in diethyl ether (20 mL). Column
chromatography (SiO2, diethyl ether/petroleum ether 1:2, length
30 cm, ø 3.5 cm) and solvent removal gave 5.45 g (18.8 mmol, 94%)
of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 2-methoxybenzoate
as colorless needles, m.p. 42 °C. Ϫ IR (CHCl3): ν˜ ϭ 3028 cmϪ1
(w), 2952 (s), 2916 (s), 2864 (m), 1728 (s, ester CϭO), 1596 (s),
1492 (s), 1452 (s), 1384 (m), 1368 (m), 1332 (m), 1280 (s), 1256 (s),
1180 (m), 1164 (m), 1136 (m), 1084 (s, CϪO), 1016 (s), 960 (m),
Fraction II: Rf ϭ 0.48 (diethyl ether/petroleum ether 2:1), orange
solid, m.p. 143 °C (dec.). Ϫ 1H NMR (400.1 MHz, [D6]acetone):
1
3
756 (s), 712 (m), 660 (m). Ϫ H NMR (400.1 MHz, CDCl3): δ ϭ
δ ϭ 0.80 (d, J18-13 ϭ 7 Hz, 3 H, 18-H), 0.89 (m, 1 H), 0.91 (d,
3
3
3
3J16/17-15 ϭ 6.4 Hz, 3 H, 16-H or 17-H), 0.93 (d, J17/16-15 ϭ 7 Hz,
0.81 (d, J18-13 ϭ 7 Hz, 3 H, 18-H), 0.91 (d, J16/17-15 ϭ 6.4 Hz, 3
3
H, 16-H or 17-H), 0.92 (d, J17/16-15 ϭ 7 Hz, 3 H, 17-H or 16-H),
3 H, 17-H or 16-H), 1.1 (m, 2 H), 1.51 (m, 2 H), 1.73 (m, 2 H),
2.12 (m, 2 H), 3.86 (s, 3 H, 7-H), 4.85 (m, 1 H), 5.21Ϫ6.35 (ABCD
line system, 4 H, 3-H, 4-H, 5-H, 6-H). Ϫ 13C NMR (100.6 MHz,
[D6]acetone): δ ϭ 15.3 (CH3, C-16 or C-17), 20.2 (CH3, C-16 or
C-17), 21.3 (CH3, C-18), 22.6 (CH2, C-11), 25.7 (CH, C-15), 31.1
(CH, C-13), 33.9 (CH2, C-12), 40.4 (CH2, C-14), 47.0 (CH, C-10),
55.7 (CH3, C-7), 74.41 (CH, C-3, C-4, C-5 or C-6), 74.42 (CH, C-
9), 84.60 (Cq, C-1), 84.61 (CH, C-3, C-4, C-5 or C-6), 96.9 (CH,
C-3, C-4, C-5 or C-6), 97.8 (CH, C-3, C-4, C-5 or C-6), 144.6 (Cq,
C-2), 163.1 (Cq, C-8), 232.0 (Cq, CO).
1.10 (m, 3 H), 1.52 (m, 2 H), 1.71 (m, 2 H), 2.12 (m, 2 H), 3.88 (s,
3
3
3
3 H, 7-H), 4.92 (ddd, J9-eq-14 ϭ 4.3 Hz, J9-ax-14 ϭ 10.9 Hz, J9-10
ϭ 10.9 Hz, 1 H, 9-H), 6.96Ϫ7.75 (ABCD system, 4 H, 3-H, 4-
H, 5-H, 6-H). Ϫ 13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 16.1
(CH3, C-16 or C-17), 20.8 (CH3, C-17 or C-16), 21.9 (CH3, C-18),
23.2 (CH2, C-11), 26.0 (CH, C-15), 31.4 (CH, C-13), 34.2 (CH2, C-
12), 40.8 (CH2, C-14), 47.1 (CH, C-10), 55.8 (CH3, C-7), 74.5 (CH,
C-9), 111.9 (CH, C-3, C-4, C-5 or C-6), 120.0 (CH, C-3, C-4, C-5
or C-6), 121.0 (Cq, C-1), 131.1 (CH, C-3, C-4, C-5 or C-6), 133.0
(CH, C-3, C-4, C-5 or C-6), 158.9 (Cq, C-2), 165.8 (Cq, C-8). Ϫ
MS (70 eV, 20 °C): m/z (%) ϭ 291 (4) [Mϩ ϩ 1], 290 (11) [Mϩ],
275 (2) [Mϩ Ϫ CH3], 235 (3), 177 (3), 154 (29), 153 (53), 152 (35),
139 (35), 138 (50), 136 (35), 135 (100) [C6H4OCH3COϩ], 123 (39),
120 (18), 109 (29), 105 (32), 95 (57), 92 (34), 83 (36), 82 (37), 81
(43), 78 (42). Ϫ HRMS (C18H26O3): calcd. 290.188195; found
290.188568. Ϫ C18H26O3 (290.19): calcd. C 74.45, H 9.02; found
C 74.37, H 9.06. Ϫ [α]2D0 ϭ Ϫ48 (c ϭ 1, Et2O).
(1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl 3,4-Dimethoxybenzoate:
Procedure 1; 3,4-dimethoxybenzoyl chloride (4.01 g, 20 mmol) in
diethyl ether (35 mL), (Ϫ)-menthol (3.12 g, 20 mmol) and pyridine
(2.4 mL, 30 mmol) in diethyl ether (20 mL). Column chromato-
graphy (SiO2, diethyl ether/petroleum ether 2:3, length 25 cm, ø
3.5 cm) and solvent removal gave 6.08 g, 19.0 mmol, 95%) of
(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 3,4-dimethoxybenzo-
ate, colorless oil. Ϫ IR (CHCl3): ν˜ ϭ 3028 cmϪ1 (w), 2960 (s), 2936
(m), 2872 (m), 1700 (s, ester CϭO), 1600 (m), 1512 (s), 1464 (s),
1420 (m), 1344 (m), 1292 (s), 1288 (s), 1228 (m), 1176 (m), 1132
(1S,2R,5S)-2-Isopropyl-5-methylcyclohexyl 2-Methoxybenzoate: As
described above, using (ϩ)-menthol. Ϫ [α]2D0 ϭ ϩ46.1 (c ϭ 1, Et2O).
1
(m), 1112 (m), 1024 (m), 980 (m), 964 (m), 880 (m). Ϫ H NMR
(1R,2S,5R)-Tricarbonyl[η6-(2-isopropyl-5-methyl)cyclohexyl 2-me-
(400.1 MHz, CDCl3): δ ϭ 0.8 (d, 3J18-13 ϭ 6.8 Hz, 3 H, 19-H), 0.91
3
3
thoxybenzoate]chromium(0)
(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl
(650 mg, 2.42 mmol), Cr(CO)6 (600 mg, 2.73 mmol) in dibutyl 2 H), 1.95 (m, 1 H), 2.12 (m, 1 H), 3.94 (s, br, 6 H, 7-H, 8-H), 4.92
[(1R,2S,5R)-3]:
Procedure
2;
(d, J17/18-16 ϭ 7 Hz, 3 H, 17-H or 18-H), 0.92 (d, J17/18-16
ϭ
2-methoxybenzoate
6.5 Hz, 3 H, 17-H or 18-H), 1.1 (m, 3 H), 1.55 (m, 2 H), 1.74 (m,
3
3
3
ether (60 mL) and THF (6 mL). The solution was heated at reflux
for 43 h with formation of an orange suspension. Column chroma-
tography (SiO2, diethyl ether/petroleum ether 1:2 Ǟ 1:1, length
35 cm, ø 3.5 cm) and solvent removal gave 560 mg (1.32 mmol,
54%, de ഠ 0%) of (1R,2S,5R)-3 as a mixture of diastereomers. Ϫ
(ddd, J10-eq-15 ϭ 4.4 Hz, J10-ax-15 ϭ 10.8 Hz, J10-11 ϭ 10.8 Hz, 1
H, 10-H), 6.9 (d, J5-6 ϭ 8.5 Hz, 1 H, 5-H), 7.6 (d, J2-6 ϭ 1.9 Hz,
1 H, 2-H), 7.7 (dd, J6-5 ϭ 8.5 Hz, J2-6 ϭ 1.9 Hz, 1 H, 6-H). Ϫ
13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 16.7 (CH3, C-17 or
C-18), 20.7 (CH3, C-17 or C-18), 22.1 (CH3, C-19), 23.8 (CH2, C-
3
4
3
4
IR (CHCl3): ν˜ ϭ 3096 cmϪ1 (w), 2956 (m), 2928 (m), 2872 (w), 12), 26.6 (CH, C-16), 31.5 (CH, C-14), 34.4 (CH2, C-13), 41.1
1980 (s, CO), 1908 (s, br, CO), 1716 (m, br, esterϪCϭO), 1524 (w), (CH2, C-15), 47.3 (CH, C-11), 56.0 (CH3, C-7 or C-8), 56.01 (CH3,
1464 (m), 1416 (w), 1292 (m), 1256 (m), 1180 (w), 1120 (m), 1080
C-7 or C-8), 74.6 (CH, C-10), 110.2 (CH, C-2, C-5 or C-6), 112.1
(m), 1012 (w). Ϫ MS (70 eV, 110 °C): m/z (%) ϭ 426 (1) [Mϩ], 370 (CH, C-2, C-5 or C-6), 123.44 (Cq, C-1), 123.46 (CH, C-2, C-5 or
(2) [Mϩ Ϫ CO], 343 (4) [Mϩ ϩ 1 Ϫ 2CO], 342 (9) [Mϩ Ϫ 2CO],
290 (1) [Mϩ Ϫ 3CO Ϫ Cr], 242 (5), 204 (16), 158 (19), 153 (25),
C-6), 148.6 (Cq, C-3 or C-4), 152.8 (Cq, C-3 or C-4), 165.9 (Cq, C-
9). Ϫ MS (70 eV, 70 °C): m/z (%) ϭ 320 (3) [Mϩ], 319 (9) [Mϩ
Ϫ
138 (40), 135 (100) [C6H4OCH3COϩ], 123 (32), 95 (93), 81 (84). 1], 183 (13), 182 (100) [C6H3(OCH3)2CO2Hϩ], 165 (27), 138 (13),
Ϫ HRMS (C21H26CrO6): calcd. 426.113449; found 426.113586. Ϫ
123 (13), 109 (5), 95 (31), 81 (27), 71 (28). Ϫ HRMS (C19H28O4):
2278
Eur. J. Org. Chem. 2000, 2273Ϫ2284

Preparation of Chiral Amine Carbonyl Chromium(0) Complexes
FULL PAPER
calcd. 320.198760; found 320.198792. Ϫ C19H28O4 (320.43): calcd.
C 71.22, H 8.81; found C 71.48, H 9.10. Ϫ [α]2D0 ϭ Ϫ72.9, (c ϭ
1, Et2O).
(Ϫ, C-3, C-4, C-5 or C-6),127.96 (ϩ, C-1), 130.8 (Ϫ, C-3, C-4, C-
5 or C-6), 158.6 (ϩ, C-2). Ϫ MS (70 eV, 25 °C): m/z (%) ϭ 209 (3)
[Mϩ ϩ 1], 208 (62) [Mϩ], 193 (4), 177 (17) [Mϩ Ϫ OCH3], 135
(100) [Mϩ Ϫ C4H9O], 121 (26), 119 (27), 108 (81), 92 (33), 91 (69),
77 (71). Ϫ HRMS (C12H16O3): calcd. 208.1099; found 208.1100. Ϫ
(1R,2S,5R)-Tricarbonyl[η6-(2-isopropyl-5-methyl)cyclohexyl 3,4-di-
methoxybenzoate]chromium(0) [(1R,2S,5R)-4]: Procedure 2;
(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 3,4-dimethoxybenzoate
(200 mg, 0.625 mmol), Cr(CO)6 (220 mg, 1.00 mmol) in dibutyl
ether (50 mL) and THF (5 mL). The solution was heated at reflux
for 18 h with formation of an orange suspension. Column chroma-
tography (SiO2, diethyl ether/petroleum ether 1:2 Ǟ 1:1, length
20 cm, ø 2.5 cm) and solvent removal gave 130 mg [0.29 mmol,
46%, de ഠ 6% (NMR)] of (1R,2S,5R)-4 as a viscous orange oil. Ϫ
IR (CHCl3): ν˜ ϭ 3096 cmϪ1 (w), 2960 (m), 2928 (m), 2872 (w),
1972 (s, CO), 1904 (s, br, CO), 1708 (m, br, ester-CϭO), 1604 (m),
1536 (w), 1512 (w), 1488 (m), 1464 (m), 1384 (m), 1288 (m), 1280
(m), 1236 (m), 1180 (w), 1104 (m), 1020 (m). Ϫ 1H NMR
20
20
20
[α]2D0 ϭ Ϫ12.2; [α] ϭ Ϫ15.0; [α] ϭ Ϫ28.4; [α] ϭ Ϫ49.8 (c ϭ
546
436
365
1, Et2O).
Tricarbonyl{η6-1-[(1ЈR,2ЈR)-1Ј,2Ј-dimethylethylenedioxy]methyl-2-
methoxybenzene}chromium(0) [(R,R)-5]:[41] Procedure 2; 1-
[(1ЈR,2ЈR)-1Ј,2Ј-dimethylethylenedioxy]methyl-2-methoxybenzene
[(R,R)-9] (1.04 g, 5.0 mmol), Cr(CO)6 (1.2 g, 5.5 mmol) in dibutyl
ether (100 mL) and THF (10 mL). The solution was heated at re-
flux for 20 h with formation of a yellow suspension. Column chro-
matography (SiO2 diethyl ether/petroleum ether 1:3 Ǟ 1:1, length
30 cm, ø 3.5 cm) and solvent removal gave 791 mg [0.23 mmol,
46%, de ഠ 11% (NMR)] of (R,R)-5 as a mixture of diastereomers
as a yellow oil.[41]
3
(400.1 MHz, [D6]acetone): δ ϭ 0.79 (2d, J13-18 ϭ 6.7 Hz, 3 H, 19-
3
Procedure for the Preparation of (η6-Arene)tricarbonylchromium
Complexes with Tetracarbonyl(η4-norbornadiene)chromium(0) (6)
(Procedure 3):[42,43] The arene (1 equiv.) and 6 (1 equiv.) in THF
were heated at reflux until no more 6 could be detected by TLC.
Liberated norbornadiene was removed from the reaction mixture
by a continuous flow of argon gas. After removal of the solvent
and residual norbornadiene at reduced pressure the product was
purified by column chromatography.
H), 0.9 (m, 1 H), 0.91 (d, J17/16-18 ϭ 7 Hz, 3 H, 17-H or 18-H),
3
0.92 (d, J17/16-18 ϭ 6.5 Hz, 3 H, 17-H or 18-H), 1.1 (m, 2 H), 1.55
(m, 2 H), 1.72 (m, 2 H), 1.98 (m, 1 H), 2.12 (m, 1 H), 3.85 (2s, 3
H, 7-H or 8-H), 3.87 (2s, 3 H, 7-H or 8-H), 4.85 (m, 1 H, 10-H),
5.72 (m, 1 H, 5-H), 6.08 (m, 1 H, 2-H), 6.19 (m, 1 H). Double set
of signals due to diastereomers. Ϫ 13C NMR (100.6 MHz, CDCl3,
DEPT): δ ϭ 15.6 (CH3, C-17 or C-18), 20.02 ϩ 20.03 (CH3, C-17
or C-18), 21.3 (CH3, C-19), 22.9 (CH2, C-12), 25.94 ϩ 25.95 (CH,
C-16), 31.11 ϩ 31.14 (CH, C-14), 33.83 ϩ 33.85 (CH2, C-13), 40.3
ϩ 40.5 (CH2, C-15), 46.9 ϩ 47.2 (CH, C-11), 56.1 ϩ 56.2 (CH3,
C-7 or C-8), 56.9 ϩ 57.1 (CH3, C-7 or C-8), 75.15 ϩ 75.29 (CH,
C-10), 75.5 ϩ 76.3 (CH, C-2, C-5 or C-6), 80.4 (Cq, C-1), 85.1 ϩ
85.4 (CH, C-2, C-5 or C-6), 90.8 ϩ 90.9 (CH, C-2, C-5 or C-6),
130.3 ϩ 130.8 (Cq, C-3 or C-4), 137.0 ϩ 137.2 (Cq, C-3 or C-4),
164.19 ϩ 164.21 (Cq, C-9), 232.14 ϩ 232.36 (Cq, CO). Ϫ MS
(70 eV, 120 °C): m/z (%) ϭ 456 (2) [Mϩ], 455 (4) [Mϩ Ϫ 1], 401
(3), 400 (8) [Mϩ Ϫ 2CO], 373 (17), 372 (52) [Mϩ Ϫ 3CO], 324 (5),
319 (4) [Mϩ Ϫ 3CO Ϫ Cr Ϫ 1], 235 (21), 234 (100) [Mϩ Ϫ 3CO
Ϫ menthyl], 233 (14), 206 (6), 189 (18), 182 (61), 165 (48), 129 (7),
95 (13), 81 (10), 77 (8), 52 (33) [52Cr]. Ϫ HRMS (C22H28CrO7):
calcd. 456.124013; found 456.123077. Ϫ C22H28CrO7 (456.45):
calcd. C 57.89, H 6.18; found C 57.88, H 6.38.
Tricarbonyl(η6-naphthalene)chromium(0) (7):[22] Procedure 3; com-
pound 6 (100 mg, 0.39 mmol) and naphthalene (50 mg, 0.39 mmol)
in THF (50 mL) were heated at reflux for 72 h. Column chromato-
graphy (SiO2, TBME/petroleum ether 1:5 Ǟ 1:3, length 20 cm, ø
2 cm) and solvent removal gave 82 mg (0.31 mmol, 80%) of 7 as a
brick-red solid.[22,68]
Pentacarbonyl[(S)-1-cyclohexylethylamine]chromium(0)
[(S)-8]:
Compound 6 (275 mg, 1.07 mmol) in (S)-1-cyclohexylethylam-
ine[44,45] (1.3 mL, 1.13 g, 8.89 mmol) was stirred for 18 h in the dark
at 20 °C. Diethyl ether (20 mL) was added in four portions, causing
precipitation of a fine yellow solid which, due to its instability,
could not be characterized. After filtration through a P4 frit and
solvent removal at reduced pressure a yellow oil was obtained. It
was purified by column chromatography (SiO2, diethyl ether/petro-
leum ether 1:1, length 30 cm, ø 2.5 cm) to give (S)-8 (147 mg,
0.46 mmol, 43%) as a yellow crystalline solid (m.p. 105 °C, dec.).
Ϫ IR (KBr): ν˜ ϭ 3340 cmϪ1 (m, amine), 3296 (w, amine), 2936
(m), 2856 (s), 2064 (m, CO), 1984 (m, CO), 1950 (m, CO), 1924 (s,
CO), 1888 (s, CO), 1872 (s, CO), 1584 (m), 1084 (m), 1020 (m), 800
(m), 656 (m). Ϫ 1H NMR (200.1 MHz, [D6]acetone): δ ϭ
0.85Ϫ1.82 (m, 14 H, 8-H, 1-H, 2-H, 3-H, 4-H, 5-H, 6-H), 2.38 (m,
1 H, 7-H), 2.62Ϫ3.04 (br, 2 H, amine). Ϫ 13C NMR (50.3 MHz,
[D6]acetone, APT): δ ϭ 17.3 (Ϫ, C-8), 26.9 (ϩ, C-2 or C-3, C-4,
C-5 or C-6), 27.09 (ϩ, C-2 or C-3, C-4, C-5 or C-6), 27.13 (ϩ, C-
2 or C-3, C-4, C-5 or C-6), 27.4 (ϩ, C-2 or C-3, C-4, C-5 or C-6),
45.2 (Ϫ, C-1), 61.1 (Ϫ, C-7), 215.6 (ϩ, COax), 215.9 (ϩ, 4COeq).
Ϫ MS (70 eV, 70 °C): m/z (%) ϭ 319 (2) [Mϩ], 318 (5) [Mϩ Ϫ 1],
291 (3) [Mϩ Ϫ CO], 263 (2) [Mϩ Ϫ 2CO], 235 (2) [Mϩ Ϫ 3CO],
208 (3), 207 (9) [Mϩ Ϫ 4CO], 180 (13), 179 (64) [Mϩ Ϫ 5CO], 156
(4), 127 (3) [amine], 126 (7), 120 (8), 106 (100), 95 (20), 79 (38), 77
(30), 52 (46) [52Cr]. Ϫ C13H17CrNO5 (320.43): calcd. C 48.91, H
5.37, N 4.39; found C 47.61, H 5.28, N 4.30. Ϫ [α]2D0 ϭ Ϫ14.8 (c ϭ
1, acetone).
1-[(1ЈR,2ЈR)-1Ј,2Ј-Dimethylethylenedioxy]methyl-2-methoxy-
benzene: 2-Methoxybenzaldehyde (7.39 g, 55.0 mmol), (2R,3R)-bu-
tane-2,3-diol (5 mL, 55.0 mmol) and p-toluenesulfonic acid (70 mg,
0.4 mmol) in benzene (20 mL) were heated at reflux for six days
with azeotropic water removal. After cooling to room temperature
the mixture was washed twice with aqueous sodium hydroxide solu-
tion (each 0.1 , 20 mL), then with water (50 mL). After drying of
the organic layer over K2CO3 and solvent removal at reduced pres-
sure, a red-brown oil was obtained and purified by column chroma-
tography (SiO2, diethyl ether/petroleum ether 1:2, length 50 cm, ø
2 cm) to give 8.02 g (38.5 mmol, 70%) of 1-[(1ЈR.2ЈR)-1Ј,2Ј-di-
methylethylenedioxy]methyl-2-methoxybenzene as a colorless oil.
Ϫ IR (CHCl3): ν˜ ϭ 3061 cmϪ1 (w), 3000 (m), 2972 (m), 2932 (m),
2884 (m), 2840 (w), 1604 (m, arom. CϭC), 1492 (m, arom. CϭC),
1464 (m), 1380 (m), 1284 (m), 1244 (s), 1088 (s, acetal CϪO), 980
(acetal CϪO), 940 (w), 908 (w). Ϫ 1H NMR (200.1 MHz, CDCl3):
3
3
δ ϭ 1.32 (2d, J9-1Ј ϭ 5.4 Hz, 3 H, 9-H or 10-H), 1.38 (2d, J10-2Ј
ϭ 5.4 Hz, 3 H, 10-H or 9-H), 3.79 (m, 2 H, 1Ј-H, 2Ј-H), 3.86 (s,
3 H, 7-H), 6.32 (s, 1 H, 8-H), 6.86Ϫ7.57 (ABCD system, 4 H, 3-
H, 4-H, 5-H, 6-H). Ϫ 13C NMR (50.3 MHz, [D6]acetone, APT):
δ ϭ 17.0 (Ϫ, C-9 or C-10), 17.4 (Ϫ, C-10 or C-9), 55.7 (Ϫ, C-7),
78.8 (Ϫ, C-1Ј or C-2Ј), 80.7 (Ϫ, C-2Ј or C-1Ј), 98.2 (Ϫ, C-8), 111.5
Preparation of Diaminetetracarbonylchromium(0) Chelate Com-
plexes From Liquid Diamines without Solvent (Procedure 4): Hexa-
(Ϫ, C-3, C-4, C-5 or C-6), 120.9 (Ϫ, C-3, C-4, C-5 or C-6), 127.95 carbonylchromium was suspended in the liquid diamine and heated
Eur. J. Org. Chem. 2000, 2273Ϫ2284 2279

M. Strotmann, H. Butenschön
FULL PAPER
at 120 °C in the dark, the mixture becoming orange-red. After cool-
ing to 20 °C, ethanol was added, and unchanged hexacarbonylchro-
mium filtered off with a P3 frit. After washing several times with
ethanol the crude product was precipitated by addition of water.
For complete crystallization the filtrate was stored for 24 h at 5 °C,
then the crystals were filtered off with a P4 frit. The solid was
washed with water and dried on the frit at 0.01 mbar. The product
(m), 2860 (w), 2004 (m, CO), 1876 (s, CO), 1848 (s, CO), 1784 (s,
CO), 1592 (m), 1024 (m), 700 (w), 672 (m), 644 (m). Ϫ H NMR
1
(200.1 MHz, [D6]acetone): δ ϭ 1.10Ϫ1.79 [m, 8 H, 3(6)-H, 4(5)-H],
2.74Ϫ3.09 (br, 4 H, amine), 3.42 [m, 2 H, 1(2)-H]. Ϫ 13C NMR
(50.3 MHz, [D6]acetone, APT): δ ϭ 25.5 [ϩ, C-4(5)], 35.8 [ϩ, C-
3(6)], 59.4 [Ϫ, C-1(2)], 216.9 (ϩ, COax), 228.1 (ϩ, COeq). Ϫ MS-
FAB: m/z (%) ϭ 278 (11) [Mϩ], 250 (3) [Mϩ Ϫ CO], 222 (4) [Mϩ
was washed from the frit with acetone and isolated as a yellow Ϫ 2CO], 207 (4), 194 (5) [Mϩ Ϫ 3CO], 167 (5), 166 (6) [Mϩ
Ϫ
powder after removal of the acetone at reduced pressure.
4CO], 165 (5), 152 (9), 150 (6) [Mϩ Ϫ 4CO Ϫ NH2], 149 (9), 136
(68) [Cr(CO)3ϩ], 108 (19) [Cr(CO)2ϩ]. Ϫ C10H14CrN2O4 (278.23):
Preparation of Chelate Diaminetetracarbonylchromium(0) Com-
plexes with Tetracarbonyl(norbornadiene)chromium(0) (6) (Proced-
ure 5): The amine (1 equiv.) and compound 6 (1 equiv.) in THF
were heated at reflux until no more 6 could be detected by TLC.
The reaction progress was indicated by a color change from orange-
yellow to yellow. After solvent removal at reduced pressure the
crude product was isolated either by crystallization (see Procedure
4) or by column chromatography.
calcd. C 43.17, H 5.07, N 10.07; found C 43.15, H 5.09, N 8.78.
(1R,2R)-(trans-1,2-Diaminocyclohexane)tetracarbonylchromium(0)
[(1R,2R)-10]: Procedure 5; (1R,2R-)-trans-1,2-diaminocyclohexane
(200 mg, 1.75 mmol) and 6 (446 mg, 1.74 mmol) in THF (30 mL)
were heated at reflux for 30 min. Crystallization (15 mL of ethanol,
50 mL of water) gave 481 mg (1.73 mmol, 99%) of (1R,2R)-10 as a
yellow powder. Ϫ [α]2D0 ϭ ϩ34 (c ϭ 0.5, acetone).
(N,NЈ-Dicyclohexyl)-1,2-ethanediamine:[46,47] Sodium tetrahydri-
rac-(1,2-Diaminopropane)tetracarbonylchromium(0)
(rac-11):[49]
doborate (2.66 g, 70.0 mmol) was added to (N,NЈ-dicyclohexyl)-1,2- Procedure 4; hexacarbonylchromium(0) (1.7 g, 7.7 mmol) and rac-
ethanediimine[74,75] (6.6 g, 30.0 mmol) in anhydrous methanol
(50 mL) and heated for 3 h at 50 °C. After solvent removal at re-
duced pressure the residue was taken up with water (100 mL). The
1,2-diaminopropane (15 mL, 180 mmol) were heated at 120 °C for
14 h in the dark. Crystallization (20 mL of ethanol, 50 mL of
water) gave 1.81 g (7.6 mmol, 98%) of rac-11, yellow powder (m.p.
mixture was extracted three times with MTBE (each 50 mL), and 195 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3372 cmϪ1 (m, amine), 3352 (m,
the collected organic layers were dried over Na2SO4. After filtration
and solvent removal at reduced pressure 6.6 g (29.5 mmol, 98%) of (w), 2012 (m, CO), 1916 (s, CO), 1868 (s, CO), 1844 (s, CO), 1772
(N,NЈ-dicyclohexyl)-1,2-ethanediamine was obtained as a colorless (s, CO), 1592 (m), 1460 (m), 1136 (m), 1048 (m), 1016 (m), 700 (w),
solid (m.p. 86 °C). Ϫ IR (KBr): ν˜ ϭ 3388 cmϪ1 (m, amine), 3276 676 (m), 644 (m). Ϫ 1H NMR (200.1 MHz, [D6]acetone): δ ϭ 1.22
(s, amine), 2924 (s), 2852 (s), 2808 (m), 1492 (m), 1452 (s), 1376 (d, 3 H, 3-H), 2.58Ϫ3.04 (br, 4 H, amine), 3.32 (br, 2 H, 1-H), 3.48
(m), 1224 (m), 1144 (m), 1124 (s), 904 (m), 860 (m), 840 (m). Ϫ 1H (br, 1 H, 2-H). Ϫ 13C NMR (50.3 MHz, [D6]acetone, APT): δ ϭ
NMR (400.1 MHz, CDCl3): δ ϭ 1.01Ϫ1.92 (m, 22 H, 3-H, 4-H, 19.7 (Ϫ, C-3), 50.4 (ϩ, C-1), 52.3 (Ϫ, C-2), 216.71 (ϩ, COax),
5-H, 6-H, 7-H, amine), 2.39 (m, 2 H, 2-H), 2.73 (s, 4 H, 1-H). Ϫ 216.77 (ϩ, COax), 227.78 (ϩ, COeq), 227.88 (ϩ, COeq). Ϫ MS-FAB:
13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 25.7 (CH2, C-5), 26.8 m/z (%) ϭ 238 (15) [Mϩ], 210 (10) [Mϩ Ϫ CO], 154 (22) [Mϩ
amine), 3316 (m, amine), 3296 (m, amine), 2980 (w), 2940 (w), 2880
Ϫ
[CH2, C-4(6)], 34.3 [CH2, C-3(7)], 47.7 (CH2, C-1), 57.6 (CH, C- 3CO]. Ϫ C7H10CrN2O4 (238.16): calcd. C 35.30, H 4.23, N 11.76;
2). Ϫ MS (70 eV, 20 °C): m/z (%) ϭ 225 (4) [Mϩ ϩ 1], 224 (20) found C 35.52, H 4.48, N 10.38.
[Mϩ], 223 (6), 191 (7), 136 (7), 126 (5), 113 (22), 112 (100), 83 (8),
rac-(1,3-Diaminopentane)tetracarbonylchromium(0) (rac-12): Pro-
69 (11).
Ϫ HRMS (C14H28N2): calcd. 224.225249; found
cedure 4; hexacarbonylchromium(0) (2.2 g, 10.0 mmol) and rac-1,3-
diaminopentane (5 mL, 125.0 mmol) were heated at 120 °C for 15 h
in the dark. Crystallization (20 mL of ethanol, 70 mL of water)
gave 2.61 g (9.8 mmol, 98%) of rac-12 as a yellow powder (m.p. 213
°C, dec.). Ϫ IR (KBr): ν˜ ϭ 3408 cmϪ1 (m, amine), 3344 (m, amine),
3300 (m, amine), 3280 (m, amine), 2936 (m), 2884 (m), 2004 (s,
CO), 1908 (s, CO), 1858 (s, CO), 1846 (s, CO), 1792 (s, CO), 1588
224.227325.
Tetracarbonyl[(N,NЈ-dicyclohexyl)-1,2-ethanediamine]chromium(0)
(9): Procedure 5; (N,NЈ-dicyclohexyl)-1,2-ethanediamine[46,47]
(220 mg, 0.98 mmol) and 6 (250 mg, 0.98 mmol) in THF (50 mL)
was heated at reflux for 30 min. Crystallization (60 mL of ethanol,
50 mL of water) gave 375 mg (0.97 mmol, 99%) of 9 as a yellow
powder (m.p. 143 °C). Ϫ IR (KBr): ν˜ ϭ 3280 cmϪ1 (m, amine),
(m), 1464 (m), 1152 (m), 1068 (m), 1016 (m), 700 (w), 660 (m), 640
1
2932 (s), 2860 (m), 2004 (s, CO), 1876 (s, CO), 1844 (s, CO), 1784 (m), 460 (m). Ϫ H NMR (200.1 MHz, [D6]acetone): δ ϭ 0.91 (t,
(s, CO), 1452 (m), 1264 (m), 1092 (m), 1060 (m), 960 (m), 696 (m), 3J5-4 ϭ 7.8 Hz, 3 H, 5-H), 1.06Ϫ1.89 (m, br, 4 H, 2-H, 4-H),
1
656 (m). Ϫ H NMR (400.1 MHz, CDCl3): δ ϭ 1.09Ϫ2.90 (m, 26
2.34Ϫ2.78 (br, 4 H, amine), 2.88Ϫ3.19 (br, 2 H, 1-H), 3.19Ϫ3.38
H, 1-H, 2-H, 3-H, 4-H, 5-H, 6-H, 7-H), 3.96 (s, br, 2 H, amine). Ϫ (br, 1 H, 3-H). Ϫ 13C NMR (50.3 MHz, [D6]acetone, APT): δ ϭ
13C NMR (100.6 MHz, CDCl3, APT): δ ϭ 25.2 (ϩ, C-5), 25.5 (ϩ, 10.0 (Ϫ, C-5), 33.6 (ϩ, C-4), 34.4 (ϩ, C-2), 47.4 (ϩ, C-1), 60.2 (Ϫ,
C-4 or C-6), 25.6 (ϩ, C-4 or C-6), 30.8 (ϩ, C-3 or C-7), 31.6 (ϩ,
C-3), 216.0 (ϩ, COax), 216.9 (ϩ, COax), 225.9 (ϩ, COeq), 226.3 (ϩ,
C-3 or C-7), 47.9 (ϩ, C-1), 62.6 (Ϫ, C-2), 215.9 (ϩ, COax), 227.1 COeq). Ϫ MS (70 eV, 130 °C): m/z (%) ϭ 267 (2) [Mϩ ϩ 1], 266 (3)
(ϩ, COeq). Ϫ MS-FAB: m/z (%) ϭ 388 (10) [Mϩ], 304 (56) [Mϩ
Ϫ
[Mϩ], 238 (2) [Mϩ Ϫ CO], 210 (4) [Mϩ Ϫ 2CO], 182 (2) [Mϩ
Ϫ
3CO], 276 (44) [Mϩ Ϫ 4CO], 225 (60) [Mϩ Ϫ 4CO Ϫ Cr ϩ 1].
C18H28CrN2O4 (388.43): calcd. C 55.66, H 7.27, N 7.21; found C
53.67, H 7.57, N 6.99.
3CO], 155 (4), 154 (15) [Mϩ Ϫ 4CO], 145 (5), 121 (7), 108 (5), 86
(7), 85 (100) [amine Ϫ NH3], 73 (38). Ϫ C9H14CrN2O4 (266.21):
calcd. C 40.61, H 5.30, N 10.51; found C 40.88, H 5.44, N 9.92.
rac-(trans-1,2-Diaminocyclohexane)tetracarbonylchromium(0) [rac-
10]: Procedure 4; hexacarbonylchromium(0) (2.4 g, 10.9 mmol) and
20 mL of a mixture of cis- and trans-1,2-diaminocyclohexane (cis/
trans ϭ 1:3.5) were heated at 120 °C for 18 h in the dark. Crystal-
Tetracarbonyl{[(S)-2-cyclohexylaminomethyl]pyrrolidine}chro-
mium(0) [(S)-13]: Procedure 5; (S)-aminocyclohexylmethyl)pyrroli-
dine[52] (213 mg, 1.17 mmol) and 11 (300 mg, 1.17 mmol) in THF
(50 mL) were heated at reflux for 30 min. Column chromatography
lization (20 mL of ethanol, 100 mL of water) gave 2.73 g (SiO2 diethyl ether/petroleum ether 1:2 Ǟ 1:0, length 35 cm, ø
(9.81 mmol, 90%) of rac-10 as a yellow powder (m.p. 165 °C, dec.). 3.5 cm) and solvent removal gave 350 mg (1.01 mmol, 87%) of (S)-
Ϫ IR (KBr): ν˜ ϭ 3356 cmϪ1 (m, amine), 3300 (m, amine), 2932 13 as a yellow solid (m.p. 138 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3296
2280
Eur. J. Org. Chem. 2000, 2273Ϫ2284

Preparation of Chiral Amine Carbonyl Chromium(0) Complexes
FULL PAPER
cmϪ1 (m, amine), 3272 (w, amine), 2924 (m), 2852 (m), 2004 (m,
CO), 1892 (s, CO), 1848 (s, CO), 1808 (s, CO), 1788 (s, CO), 1452
56.7 (ϩ, C-5), 60.5 (Ϫ, C-1), 214.2 (ϩ, COax), 215.9 (ϩ, COax),
225.9 (ϩ, COeq), 227.3 (ϩ, COeq). Ϫ MS (70 eV, 170 °C): m/z (%) ϭ
(m), 1260 (w), 1076 (w), 1016 (w), 940 (w), 804 (w), 696 (w), 656 209 (2), 208 (8) [Mϩ Ϫ 4CO], 135 (2), 123 (3), 86 (11), 70 (100)
1
(m), 636 (w), 456 (w). Ϫ H NMR (400.1 MHz, [D6]acetone): δ ϭ [C4H8Nϩ], 52 (3) [52Crϩ].
Ϫ
HRMS (C9H20CrN2): calcd.
0.86Ϫ2.10 (m, 14 H, 2-H, 3-H, 7-H, 8-H, 9. H, 10-H, 11-H), 2.31
(m, 1 H, 6-H), 2.64Ϫ2.88 (m, 3 H, 1-H, 4-H), 3.28Ϫ3.41 (m, 2 H,
5-H), 3.80 (br, 1 H, amine), 4.55 (br, 1 H, amine). Ϫ 13C NMR
(100.6 MHz, [D6]acetone, DEPT): δ ϭ 24.9 (CH2, C-9), 25.2 (CH2,
C-8 or C-10), 25.5 (CH2, C-8 or C-10), 27.1 (CH2, C-7 or C-11),
27.4 (CH2, C-7 or C-11), 31.0 (CH2, C-3), 31.2 (CH2, C-2), 53.9
(CH, C-4), 55.5 (CH, C-5), 59.6 (CH, C-6), 62.2 (CH, C-1), 214.4
(Cq, COax), 216.6 (Cq, COax), 226.5 (Cq, COeq), 227.6 (Cq, COeq).
208.103159; found 208.102539 Ϫ [α]2D0 ϭ Ϫ108 (c ϭ 0.5, acetone).
Diazadiene(S,S,S,S)-16:
A 30% aqueous solution of glyoxal
(10.67 mL, 50.0 mmol) was added dropwise at 0 °C to a stirred
solution of (ϩ)-(4S,5S)-5-amino-2,2-dimethyl-4-phenyl-1,3-diox-
ane [(S,S)-15][53] (20.7 g, 100.0 mmol) in methanol (50 mL). After
complete addition the mixture was warmed to 20 °C and stirred at
this temperature for 2 h with formation of a beige suspension. The
precipitate was isolated by filtration and washed three times with
cold methanol (25 mL each) and then dried at 0.01 mbar. Partial
solvent evaporation from the mother liquor caused more product
to precipitate. Overall 21.45 g (49.4 mmol, 99%) of (S,S,S,S)-16 was
isolated as a colorless powder (m.p. 208 °C, dec.). Ϫ IR (CHCl3):
ν˜ ϭ 3064 cmϪ1 (w), 2996 (s), 2944 (m), 2872 (m), 1624 (m, imine),
1496 (w), 1452 (m), 1380 (s), 1268 (s), 1236 (s), 1196 (s), 1168 (s),
1124 (s), 1088 (s), 1056 (m, CϪO), 1028 (m, CϪO), 980 (m), 956
Ϫ MS (70 eV, 220 °C): m/z (%) ϭ 346 (2) [Mϩ], 262 (1) [Mϩ
Ϫ
3CO], 235 (14), 234 (40) [Mϩ Ϫ 4CO], 149 (15), 112 (24), 98 (6),
83 (11), 70 (100) [C4H8Nϩ]. Ϫ MS-FAB: m/z (%) ϭ 346 (35) [Mϩ],
290 (33) [Mϩ Ϫ 2CO], 262 (94) [Mϩ Ϫ 3CO], 234 (36) [Mϩ
Ϫ
4CO].
Ϫ HRMS (C15H22CrN2O4): calcd. 346.098467; found
346.098694. Ϫ C15H22CrN2O4 (346.34): calcd. C 52.02, H 6.40, N
8.09; found C 52.60, H 6.71, N 7.46. Ϫ [α]2D0 ϭ ϩ10 (c ϭ 0.1, acet-
one).
1
(m), 888 (m), 848 (s), 568 (m), 528 (m). Ϫ H NMR (400.1 MHz,
(S)-2-Butylaminomethyl)pyrrolidine: (S)-2-(Butylaminocarbonyl)-5-
oxopyrrolidine[51] (2.71 g, 14.73 mmol) in THF (35 mL) was added
dropwise over 5 h to a cold (0 °C) suspension of lithium aluminium
hydride (1.52 g, 40 mmol) in THF (40 mL). After complete addi-
tion the mixture was heated at reflux for 3 h. After cooling to 0
°C excess lithium aluminium hydride was carefully hydrolyzed by
addition of a saturated aqueous solution of sodium sulfate. The
mixture was extracted 12 times with diethyl ether (each 50 mL),
and the collected organic layers were dried over MgSO4. After fil-
CDCl3): δ ϭ 1.58 (s, 6 H, 6-H or 7-H), 1.60 (s, 6 H, 7-H or 6-H),
3
3
3
3.31 (ddd, J2-5 ϭ 2.1 Hz, J2-5 ϭ 2.8 Hz, J2-3 ϭ 2.4 Hz, 2 H, 2-
3
2
H), 3.78 (dd, J5-2 ϭ 2.1 Hz, J5-5 ϭ 12.1 Hz, 2 H, 5-H), 4.34 (dd,
3J5-2 ϭ 2.8 Hz, 2J5-5 ϭ 12.1 Hz, 2 H, 5-H), 5.23 (d, J3-2 ϭ 2.4 Hz,
3
2 H, 3-H), 7.08Ϫ7.22 (m, 10 H, 9-H, 10-H, 11-H, 12-H, 13-H),
7.45 (s, 2 H, 1-H). Ϫ 13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ
19.9 (CH3, C-6 or C-7), 29.8 (CH3, C-7 or C-6), 65.7 (CH2, C-5),
68.3 (CH, C-2), 74.2 (CH, C-3), 100.2 (Cq, C-4), 126.8 [CH, C-
10(12)], 127.9 (CH, C-11), 128.6 [CH, C-9(13)], 138.8 (Cq, C-8),
tration and solvent removal at reduced pressure the crude product 164.0 (CH, C-1). Ϫ MS (70 eV, 150 °C): m/z (%) ϭ 438 (1) [Mϩ
was purified by fractional distillation at 0.05 mbar to give 1.65 g
2], 437 (4) [Mϩ ϩ 1], 436 (11) [Mϩ], 421 (6) [Mϩ Ϫ CH3], 378 (2)
(10.58 mmol, 72%) of (S)-2-butylaminomethyl)pyrrolidine as a [Mϩ Ϫ (CH3)2CO], 348 (4) [Mϩ Ϫ (CH3)2COOCH2], 301 (19), 300
ϩ
clear, light- and air-sensitive liquid (b.p. 46 °C, 0.05 mbar). Ϫ IR
(96) [Mϩ Ϫ (CH3)2CO Ϫ C6H6], 299 (6), 273 (21), 272 (98) [Mϩ Ϫ
(cap. film): ν˜ ϭ 3296 cmϪ1 (br, m, amine), 2956 (s), 2928 (s), 2868 (CH3)2COOCH2 Ϫ C6H6], 183 (8), 136 (14), 134 (8), 133 (31), 130
(s), 2816 (m), 1600 (w), 1556 (m), 1456 (s), 1404 (s), 1372 (s), 1328 (9), 115 (8), 109 (18), 108 (100) [C6H5CH2OHϩ], 107 (77), 105 (43),
(s), 1132 (m), 812 (m). Ϫ 1H NMR (400.1 MHz, CDCl3): δ ϭ 0.91
103 (17), 95 (7), 91 (19) [C6H5CH2ϩ], 82 (19), 81 (15), 77 (25)
3
(t, J8-9 ϭ 7.2 Hz, 3 H, 9-H), 1.32Ϫ1.91 (m, 8 H, 2-H, 3-H, 7-H, [C6H5ϩ].
Ϫ
HRMS (C26H32N2O4): calcd. 436.236208; found
436.234406. Ϫ C26H32N2O4 (436.55): calcd. C 71.54, H 7.39, N
2.86Ϫ2.94 (m, 2 H, 5-H), 3.2 (m, 1 H, 1-H). Ϫ 13C NMR 6.42; found C 71.45, H 7.34, N 6.37. Ϫ [α]2D0 ϭ ϩ112.6 (c ϭ 1, acet-
8-H), 1.55 (br, 2 H, amine), 2.50Ϫ2.61 (m, 4 H, 4-H, 6-H),
(100.6 MHz, CDCl3, APT): δ ϭ 14.6 (Ϫ, C-9), 21.1 (ϩ, C-8), 26.3
(ϩ, C-2 or C-3 or C-7), 30.4 (ϩ, C-2 or C-3 or C-7), 32.9 (ϩ, C-2
or C-3 or C-7), 47.13 (ϩ, C-6), 50.6 (ϩ, C-4), 56.1 (ϩ, C-5), 59.0
(Ϫ, C-1). Ϫ MS (70 eV, 20 °C): m/z (%) ϭ 157 (3) [Mϩ ϩ 1], 156
(3) [Mϩ], 113 (8), 88 (9), 87 (9), 86 (89), 85 (15), 84 (15), 71 (40),
70 (100) [C4H8Nϩ]. Ϫ HRMS (C9H20N2): calcd. 156.162649; found
156.162354. Ϫ [α]2D0 ϭ ϩ124.7 (c ϭ 0.43, acetone).
one).
Diamine (S,S,S,S)-17: All operations were performed under argon
in the dark. Sodium tetrahydridoborate (0.44 g, 12.0 mmol) was
added to a stirred solution of (S,S,S,S)-16 (2.18 g, 5.0 mmol) in
anhydrous methanol (25 mL) at Ϫ8 °C. After complete addition
the mixture was heated at 50 °C for 3 h. The solvent was then
removed at reduced pressure, and the residue was taken up with
water (50 mL). The aqueous layer was extracted four times with
TBME (each 50 mL), the collected organic layers were dried over
[((S)-2-Butylaminomethyl)pyrrolidine]tetracarbonylchromium(0)
[(S)-14]: Procedure 5; (S)-2-butylaminomethyl)pyrrolidine (0.73 g,
4.68 mmol) and 6 (1.118 g, 4.61 mmol) in THF (50 mL) were sodium sulfate, and after filtration the solvent was removed at re-
heated at reflux for 60 min. Column chromatography (SiO2, diethyl
ether/petroleum ether 1:2 Ǟ 1:0, length 35 cm, ø 3.5 cm) and solv-
duced pressure to give 2.2 g (5.0 mmol, 100%) of (S,S,S,S)-17 as a
colorless oil. Ϫ IR (CHCl3): ν˜ ϭ 3312 cmϪ1 (w, amine), 3064 (w),
ent removal gave 1.40 g (4.38 mmol, 95%) of (S)-14, yellow solid 2996 (s), 2940 (m), 2868 (m), 1496 (m), 1448 (m), 1380 (s), 1264
(m.p. 113 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3412 cmϪ1 (m, amine), 3304
(m), 1232 (s), 1196 (s), 1168 (m), 1148 (m), 1072 (s), 1028 (m), 984
(m, amine), 2956 (m), 2928 (m), 2872 (m), 2000 (s, CO), 1916 (s, (m), 844 (s). Ϫ H NMR (400.1 MHz, CDCl3): δ ϭ 1.49 (s, 6 H,
CO), 1868 (s, CO), 1836 (s, CO), 1804 (s, CO), 1772 (s, CO), 1616 6-H or 7-H), 1.51 (s, 6 H, 7-H or 6-H), 1.93 (m, 2 H, 1-H), 2.0 (s,
1
(w), 1456 (m), 1376 (w), 1124 (w), 1076 (w), 1032 (w), 916 (w), 656 br, 2 H, amine), 2.35 (m, 2 H, 1-H), 2.52 (m, 2 H, 2-H), 3.81 (dd,
1
(m), 636 (m). Ϫ H NMR (400.1 MHz, [D6]acetone): δ ϭ 0.92 (t,
3J5-2 ϭ 2.0 Hz, 2J5-5 ϭ 12.0 Hz, 2 H, 5-H), 3.99 (dd, 3J5-2 ϭ 2.0 Hz,
3J8-9 ϭ 7.2 Hz, 3 H, 9-H), 1.19Ϫ2.10 (m, 9 H), 2.62Ϫ3.13 (m, 4 2J5-5 ϭ 12.0 Hz, 2 H, 5-H), 5.04 (d, J3-2 ϭ 2.0 Hz, 2 H, 3-H),
3
H), 3.24Ϫ3.41 (m, 2 H), 3.87 (br, 1 H, amine), 4.48 (br, 1 H, amine).
7.22Ϫ7.36 (m, 10 H, 9-H, 10-H, 11-H, 12-H, 13-H). Ϫ 13C NMR
(100.6 MHz, CDCl3, DEPT): δ ϭ 18.8 (CH3, C-6 or C-7), 29.6
Ϫ
13C NMR (100.6 MHz, [D6]acetone, APT): δ ϭ 12.9 (Ϫ, C-9),
19.5 (ϩ, C-8), 26.65 (ϩ, C-2 or C-3 or C-7), 26.66 (ϩ, C-2 or C-3 (CH3, C-7 or C-6), 47.5 (CH2, C-1), 55.2 (CH, C-2), 63.6 (CH2, C-
or C-7), 30.3 (ϩ, C-2 or C-3 or C-7), 54.9 (ϩ, C-6), 55.1 (ϩ, C-4),
5), 73.4 (CH, C-3), 99.1 (Cq, C-4), 125.9 (CH, C-11), 127.1 [CH,
2281
Eur. J. Org. Chem. 2000, 2273Ϫ2284

M. Strotmann, H. Butenschön
FULL PAPER
C-10(12)], 128.0 [CH, C-9(13)], 139.7 (Cq, C-8). Ϫ MS (70 eV, 100 [(R)-2,2Ј-Diamino-1,1Јbinaphthyl]tetracarbonylchromium [(R)-21]:
°C): m/z (%) ϭ 440 (3) [Mϩ], 425 (29) [Mϩ Ϫ CH3], 382 (3) [Mϩ
Procedure 5; (R)-2,2Ј-diamino-1,1Јbinaphthyl [(R)-DABN, Aldrich]
Ϫ (CH3)2CO], 367 (4), 293 (31), 277 (29), 261 (7), 233 (16), 220 (750 mg, 2.64 mmol) and compound 6 (650 mg, 2.5 mmol) were
(100), 208 (11), 176 (8), 162 (37), 144 (21), 132 (74), 117 (26), 108 heated at reflux for 2 h. Column chromatography (SiO2, TBME/
(13) [C6H5CH2OHϩ], 97 (64), 91 (30) [C6H5CH2ϩ], 84 (25), 77 (12)
petroleum ether 1:5 Ǟ 1:2, length 30 cm, ø 3.5 cm) and solvent
[C6H5ϩ], 69 (33). Ϫ HRMS (C26H36N2O4): calcd. 440.267508; removal gave 79 mg (1.77 mmol, 70%) of (R)-21, yellow, very air-
found 440.263519. Ϫ [α]2D0 ϭ ϩ70.8 (c ϭ 0.6, THF).
sensitive solid (m.p. 83 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3380 cmϪ1 (s,
br, amine), 3052 (m), 2960 (m), 2064 (w), 1980 (m, CO), 1932 (s,
CO), 1888 (s, CO), 1820 (m, CO), 1620 (s), 1508 (m), 1472 (w),
1432 (w), 1380 (m), 1348 (w), 1096 (m), 1024 (m), 816 (s). Ϫ 1H
NMR (400.1 MHz, [D6]benzene): δ ϭ 3.07 (s, br, 4 H, amine),
6.67Ϫ7.72 (m, 12 H, 3-H, 4-H, 6-H, 7-H, 8-H, 9-H). Ϫ 13C NMR
(100.6 MHz, [D6]benzene, APT): δ ϭ 113.3 (ϩ, C-5) 119.1 (Ϫ, C-
3), 123.3 (Ϫ, C-4 or C-6 or C-7 or C-8 or C-9), 125.3 (Ϫ, C-4 or
C-6 or C-7 or C-8 or C-9), 127.9 (Ϫ, C-4 or C-6 or C-7 or C-8 or
C-9), 129.2 (Ϫ, C-4 or C-6 or C-7 or C-8 or C-9), 129.6 (ϩ, C-1
or C-10), 130.2 (Ϫ, C-4 or C-6 or C-7 or C-8 or C-9), 135.2 (ϩ,
C-1 or C-10), 144.0 (ϩ, C-2), 217.0 (ϩ, COax), 233.5 (ϩ, COeq). Ϫ
MS-FAB: m/z (%) ϭ 448 (10) [Mϩ], 420 (9) [Mϩ Ϫ CO], 364 (22)
[Mϩ Ϫ 3CO], 336 (59) [Mϩ Ϫ 4CO], 284 (100) [Mϩ Ϫ 4CO Ϫ Cr].
Ϫ [α]2D0 ϭ ϩ97.4 (c ϭ 1, THF).
Diamine Complex (S,S,S,S)-18: Procedure 5; compound (S,S,S,S)-
17 (200 mg, 0.45 mmol) and 6 (110 mg, 0.43 mmol) in THF
(50 mL) were heated at reflux for 45 min. Column chromatography
(SiO2, TBME /petroleum ether 1:3 Ǟ 1:1, length 35 cm, ø 2.5 cm)
and solvent removal gave 198 mg (0.33 mmol, 76%) of (S,S,S,S)-18
as a yellow, air-sensitive solid (m.p. 103 °C, dec.). Ϫ IR (KBr): ν˜ ϭ
3264 cmϪ1 (m, amine), 3006 (w), 2992 (m), 2944 (m), 2876 (w),
2004 (s, CO), 1864 (s, CO), 1824 (s, CO), 1496 (w), 1472 (m), 1448
(m), 1244 (m), 1204 (s), 1096 (m), 952 (m), 856 (m), 740 (m), 700
1
(m). Ϫ H NMR (400.1 MHz, [D6]acetone): δ ϭ 1.41 (s, 6 H, 6-H
or 7-H), 1.57 (s, 6 H, 7-H or 6-H), 3.0 (s, br, 2 H, amine), 3.15 (m,
2
2 H, 1-H), 3.28 (m, 2 H, 1-H), 3.29 (m, 2 H, 2-H), 4.20 (d, J5-5
ϭ
3
2
13.4 Hz, 2 H, 5-H), 4.46 (dd, J5-2 ϭ 2.1 Hz, J5-5 ϭ 13.4 Hz, 2 H,
5-H), 5.49 (d, 3J3-2 ϭ 2.7 Hz, 2 H, 3-H), 7.42Ϫ7.50 (m, 10 H, 9-H,
10-H, 11-H, 12-H, 13-H). Ϫ 13C NMR (100.6 MHz, [D6]acetone,
APT): δ ϭ 17.9 (Ϫ, C-6 or C-7), 26.3 (Ϫ, C-7 or C-6), 49.7 (ϩ, C-
1), 56.6 (Ϫ, C-2), 59.1 (ϩ, C-5), 73.2 (Ϫ, C-3), 98.9 (ϩ, C-4), 124.9
[Ϫ, C-10(12)], 128.0 (Ϫ, C-11), 129.2 [Ϫ, C-9(13)], 137.7 (ϩ, C-8),
214.5 (ϩ, COax), 225.6 (ϩ, COeq). Ϫ MS (70 eV, 140 °C): m/z (%) ϭ
493 (7) [Mϩ Ϫ 4CO ϩ 1], 492 (16) [Mϩ Ϫ 4CO], 426 (10), 425
(25), 382 (4), 367 (6), 337 (5), 293 (28), 277 (34), 261 (8), 233 (16),
220 (100), 208 (9), 176 (6), 163 (32), 144 (15), 132 (58), 117 (16),
97 (43), 91 (22) [C6H5CH2ϩ], 84 (20), 77 (10) [C6H5ϩ], 69 (17), 52
(6) [52Cr]. Ϫ MS-FAB: m/z (%) ϭ 492 (94) [Mϩ Ϫ 4CO]. Ϫ HRMS
Tetracarbonyl[L-methionine methyl ester]chromium(0) [(R)-22]: Tri-
ethylamine (1.9 mL, 13.5 mmol) was added to hexacarbonylchrom-
ium(0) (700 mg, 3.18 mmol) and -methionine methyl ester hydro-
chloride (450 mg, 2.25 mmol) in THF (50 mL). The mixture was
heated at reflux for 40 h, the color changing from colorless to yel-
low and then orange. Column chromatography (SiO2, diethyl ether/
petroleum ether 1:2 Ǟ 1:0, length 30 cm, ø 3.5 cm) and solvent
removal gave 362 mg (1.10 mmol, 49%) of (R)-22 as an orange,
crystalline solid (m.p. 141 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3348 cmϪ1
(m, amine), 3288 (m, amine), 2956 (w), 2920 (w), 2068 (w), 2008
(s, CO), 1872 (s, CO), 1832 (s, CO), 1724 (s, ester), 1652 (m), 1608
(m), 1256 (m), 1229 (m), 1084 (m), 1032 (m), 584 (m), 456 (m). Ϫ
1H NMR (200.1 MHz, [D6]acetone): δ ϭ 2.44 (s, 3 H, 4-H),
2.66Ϫ2.85 (m, 4 H, 2-H, 3-H), 3.12Ϫ3.46 (m, 3 H, 1-H, amine),
3.64 (s, 3 H, 6-H). Ϫ 13C NMR (100.6 MHz, [D6]acetone, DEPT):
δ ϭ 22.4 (CH3, C-4), 27.7 (CH2, C-3), 36.3 (CH2, C-2), 51.5 (CH3,
C-6), 59.2 (CH, C-1), 173.0 (Cq, C-5), 215.3 (Cq, COax), 215.9 (Cq,
COax), 224.6 (Cq, COeq), 225.1 (Cq, COeq). Ϫ MS (70 eV, 160 °C):
m/z (%) ϭ 327 (1) [Mϩ], 326 (4) [Mϩ Ϫ 1], 298 (2) [Mϩ Ϫ 1 Ϫ
(C26H36N2O4Cr): calcd. 492.208018; found 492.206757.
Ϫ
C30H36CrN2O8 (604.62): calcd. C 59.60, H 6.00, N 4.63; found C
57.86, H 6.11, N 4.49. Ϫ [α]2D0 ϭ ϩ91.6 (c ϭ 0.225, acetone).
Tetracarbonyl{(R)-1-[5-chloro-2-(methylamino)phenyl]-1,2,3,4-
tetrahydroisoquinoline}chromium(0) (R)-20: Procedure 5; (R)-1-[5-
chloro-2-(methylamino)phenyl]-1,2,3,4-tetrahydroisoquinoline tart-
rate [(R)-19, Aldrich] (348 mg, 1.0 mmol), compound 6 (230 mg,
0.9 mmol), and triethylamine (2 mL, 1.45 g, 14.0 mmol) in THF
(50 mL) were heated at reflux for 2 h. Column chromatography
(SiO2, TBME/petroleum ether 1:1 Ǟ 1:0, length 40 cm, ø 2.5 cm)
and solvent removal gave 263 mg (0.6 mmol, 67%) of (R)-20 as an
orange, air-sensitive solid (m.p. 85 °C, dec.). Ϫ IR (KBr): ν˜ ϭ 3298
cmϪ1 (w, amine), 3260 (w, amine), 3004 (w), 2976 (w), 2928 (w),
2012 (m, CO), 1980 (m, CO), 1896 (s, CO), 1872 (s, CO), 1828 (s,
CO), 1488 (m), 1228 (m), 1076 (w), 896 (w). Ϫ 1H NMR
(400.1 MHz, [D6]acetone): δ ϭ 2.45Ϫ3.29 (m, 9 H, 2-H, 3-H, 16-
H, amine), 5.15 (s, br, 1 H, 1-H), 6.38Ϫ7.42 (m, 7 H, 5-H, 6-H, 7-
H, 8-H, 11-H, 13-H, 14-H). Ϫ 13C NMR (100.6 MHz, [D6]acetone,
APT): δ ϭ 27.8 (ϩ, C-3), 40.0 (Ϫ, C-16), 46.8 (ϩ, C-2), 54.2 (Ϫ,
C-1), 114.9 (Ϫ, C-14), 125.8 (Ϫ, C-5 or C-6 or C-7 or C-8 or C-11
CO], 243 (5) [Mϩ Ϫ 3CO], 221 (16), 220 (33), 215 (21) [Mϩ
Ϫ
4CO], 192 (11), 164 (13) [Cr(CO4)ϩ], 163 (38) [Mϩ Ϫ Cr Ϫ 4CO],
146 (20), 132 (10) [Mϩ Ϫ Cr Ϫ 4CO Ϫ OCH3], 131 (36), 115 (41),
108 (37) [Cr(CO2)ϩ], 103 (55) [Mϩ Ϫ Cr Ϫ 4CO Ϫ CO2CH3 Ϫ H],
80 (51) [CrCOϩ], 61 (100) [CH3SCH2ϩ], 52 (57) [52Crϩ]. Ϫ MS-
FAB: m/z (%) ϭ 327 (24) [Mϩ], 311 (13) [Mϩ Ϫ NH2], 299 (14)
[Mϩ Ϫ CO], 271 (2) [Mϩ Ϫ 2CO], 243 (41) [Mϩ Ϫ 3CO], 215 (14)
[Mϩ Ϫ 4CO]. Ϫ HRMS (C10H13CrNO6S): calcd. 326.986869;
found 326.986542. Ϫ C10H13CrNO6S (326.99): calcd. C 36.70, H
4.00; found C 36.44, H 4.05. Ϫ [α]2D0 ϭ Ϫ5.4 (c ϭ 0.5, acetone).
or C-13), 127.0 (ϩ, C-4 or C-9 or C-10 or C-12), 127.5 (Ϫ, C-5 or Procedure for the Complexation of Arenes with Chelating Diamine
C-6 or C-7 or C-8 or C-11 or C-13), 127.7 (Ϫ, C-5 or C-6 or C-7
or C-8 or C-11 or C-13), 128.9 (Ϫ, C-5 or C-6 or C-7 or C-8 or C-
11 or C-13), 129.3 (Ϫ, C-5 or C-6 or C-7 or C-8 or C-11 or C-13),
Tetracarbonylchromium(0) Complexes: The diamine tetracar-
bonylchromium(0) chelate complex (1 equiv.) and the arene (2
equiv.) were suspended or dissolved in the solvent (see Table 1) and
129.9 (Ϫ, C-5 or C-6 or C-7 or C-8 or C-11 or C-13), 133.26 (ϩ, stirred in the dark. Boron trifluorideϪdiethyl ether adduct (8
C-4 or C-9 or C-10 or C-12), 133.28 (ϩ, C-4 or C-9 or C-10 or C- equiv.) was added dropwise, and the mixture was heated at the tem-
12), 135.0 (ϩ, C-4 or C-9 or C-10 or C-12), 213.0 (ϩ, COax), 213.6 perature given in Table 1 until no more diamine tetracarbonylchro-
(ϩ, COax), 226.0 (ϩ, COeq), 226.7 (ϩ, COeq). Ϫ MS-FAB: mium(0) complex could be detected by TLC (12Ϫ24 h). The reac-
m/z (%) ϭ 438 (19) [Mϩ], 410 (11) [Mϩ Ϫ CO], 354 (100) [Mϩ
Ϫ
tion progress was indicated by a color change from orange-red to
yellow. The mixture was cooled to 0 °C, and excess boron
3CO], 326 (62) [Mϩ Ϫ 4CO], 274 (40) [Mϩ Ϫ 4CO Ϫ 52Cr]. Ϫ
C20H17ClCrN2O4 (436.81): calcd. C 54.99, H 3.92, N 6.41; found trifluorideϪdiethyl ether adduct was hydrolyzed with water. After
C 55.26, H 4.49, N 6.10. Ϫ [α]2D0 ϭ Ϫ152.0 (c ϭ 0.1, acetone).
extraction of the aqueous layer with diethyl ether the collected or-
2282
Eur. J. Org. Chem. 2000, 2273Ϫ2284

Preparation of Chiral Amine Carbonyl Chromium(0) Complexes
FULL PAPER
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fied by column chromatography, and de was determined by NMR
spectroscopy. Results are summarized in Table 1.
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Procedure for the Complexation of Arenes with Tetracarbonyl(L-me-
thionine methyl ester)chromium(0) [(S)-22]: A suspension of (S)-22
(1 equiv.) and the arene (2 equiv.) in the appropriate solvent (see
Table 1) was stirred in the dark. Boron trifluorideϪdiethyl ether
adduct (6 equiv.) was added dropwise, and the mixture was heated
at the temperature given in Table 1, until no more (S)-22 was de-
tected by TLC (10Ϫ20 h). The mixture was then cooled to 0 °C,
and the excess boron trifluorideϪdiethyl ether adduct was hy-
drolyzed with water. After extraction of the aqueous layer with
diethyl ether the collected organic layers were dried over MgSO4.
The crude product was purified by column chromatography, and
de determined by NMR spectroscopy. Results are summarized in
Table 1.
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Acknowledgments
This work was kindly supported by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie. We thank
Professor Dr. V. N. Kalinin, Moscow, for helpful discussions and
for hospitality during a visit by M. S. We thank Boehringer
Mannheim GmbH, Chemetall GmbH, Degussa-Hüls AG, Haar-
mann & Reimer GmbH, Merck KGaA, Phenolchemie GmbH and
Wacker Chemie GmbH for donations of chemicals and solvents.
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