Highly regio- and diastereoselective chromium(0)-catalysed cyclopropanation of 1-alkoxy-1,3-dienes with diazo compounds

Article abstract of DOI:10.1002/ejoc.200300687

Pentacarbonyl(η²-cis-cyclooctene)chromium(0) (1) is an efficient catalyst for diazo decomposition and selective [2+1]-cycloaddition reactions of the resulting carbene intermediates with electron-rich dienes. The cyclopropanation of 1-alkoxy-1,3

Full text of DOI:10.1002/ejoc.200300687

FULL PAPER
Highly Regio- and Diastereoselective Chromium(0)-Catalysed
Cyclopropanation of 1-Alkoxy-1,3-dienes with Diazo Compounds[
‡]
[a]
[b]
[a]
Norbert D. Hahn, Martin Nieger, and Karl Heinz Dötz*
Keywords: Cyclopropanation / Vinylcyclopropanes / Chromium / Catalysis / Carbenes / Diazo compounds
2
Pentacarbonyl(η -cis-cyclooctene)chromium(0) (1) is an effi-
the less substituted C=C bond. The pentacarbonylchromium-
cient catalyst for diazo decomposition and selective [2+1]-
catalysed cyclopropanation with ethyl α-diazophenylacetate
cycloaddition reactions of the resulting carbene interme- (3) gives the corresponding vinylcyclopropanecarboxylates
diates with electron-rich dienes. The cyclopropanation of 1-
alkoxy-1,3-butadienes 4−8 with 9-diazo-9H-fluorene (2)
yields vinylspirocyclopropanes 9−13 in good to excellent
yields, as single regioisomers arising from carbene transfer to
16−20 in very good yields and with exceptionally high trans
stereoselectivities (Ͼ 95%).
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Since the early research results of Loose[1] and Wolff,[2]
who observed that the decomposition temperatures of diazo
ketones and diazoacetic esters were significantly lowered by
the presence of copper powder, cupric sulfate or silver salts,
the catalytic decomposition of diazo compounds to form
reactive carbenes has become a standard method in organic
synthesis. For example, it is used in CH insertions, OH in-
sertions, the cyclopropanation of olefins and the Buchner
[
3]
reaction. In particular, the opportunity to synthesise
cyclopropanes by the reaction of diazo compounds with al- Figure 1. Proposed mechanism for the metal-catalysed cyclopro-
panation of olefins with diazo compounds[
9b]
kenes, catalysed by copper, rhodium, platinum or ru-
thenium complexes, has become a powerful tool for the
stereoselective construction of three-membered ring sys-
tems. The mechanisms of these reactions are assumed to
proceed via metalϪcarbene complex intermediates of type
A (Figure 1).
arrangement of the resulting vinylcyclopropanes.[7] This ap-
proach has been used in the elegant synthesis of several
fused cyclopentanoid terpenes, such as retigeranic acid.[
One important method to generate vinylcyclopropanes in a
selective fashion is the [2ϩ1]-cycloaddition reaction of di-
azo compounds and dienes, catalysed by metal complexes
(Figure 2).
[
4]
8]
Cyclopropanes have proved to be very useful building
blocks in synthetic chemistry.[5] In particular, vinylcyclopro-
panes represent a structural key feature in a wide range of
bioactive natural and non-natural molecules,[ and have
therefore been the focus of recent research. Vinylcyclopro-
panes are important intermediates, as shown, for example,
in the [4ϩ1]-annulation strategy, based on an intra-/inter-
molecular cyclopropanation of dienes followed by re-
6]
[
‡]
a]
[25]
Reactions of Complex Ligands, 97. Part 96: Ref.
[
Kekul e´ -Institut für Organische Chemie und Biochemie der
Rheinischen Friedrich-Wilhelms-Universität,
Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany
Fax: (internat.) ϩ 9-(0)228-735813
Figure 2. Metal complex catalysed [2ϩ1]-cycloaddition reaction of
diazo compounds with dienes
E-mail: doetz@uni-bonn.de
[
b]
Institut für Anorganische Chemie der Rheinischen Friedrich-
Wilhelms-Universität,
Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany
The reaction of electron-rich olefins with 9-diazo-9H-flu-
orene (2) catalysed by the pentacarbonylchromium(0) frag-
Eur. J. Org. Chem. 2004, 1049Ϫ1056
DOI: 10.1002/ejoc.200300687
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1049

N. D. Hahn, M. Nieger, K. H. Dötz
FULL PAPER
ment, and a proposed mechanism, have been described pre-
The less electron-rich aryl-substituted 1,3-butadienes (e.g.
viously by our group.[ We now present the first chromium 1-phenyl-1,3-butadiene and 1,4-diphenyl-1,3-butadiene)
complex catalysed reaction of 1-alkoxy-1,3-butadiene with and 1-acetoxy-1,3-butadiene did not produce the desired
diazo compounds to generate vinylcyclopropanes in an ef- cyclopropanation products under these conditions. 9,9Ј-Bi-
9]
[
12]
ficient, direct and stereoselective way.
fluorenylidene (14)
and bis(9,9Ј-9H-fluorenylidene)azine
[
13]
(
15)
were identified as side products in all of the cyclo-
propanation reactions, even though 9-diazo-9H-fluorene (2)
was added slowly over the course of the reaction.
The cyclopropanation of 1-alkoxy-1,3-butadienes pro-
Results and Discussion
Cyclopropanations with 9-Diazo-9H-fluorene (2)
The present study aims to extend the scope of the chro- ceeded regioselectively, to yield the vinylcyclopropanes
mium-catalysed cyclopropanation reaction from olefins to 9Ϫ13 as single regioisomers. The products were identified
electron-rich dienes. The dienes 4Ϫ6, which differ in their by the chemical shifts and the coupling constants of 2-H
1
steric and electronic properties, were used to study the re- and 3-H in the H NMR spectra (Table 2), and the chemical
gioselectivity of the reaction. Of further interest was the shift of the signal of the quaternary C-1 atom. Neither GC-
extent to which a bulky chiral auxiliary like (Ϫ)-menthol or MS analysis nor NMR spectroscopic analysis of the crude
(
1R)-1-phenylethanol (used in 7 and 8) affects the regiose- reaction mixture indicated the formation of additional re-
lectivity, and also the diastereoselectivity, of the reaction.
gioisomers. The incorporation of chiral auxiliaries, such as
[
14]
(Ϫ)-menthol or (1R)-phenylethanol,
into the diene did
not result in any detectable diastereoselectivity in the for-
mation of 12 or 13. The chiral centres in these alkoxy sub-
stituents were probably too far away from the less substi-
tuted diene terminus, i.e. that involved in the carbene trans-
fer in the transition state, to influence the course of the re-
action.
The structure of (2R)-12 was independently established
by X-ray analysis, thus confirming that the regioselective
cyclopropanation occurs across the 3-positions of the diene.
Scheme 1. 1-Alkoxy-1,3-butadienes 4Ϫ8 applied to cyclopropan-
ation
A solution of 9-diazo-9H-fluorene (2)[10] in dichloro-
methane was added at room temp. over a period of 8 h to
X-ray Crystal Structure of Spiro-Vinylcyclopropane (2R)-12
Crystals of (2R)-12 suitable for X-ray analysis were
a solution of 1-alkoxy-1,3-butadiene (molar ratio 2/diene ϭ
2
1
:1) and 2 mol % pentacarbonyl(η -cis-cyclooctene)chrom- grown from a dilute solution of 12 in acetone at room temp.
[
11]
ium(0) (1) in dichloromethane, and the reaction mixture by slow evaporation of the solvent (Figure 3, Table 4). The
was stirred for a further 8 h. The spiro-vinylcyclopropanes assignment of the (R) configuration to the newly formed
9Ϫ13 were obtained in 51Ϫ97% yield after chromato- stereogenic centre was based on the stereochemical infor-
graphic work-up (Scheme 2, Table 1).
mation from the (Ϫ)-menthyl group. The C3ϪC5 bond
˚
[
[
1.552(2) A] is significantly longer than the C3ϪC4
1.492(2) A] and C4ϪC5 [1.518(3) A] bonds. This remark-
˚
˚
able fact is consistent with the features previously reported
[
15]
for the vinylspiro[2.4]heptane skeleton,
and may result
from the influence of the spiro centre C-5 atom and the
vinyl substituent.
Cyclopropanations with Ethyl α-Diazophenylacetate (3)
The cyclopropanation reactions of 1-alkoxy-1,3-buta-
dienes with 9-diazo-9H-fluorene (2) afford the products as
single regioisomers. These results have been extended to the
Scheme 2. Synthesis of spiro-vinylcyclopropanes 9Ϫ13
pentacarbonylchromium-catalysed
with ethyl α-diazophenylacetate (3).
[2ϩ1]-cycloaddition
[
16]
We wondered
Table 1. Cyclopropanation of 1-alkoxy-1,3-dienes with 9-diazo-9H-
fluorene (2) catalysed by chromium complex 1
whether this type of carbene-transfer reagent would give a
significant trans selectivity in the cyclopropanation reac-
tion. Earlier reports on cyclopropanations of electron-rich
alkenes with ethyl diazoacetate (EDA) describe only moder-
Vinylcyclopropane
R
R1
Yield [%] de [%]
[
17]
ate trans selectivities.
Even the cyclopropanation of 1-
9
Me
Et
H
Me
Ϫ
Me
Me
97
62
51
83
76
10
11
12
13
alkoxy-1,3-dienes with ethyl α-diazoacetate only gave poor
ϪCH
(Ϫ)-menthyl
(1R)-Ph(Me)CH
2
ϪCH
2
ϪCH
2
[18]
selectivity. In order to increase the diastereoselectivity, a
0
0
bulky substituent, such as phenyl, was introduced at the α-
position of ethyl α-diazoacetate. This resulted in a remark-
1050
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Eur. J. Org. Chem. 2004, 1049Ϫ1056

Chromium(0)-Catalysed Cyclopropanation of 1-Alkoxy-1,3-dienes with Diazo Compounds
FULL PAPER
Table 2. Selected NMR spectroscopic data of spiro-vinylcyclopropanes 9Ϫ13
Vinylcyclopropane
C-1[a]
δ in ppm)
2-H
3-H 3
(
(δ in ppm)
(3JH,H in Hz)
(δ in ppm)
( JH,H in Hz)
cis
trans
cis
trans
[
[
[
[
[
[
[
b]
b]
c]
c]
c]
b]
b]
9
0
1
2
2
3
3
35.1
33.6
33.9
34.7
34.5
33.6
33.6
2.56
2.70
2.30
2.56
2.56
2.64
2.62
8.9/7.6
9.2/7.1
9.2/7.5
9.5/8.0
9.5/8.0
9.6/8.5
10.6/8.2
1.85
2.10
1.66
1.90
1.87
1.98
1.84
2.11
2.10
1.73
1.83
1.84
2.02
2.00
7.6
7.1
7.5
8.0
8.0
8.5
8.2
8.9
9.2
9.2
9.5
9.5
9.6
10.6
1
1
1
1
1
1
(2R)
(2S)
(diastereomer I)
(diastereomer II)
[
a]
Quaternary carbon atom. [b] Recorded in CDCl . [c] Recorded in C
D .
3 6 6
Figure 3. Molecular structure of (Ϫ)-menthyl-derived vinylcyclopropane (2R)-12; the numbering of atoms does not correspond to the
numbering used in the NMR spectra
able increase in the trans selectivity. Furthermore, a prefer- (3) in dichloromethane was added at 5 °C over a period of
ential attack at the unsubstituted position of electron-rich 4 h to a solution of 1-alkoxy-1,3-butadiene (molar ratio 3/
2
1
,3-butadienes has been observed for diazoacetates in the diene ϭ 1:2) and 5 mol % pentacarbonyl(η -cis-cyclooc-
[
2ϩ1]-cycloaddition catalysed by rhodium, copper or pal- tene)chromium(0) (1) in dichloromethane. The resulting
[
19]
ladium.
Davies et. al. conducted several studies to syn- mixture was stirred for a further 8 h. Only the trans-vinyl-
thesise vinylcyclopropanes, and described another very cyclopropanes 16Ϫ20 were isolated, in 57Ϫ78% yield after
interesting procedure, in which the vinyl functionality chromatographic work-up (Scheme 3, Table 3).
within the diazo component was introduced diastereoselec-
In these reactions, the previously observed dimer or azine
tively and even enantioselectively. However, the synthesis side products could not be detected by GC-MS, TLC, or
of the starting materials for this procedure requires more NMR spectroscopy of the crude reaction mixture. Thus,
[
20]
steps. Our experiments have led us to a further improve- unchanged starting material was conveniently recovered.
ment in the synthesis of vinylcyclopropanes. We are now Obviously, the catalyst precursor 1 suffers from partial
able to present a highly regio- and diastereoselective route deactivation during the cyclopropanation reaction; how-
to these compounds from easily available electron-rich di- ever, the reaction can be driven to completion upon ad-
enes: only the 3-position of the conjugated dienes was at- dition of further amounts of the chromium catalyst precur-
tacked, and this occurred with an extremely high trans sel- sor 1. Attempts to induce chirality using alkoxy auxiliaries
ectivity (Ͼ 95%). A solution of ethyl α-diazophenylacetate in the diene were unsuccessful.
Eur. J. Org. Chem. 2004, 1049Ϫ1056
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1051

N. D. Hahn, M. Nieger, K. H. Dötz
FULL PAPER
tion temperature 70 °C, heating rate 20 °C/min to 250 °C, hold for
1
min, then 50 °C/min to 280 °C, this was held for 10 min. TLC
was carried out on Merck pre-coated silica gel sheets, 60F254
.
Starting Materials: Liquid starting compounds were degassed un-
2
der vacuum and saturated with argon. Pentacarbonyl(η -cis-cyclo-
[
11]
[10]
octene)chromium(0) (1),
9-diazo-9H-fluorene (2),
ethyl α-di-
16]
azophenylacetate
(3),[
(E)-1-ethoxy-2-methyl-1,3-butadiene
(E)-2-methyl-1-(Ϫ)-
(1E,1ЈR/S)-2-methyl-1-(1Ј-phenyl-
5),[ 5-ethenyl-3,4-dihydro-2H-pyran (6)
21]
[22]
(
[14]
menthoxy-1,3-butadiene (7),
ethoxy)-1,3-butadiene (8),[ were prepared according to literature
procedures. All other chemicals were used as received from com-
mercial sources.
14]
Scheme 3. Synthesis of trans-vinylcyclopropanes 16Ϫ20
General Procedure for the Chromium Complex Catalysed Reactions
of 9-Diazo-9HϪfluorene (2) with 1-Alkoxy-1,3-butadienes: A solu-
2 2
tion of 9-diazo-9H-fluorene (2) in CH Cl (30 mL) was added over
a period of 8 h at room temp. to a stirred solution containing an
equimolar amount of the corresponding 1-alkoxy-1,3-butadiene
Table 3. [2ϩ1]-Cycloaddition of 1-alkoxy-1,3-dienes with ethyl α-
diazophenylacetate (3) catalysed by chromium complex 1
R1 Yield [%] trans [%] de [%]
and 2 mol % of chromium(0) complex 1 in CH
2 2
Cl (10 mL). Evol-
Vinylcyclopropane R
ution of N was accompanied by a colour change of the reaction
2
mixture, from yellow to violet. After stirring for a further 8 h fol-
lowed by removal of the solvent under reduced pressure, work-up
was performed by column chromatography.
16
17
18
19
20
Me
Et
ϪCH
(Ϫ)-menthyl
H
78
Me 57
ϪCH Ϫ 64
Me 67
(1R)-Ph(Me)CH Me 59
Ͼ 95
Ͼ 95
Ͼ 95
Ͼ 95
Ͼ 95
2
ϪCH
2
2
0
0
2-[(E)-2ЈЈ-Methoxyvinyl]spiro[cyclopropane-1,9Ј[9ЈH]-fluorene] (9):
Reaction of 2 (0.57 g, 3 mmol) with 4 (0.25 g, 3 mmol) in the pres-
ence of 1 (0.02 g, 0.06 mmol, 2 mol %) gave 9 (0.72 g, 97%) after
work-up (eluent: petroleum ether/CH
2
Cl
2 f
, 2:1, R ϭ 0.43) as a
The vinylcyclopropanes were identified by H and 13C colourless oil. GC-MS: t
1
ϭ 9.48 min. H NMR (500 MHz,
1
R
2
3
NMR spectroscopy. The trans selectivity was confirmed by CDCl
3
): δ ϭ 1.85 (dd, JH,H ϭ 5.2, JH,H ϭ 7.6 Hz, 1 H, H-3cis),
2
.11 (dd, 2JH,H ϭ 5.2, JH,H ϭ 8.9 Hz, 1 H, H-3trans), 2.36 (dddd,
3
NOESY NMR spectroscopy.
3
3
3
4
J
H,H ϭ 7.6, JH,H ϭ 7.6, JH,H ϭ 8.9, JH,H ϭ 1.0 Hz, 1 H, H-2),
3.35 (s, 3 H, OCH
3
), 4.77 (dd, JH,H ϭ 12.6, 3JH,H ϭ 7.6 Hz, 1 H,
3
3
4
H-1ЈЈ), 6.38 (dd, JH,H ϭ 12.6, JH,H ϭ 0.9 Hz, 1 H, H-2ЈЈ), 6.89
Conclusions
3
3
(
d, JH,H ϭ 7.0 Hz, 1 H, Ar-H), 7.03 (d, JH,H ϭ 7.6 Hz, 1 H, Ar-
3
H), 7.12Ϫ7.24 (m, 4 H, Ar-H), 7.67 (d, JH,H ϭ 7.7 Hz, 1 H, Ar-
The catalytic system involving 9-diazo-9H-fluorene (2)
and the (cis-cyclooctene)chromium(0) complex 1 has been
successfully applied to electron-rich dienes. The [2ϩ1]-
cycloaddition proceeds in a highly regioselective way at the
3
13
H), 7.71 (d, JH,H ϭ 7.6 Hz, 1 H, Ar-H) ppm. C NMR (125 MHz,
CDCl ): δ ϭ 23.0 (C-3), 29.9 (C-2), 35.1 (C-1), 56.9 (OCH ), 100.0
C-1ЈЈ), 118.2, 119.7, 120.0, 121.8, 125.8, 126.0, 126.8 (8 ϫ Ar-C),
3
3
(
1
q
29.3, 140.7, 144.4, 148.2 (4 ϫ Ar-C ), 150.2 (C-2ЈЈ) ppm. MS
ϩ
ϩ
unsubstituted 3-position of the conjugated dienes to furnish (70 eV): m/z (%) ϭ 248 (69) [M ], 233 (5) [M Ϫ CH ], 215 (100),
3
ϩ
ϩ
the corresponding cyclopropanes in good to excellent yields. [M Ϫ CH
3
ϩ
Ϫ H
2
O], 189 (15), [M Ϫ CH
3 2 2 2
Ϫ H O Ϫ C H ], 165
ϩ
(
25) [C13H ]. HR-MS: calcd. 248.1201, found 248.1202 for [M ].
9
These results could be extended to α-diazophenylacetate 3.
It turned out that this new system also exhibits great dia-
stereoselectivities: all the reactions were strictly trans-selec-
tive, reflecting the mild reaction conditions.
2
-[(E)-2ЈЈ-Ethoxy-1ЈЈ-methylvinyl)spiro[cyclopropane-1,9Ј[9ЈH]-
fluorene] (10): Reaction of 2 (0.57 g, 3 mmol) with 5 (0.34 g,
mmol) in the presence of 1 (0.02 g, 0.06 mmol, 2 mol %) gave 10
0.51 g, 62%) after work-up (eluent: CH Cl /cyclohexane, 3:2, R
ϭ 10.74 min. H NMR
ϭ 7.1 Hz, 3 H, OCH CH ),
3
(
2
2
f
ϭ
1
0
.63) as a yellowish oil. GC-MS: t
R
3
Experimental Section
(500 MHz, CDCl ): δ ϭ 1.46 (t, J
3
H,H
2
3
3
1
J
3
.50 (s, 3 H, CH ), 2.10 (d, JH,H ϭ 7.1 Hz, 1 H, H-3cis), 2.10 (d,
3
3
H,H ϭ 7.1, 3
9.2 Hz, 1 H, H-2), 4.01 (q, JH,H ϭ 7.0 Hz, 2 H, OCH CH
(s, 1 H, H-2ЈЈ), 7.21 (d, JH,H ϭ 7.4 Hz, 1 H, Ar-H), 7.39Ϫ7.41 (m,
General Remarks: All reactions were performed in flame-dried
glassware and under dry argon. Dichloromethane was dried by dis-
tillation from calcium hydride and saturated with argon. Silica gel
H,H ϭ 9.2 Hz, 1 H, H-3trans), 2.70 (dd,
J
H,H
J ϭ
3
2
3
), 6.38
3
3
4
(
E. Merck, grade 60, 0.062Ϫ0.200 mm) was used for column chro-
2 H, Ar-H), 7.45 (dt, JH,H ϭ 7.4, JH,H ϭ 1.1 Hz, 1 H, Ar-H),
1
13
3
matography. H and C NMR spectra were recorded with Bruker
AVANCE 300, AVANCE 400 and DRX 500 instruments. All
chemical shifts are given relative to TMS as external standard; δ
values are given in ppm, J values are given in Hz. MS (EI) and
HR-MS (EI) were recorded with Kratos MS-50 and Thermoquest
7.48Ϫ7.53 (m, 2 H, Ar-H), 7.99 (t,
J
H,H ϭ 7.1 Hz, 2 H, Ar-H)
): δ ϭ 14.4 (OCH CH ), 15.4
), 22.1 (C-3), 33.6 (C-1), 35.0 (C-2), 67.5 (OCH CH ), 110.6
(C-1ЈЈ), 118.3, 119.6, 119.7, 120.8, 125.6, 125.7 126.2, 126.6 (8 ϫ
Ar-C), 139.4, 140.1, 144.6, 148.5 (4 ϫ Ar-C ), 144.8 (C-2ЈЈ) ppm.
1
3
ppm. C NMR (125 MHz, CDCl
(CH
3
2
3
3
2
3
q
ϩ
ϩ
3
MAT 95 XL instruments. GC-MS was performed using a MS (70 eV): m/z (%) ϭ 276 (100) [M ], 261 (5) [M Ϫ CH ], 247
ϩ
ϩ
ϩ
HewlettϪPackard 5890 Series-II Gas Chromatograph with 5972
(20) [M Ϫ C
Ϫ H
2
H
5
], 230 (30) [M Ϫ H ], 215 (55) [M
2
O Ϫ C
2
ϩ
H
4
Series-Mass Selective Detector, using an HP-5 column (crosslinked Ϫ CH
3
2
O Ϫ C ], 165 (100) [C13H ]. HR-MS: calcd.
2
H
4
9
ϩ
5
% PH ME Siloxane, 12m ϫ 0.2 mm ϫ 0.33µm); program: injec-
276.1514, found 276.1522 for [M ].
1052
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Chromium(0)-Catalysed Cyclopropanation of 1-Alkoxy-1,3-dienes with Diazo Compounds
FULL PAPER
2
-(3ЈЈ,4ЈЈ-Dihydro-2H-pyran-5ЈЈ-yl)spiro[cyclopropane-1,9Ј[9ЈH]-
fluorene] (11): Reaction of 2 (0.57 g, 3 mmol) with 6 (0.33 g, 24.0 (C-3ЈЈЈ), 26.7 (C-7ЈЈЈ), 31.8 (C-5ЈЈЈ), 34.5 (C
mmol) in the presence of 1 (0.02 g, 0.06 mmol, 2 mol %) gave 11 35.6 (C-2), 42.2 (C-6ЈЈЈ), 48.3 (C-2ЈЈЈ), 81.6 (C-1ЈЈЈ), 109.4 (C
0.42 g, 51%) after work-up (eluent: CH Cl /cyclohexane, 1:1, R 118.9, 120.3, 120.4, 121.6, 126.2, 126.4, 126.5, 127.2 (8 ϫ Ar-C),
ϭ 13.15 min. H NMR 144.7 (C-2ЈЈ), 140.2, 141.1, 145.5, 149.2 (4 ϫ Ar-C
δ ϭ 15.0 (CH
3
), 17.0 (CH
3
), 21.1 (CH
3
), 22.4 (C-3), 22.5 (CH
-1), 34.7 (C-4ЈЈЈ),
-1ЈЈ),
3
),
q
3
(
q
2
2
f
ϭ
1
0.46) as a yellowish oil. GC-MS: t
R
q
) ppm. MS
ϩ
ϩ
(500 MHz, C
6
D
6
): δ ϭ 1.01Ϫ1.11 (m, 1 H, CH
2
), 1.18Ϫ1.42 (m, 3
(70 eV): m/z (%) ϭ 386 (7) [M ], 248 (75) [M Ϫ C10
H
18], 178 (90)
2
3
ϩ
ϩ
ϩ
H, CH
2
), 1.66 (dd, JH,H ϭ 4.9, JH,H ϭ 7.5 Hz, 1 H, H-3cis), 1.73 [M Ϫ C10
H18 Ϫ C
4
H
6
O], 165 (100) [C13
H
9
], 83 (95) [M
Ϫ
2
3
3
(dd, JH,H ϭ 4.9, JH,H ϭ 9.2 Hz, 1 H, H-3trans), 2.30 (dd, JH,H
ϭ
C
10
ϩ
H
18 Ϫ C13H ]. HR-MS: calcd. 386.2609, found 386.2608 for
9
3
3
7
2
7
7
.5, JH,H ϭ 9.2 Hz, 1 H, H-2), 3.65 (t, JH,H ϭ 4.8 Hz, 2 H, H- [M ].
ЈЈ), 6.66 (s, 1 H, H-6ЈЈ), 6.83 (d, 3
J
H,H ϭ 7.4 Hz, 1 H, Ar-H),
3
Crystal Structure Determination of Vinylspirocyclopropane (2R)-12:
Pale yellow crystals of (2R)-12 were grown from acetone at room
temp. Crystallographic data were collected with a NoniusϪKappa
CCD diffractometer at 123 K. The molecular structure was solved
.18Ϫ7.34 (m, 5 H, Ar-H), 7.74 (d, JH,H ϭ 7.4 Hz, 1 H, Ar-H),
3
13
.77 (d, JH,H ϭ 7.8 Hz, 1 H, Ar-H) ppm. C NMR (125 MHz,
): δ ϭ 21.1 (C-3ЈЈ), 22.3 (C-4ЈЈ), 24.4 (C-3), 33.9 (C-1), 34.6
C-2), 65.5 (C-2ЈЈ), 109.6 (C-5ЈЈ), 118.6, 120.1, 120.2, 121.2, 126.0,
26.2 126.3, 127.1 (8 ϫ Ar-C), 139.9, 140.8, 145.0, 148.9 (4 ϫ Ar-
6 6
C D
(
1
[23]
by direct methods (SHELXS-97). The non-hydrogen atoms were
2
[24]
ϩ
refined anisotropically on F (SHELXL-97);
hydrogen atoms
q
C ), 143.6 (C-6ЈЈ) ppm. MS (70 eV): m/z (%) ϭ 274 (89) [M ], 215
ϩ
ϩ
were refined isotropically using a riding model. Selected bond
lengths [A] and bond angles [°] (for the atom numbering, see Fig-
(100) [M Ϫ H
2 3 5 9
O Ϫ C H ], 165 (40) [C13H ]. HR-MS: calcd.
˚
ϩ
274.1358, found 274.1358 for [M ].
ure 3; standard deviations are given in parentheses): C(2)ϪC(3)
1.485(2), C(4)ϪC(3) 1.492(2), C(4)ϪC(5) 1.518(3), C(5)ϪC(6)
(
2R/S,1ЈЈЈR,2ЈЈЈS,5ЈЈЈR)-2-[(E)-2ЈЈ-(2ЈЈЈ-Isopropyl-5ЈЈЈ-methyl-
cyclohexanoxy)-1ЈЈ-methylvinyl]spiro[cyclopropane-1,9Ј[9ЈH]-
fluorene][(2R/S)-12]: Reaction of 2 (0.57 g, 3 mmol) with 7 (0.67 g,
1.485(2),
C(2)ϪC(3)ϪC(4) 123.02(14), C(2)ϪC(3)ϪC(5) 119.59(14),
59.75(11), C(3)ϪC(4)ϪC(5) 62.09(11),
C(5)ϪC(17)
1.487(3),
C(5)ϪC(3)
1.552(2),
3
(
R
mmol) in the presence of 1 (0.02 g, 0.06 mmol, 2 mol %) gave 12 C(4)ϪC(3)ϪC(5)
0.96 g, 83%) after work-up (eluent: CH Cl /petroleum ether, 1:1,
ϭ 0.51) as yellowish crystals or yellowish oil. The (2R/S) dia-
2
2
C(6)ϪC(5)ϪC(17) 104.60(14), C(6)ϪC(5)ϪC(4) 123.24(15),
C(17)ϪC(5)ϪC(4) 124.08(15), C(6)ϪC(5)ϪC(3) 119.66(14),
C(17)ϪC(5)ϪC(3) 121.93(13), C(4)ϪC(5)ϪC(3) 58.16(11). Crystal-
lographic data (excluding structure factors) for the structures re-
ported in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publication no. CCDC-
221923. Copies of the data can be obtained free of charge at
www.ccdc.cam.ac.uk./conts/retrieving.html (or from the Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336Ϫ033; E-mail:
deposit@ccdc.cam.ac.uk).
f
stereomers could not be separated by column chromatography.
Their NMR spectrum was recorded as a mixture of diastereomers.
Their signals could be assigned to the (2R) and the (2S) dia-
stereomer on the basis of an independent X-ray analysis for the
(2R) isomer.
1
(
0
2R)-12: GC-MS: t
R
ϭ 12.68 min. H NMR (500 MHz, C
6
D
6
): δ ϭ
), 0.94
), 1.01 (d,
), 1.2Ϫ1.65 (m, 5 H,
ЈЈЈ), 1.83 (dd, 3JH,H ϭ 9.5,
e
3
.91 (m, 1 H, H-4
m, 1 H, H-6
ЈЈЈ), 0.98 (d, 3
H,H ϭ 7.1 Hz, 3 H, CH ), 1.52 (s, 3 H, CH
H-3 ЈЈЈ, H-2 ЈЈЈ, H-5 ЈЈЈ, H-3 ЈЈЈ, H-4
H,H ϭ 5.0 Hz, 1 H, H-3trans), 1.90 (dd, 3
.0 Hz, 1 H, H-3cis), 2.00 (m, 1 H, H-6 ЈЈЈ), 2.40 (dquint, JH,H
a
ЈЈЈ), 0.93 (d, JH,H ϭ 6.7 Hz, 3 H, CH
3
(
a
JH,H ϭ 7.2 Hz, 3 H, CH
3
3
J
3
3
(2R/S,1ЈЈЈR)-2-[(E)-2ЈЈ-(1ЈЈЈ-Phenylethoxy)-1ЈЈ-methyl-
vinyl]spiro[cyclopropane-1,9Ј[9ЈH]-fluorene] [(2R/S)-13]: Reaction of
2 (0.57 g, 3 mmol) with 8 (0.56 g, 3 mmol) in the presence of 1
(0.02 g, 0.06 mmol, 2 mol %) gave 13 (0.80 g, 76%) after work-up
a
a
a
e
2
2
J
JH,H ϭ 8.0,
J
H,H
ϭ
ϭ
ϭ
ϭ
3
5
2
8
4
e
3
3
3
.7, JH,H ϭ 7.1 Hz, 1 H, H-7ЈЈЈ), 2.56 (dd, JH,H ϭ 9.5, JH,H
.0 Hz, 1 H, H-2), 3.30 (ddd, JH,H ϭ 10.8, JH,H ϭ 10.8, JH,H
3
3
3
2 2 f
(eluent: CH Cl /petroleum ether, 3:2, R ϭ 0.41) as a colourless
3
oil. The (2R/S) diastereomers could not be separated by column
chromatography. Their NMR spectrum was recorded as a mixture
of diastereomers.
.5 Hz, 1 H, H-1ЈЈЈ), 6.26 (s, 1 H, H-2ЈЈ), 6.93 (d, JH,H ϭ 5.9 Hz,
H, Ar-H), 7.25Ϫ7.46 (m, 5 H, Ar-H), 7.83 (dd, 3JH,H ϭ 6.5,
1
3
13
J
H,H ϭ 5.9 Hz, 2 H, Ar-H) ppm. C NMR (125 MHz, C
6
D
6
):
),
δ ϭ 15.0 (CH
3
), 17.1 (CH
4.2 (C-3ЈЈЈ), 26.5 (C-7ЈЈЈ), 31.8 (C-5ЈЈЈ), 34.5 (C
5.7 (C-2), 42.5 (C-6ЈЈЈ), 48.2 (C-2ЈЈЈ), 81.9 (C-1ЈЈЈ), 110.0 (C
18.9, 120.3, 120.4, 121.7, 126.2, 126.4, 126.5, 127.2 (8 ϫ Ar-C),
3
), 21.0 (CH
3
), 22.5 (C-3), 22.6 (CH
3
ϭ 12.35 min. 1H NMR (500 MHz,
Diastereomer I: GC-MS: t
CDCl ): δ ϭ 1.54 (s, 3 H, CH
CH
R
2
3
1
1
q
-1), 34.7 (C-4ЈЈЈ),
-1ЈЈ),
3
3
3
), 1.74 (d,
JH,H ϭ 6.6 Hz, 3 H,
3
2
q
), 1.98 (dd, JH,H ϭ 8.5, JH,H ϭ 4.9 Hz, 1 H, H-3a), 2.02 (dd,
3
3
2
3
J
H,H ϭ 9.6, JH,H ϭ 4.9 Hz, 1 H, H-3b), 2.64 (dd, JH,H ϭ 8.6,
44.9 (C-2ЈЈ), 140.2, 141.1, 145.5, 149.2 (4 ϫ Ar-C
70 eV): m/z (%) ϭ 386 (7) [M ], 248 (75) [M Ϫ C10
q
) ppm. MS
3JH,H ϭ 9.6 Hz, 1 H, H-2), 5.00 (q, JH,H ϭ 6.6 Hz, 1 H, H-1ЈЈ),
3
ϩ
ϩ
(
H18], 178 (90)
4
6
.38 (q, JH,H ϭ 1.6 Hz, 1 H, H-2ЈЈ), 6.75Ϫ8.0 (m, 13 H, Ar-H)
ϩ
ϩ
ϩ
[M
Ϫ C10
H18 Ϫ C
4
H
6
O], 165 (100) [C13
H
9
], 83 (95) [M
Ϫ
13
ppm. C NMR: δ ϭ (125 MHz, CDCl
3
): δ ϭ 14.6 (CH
-1), 35.0 (C-2), 79.8 (C-1ЈЈЈ), 111.2 (C
18.2, 119.6, 119.7, 120.8, 125.5, 125.7, 2 ϫ 126.0, 126.2, 126.6,
3
), 22.2 (C-
C
10
ϩ
H
18 Ϫ C13
H
9
]. HR-MS: calcd. 386.2609, found 386.2608 for
3
1
), 23.8 (CH
3
), 33.6 (C
q
q
-1ЈЈ),
[M ].
1
127.5, 2 ϫ 128.6 (13 ϫ Ar-C), 143.7 (C-2ЈЈ), 139.4, 140.1, 143.3,
144.5, 148.5 (5 ϫ Ar-C ) ppm. MS (70 eV): m/z (%) ϭ 352 (5)
(
0
2S)-12: GC-MS: t
R
ϭ 12.74 min. H NMR (500 MHz, C
6
D
6
): δ ϭ
ЈЈЈ), 0.94
3
), 0.98 (d,
3
q
.90 (d, JH,H ϭ 7.1 Hz, 3 H, CH
3
), 0.91 (m, 1 H, H-4
a
ϩ
ϩ
ϩ
ЈЈЈ), 0.95 (d, 3
[M ], 247 (80) [M Ϫ C
8
H
H
9
O], 229 (30) [M Ϫ C
]. HR-MS: calcd. 352.1827, found
8
H
11O], 165 (100)
(
m, 1 H, H-6
a
J
H,H ϭ 6.5 Hz, 3 H, CH
), 1.51 (s, 3 H, CH ), 1.2Ϫ1.65 (m, 5 H,
3 3
ϩ
ϩ
3
9 8
[C13H ], 105 (65) [C
9
JH,H ϭ 7.2 Hz, 3 H, CH
ϩ
H-3 ЈЈЈ, H-2 ЈЈЈ, H-5 ЈЈЈ, H-3
a
a
a
e
ЈЈЈ, H-4
e
ЈЈЈ), 1.84 (dd, 3JH,H ϭ 9.5,
352.1833 for [M ].
Diastereomer II: GC-MS: t
CDCl ): δ ϭ 1.50 (s, 3 H, CH
CH ), 1.84 (dd, JH,H ϭ 8.2, JH,H ϭ 4.9 Hz, 1 H, H-3a), 2.00 (dd,
2
H,H ϭ 4.9 Hz, 1 H, H-3trans), 1.87 (dd, 3
2
ϭ 12.44 min. 1H NMR (500 MHz,
), 1.73 (d, 3JH,H ϭ 6.6 Hz, 3 H,
J
JH,H ϭ 8.0,
J
H,H
ϭ
ϭ
ϭ
ϭ
R
3
4
2
8
4
.9 Hz, 1 H, H-3cis), 2.08 (m, 1 H, H-6
.7, JH,H ϭ 7.1 Hz, 1 H, H-7ЈЈЈ),2.56 (dd, JH,H ϭ 9.5, JH,H
.0 Hz, 1 H, H-2), 3.34 (ddd, JH,H ϭ 10.6, JH,H ϭ 10.6, JH,H
.6 Hz, 1 H, H-1ЈЈЈ), 6.28 (s, 1 H, H-2ЈЈ), 6.94 (d, JH,H ϭ 6.0 Hz,
e
ЈЈЈ), 2.39 (dquint, JH,H
3
3
3
3
3
3
2
3
3
3
3
3
2
3
JH,H ϭ 10.6, JH,H ϭ 4.9 Hz, 1 H, H-3b), 2.62 (dd, JH,H ϭ 8.2,
3
3JH,H ϭ 10.6 Hz, 1 H, H-2), 4.97 (q, JH,H ϭ 6.6 Hz, 1 H, H-1ЈЈЈ),
3
4
1
H, Ar-H), 7.25Ϫ7.46 (m, 5 H, Ar-H), 7.79 (dd, 3JH,H ϭ 7.4, 6.37 (q, JH,H ϭ 1.7 Hz, 1 H, H-2ЈЈ), 6.75Ϫ8.0 (m, 13 H, Ar-H)
3
13
13
J
H,H ϭ 6.0 Hz, 2 H, Ar-H) ppm. C NMR (125 MHz, C
6
D
6
): ppm. C NMR (125 MHz, CDCl
3
): δ ϭ 14.6 (CH
3
), 21.8 (C-3),
Eur. J. Org. Chem. 2004, 1049Ϫ1056
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1053

N. D. Hahn, M. Nieger, K. H. Dötz
FULL PAPER
δ ϭ 14.1 (CH
60.9 (OCH ), 101.7 (C-1Ј), 127.2, 2 ϫ 128.1, 2 ϫ 132.2 (5 ϫ Ar-
C), 136.9 (Ar-C ), 148.9 (C-2Ј), 173.5 (CϭO) ppm. MS (70 eV):
m/z (%) ϭ 246 (67) [M ], 173 (95) [M Ϫ C
3 3
), 21.9 (C-3), 28.2 (C-2), 34.7 (C-1), 55.3 (OCH ),
Table 4. Crystal data and structure refinement parameters of
(2R)-12
2
q
ϩ
ϩ
ϩ
(2R)-12
3
H
5
O
2
], 157 (100) [M
ϩ
Ϫ C
[M Ϫ C
3
H
5
O
2
Ϫ CH
Ϫ C
(20) [C H ]. HR-MS: calcd. 246.1256, found 246.1260 for [M ].
3
], 141 (85) [M Ϫ C
3
H
5
O
2
ϩ
Ϫ OCH ], 129 (95)
3
ϩ
ϩ
Empirical formula
C
386.55
123(2)
0.71073
monoclinic
28
H
34
O
3
H
5
O
2
2
H
4
O], 105 (25) [C
7 5 7 7
H O ], 91 (45) [C H ], 77
ϩ
ϩ
M
r
6
5
T [K]
˚
Ethyl trans-2-[(E)-2Ј-Ethoxy-1Ј-methylvinyl]-1-phenylcyclopropane-
carboxylate (17): Reaction of 3 (0.57 g, 3 mmol) with 5 (0.68 g,
6 mmol) in the presence of 1 (0.05 g, 0.15 mmol, 5 mol %) gave 17
(0.47 g, 57%) after work-up (eluent: CH Cl /petroleum ether, 2:1,
Wavelength [A]
Crystal system
Space group
1
P2 (no.4)
˚
a [A]
7.6262(1)
6.1798(1)
24.4208(5)
98.705(1)
1137.66(3)
2
2
2
˚
1
b [A]
R ϭ 0.30) as a colourless oil. GC-MS: t ϭ 8.80 min. H NMR
f
R
˚
c [A]
3
(
(
300 MHz, CD
2
Cl
2
): δ ϭ 0.94 (t, JH,H ϭ 7.1 Hz, 3 H, CH
), 1.07 (d, 4JH,H ϭ 1.1 Hz, 3 H, CH
3
3
), 1.05
),
H,H ϭ 4.8 Hz, 1 H, H-3a), 1.62 (dd,
β [°]
3
t, JH,H ϭ 6.9 Hz, 3 H, CH
3
˚
3
V [A ]
2
1
.52 (dd, 3
J
H,H ϭ 7.4,
J
Z
ρ
µ[mm
3
2
3
calcd.[g cmϪ3]
Ϫ1
J
H,H ϭ 9.2, JH,H ϭ 4.8 Hz, 1 H, H-3b), 2.32 (dd, JH,H ϭ 7.4,
1.128
0.066
3J
ϭ 9.2 Hz, 1 H, H-2), 3.48 (q, J
3
H,H
ϭ 6.9 Hz, 1 H, OCH2),
]
H,H
3
.52 (q, 3JH,H ϭ 6.9 Hz, 1 H, OCH
2
), 3.95 (q, 3JH,H ϭ 7.1 Hz, 1
F(000)
Crystal size [mm]
Diffractometer
420
), 3.99 (q, 3JH,H ϭ 7.1 Hz, 1 H, OϪCH
), 5.69 (q, JH,H
4
ϭ
0.60 ϫ 0.40 ϫ 0.20
Nonius-Kappa CCD
H, OCH
2
2
1.1 Hz, 1 H, H-2Ј), 7.1Ϫ7.3 (m, 5 H, Ar-H) ppm. 13C NMR
(75 MHz, CD Cl ): δ ϭ 12.9 (CH ), 14.1 (CH ), 15.0 (CH ), 17.4
Radiation
θ range for data collection [°]
Index range
Mo-K
α
2
2
3
3
3
2.95Ϫ25.00°
Ϫ9 Յ h Յ 9
Ϫ7 Յ k Յ 7
Ϫ29 Յ l Յ 29
18580
3977
263/1
1.058
0.0362
0.0920
(
C-3), 32.9 (C-2), 34.9 (C
q
-1), 61.0 (OCH
2
), 67.5 (OCH
2
), 109.3
(
q q
C -1Ј), 126.9, 2 ϫ 127.7, 2 ϫ 131.5 (5 ϫ Ar-C), 136.3 (Ar-C ),
1
44.3 (C-2Ј), 173.9 (CϭOϪ) ppm. MS (70 eV): m/z (%) ϭ 274 (35)
ϩ
ϩ
ϩ
[M ], 228 (30) [M Ϫ C
2
H
6
O], 201 (55) [M Ϫ C
3
H
5
O
2
], 171 (100)
H
2 6
Collected reflections
Unique reflections
Parameters/restraints
Goodness-of-fit on F2
R (F) for I Ͼ 2σ(I)
ϩ
ϩ
[M
Ϫ C
3
H
5
O
2
Ϫ C
2
H
6
], 155 (50) [M Ϫ C
3
H
5
O
2
Ϫ C O], 143
ϩ
ϩ
(
55) [M Ϫ C Ϫ C
3
H
5
O
2
Ϫ C
2
H
6
2 3 3 5 2
H ], 128 (40) [M ϪC H O Ϫ
ϩ
C
4
H
9
O], 91 (45) [C H ]. HR-MS: calcd. 274.1569, found 274.1578
7 7
ϩ
for [M ].
2
wR2 (F ) for all data
Ethyl trans-2-(3Ј,4Ј-Dihydro-2H-pyran-5Ј-yl)-1-phenylcyclopropane-
carboxylate (18): Reaction of 3 (0.57 g, 3 mmol) with 6 (0.66 g,
6
mmol) in the presence of 1 (0.05 g, 0.15 mmol, 5 mol %) gave 18
(0.52 g, 64%) after work-up (eluent: CH Cl /petroleum ether, 3:2,
ϭ 0.26) as a colourless oil. GC-MS: t ϭ 11.63 min. H NMR
): δ ϭ 1.08 (t, JH,H ϭ 7.2 Hz, 3 H, CH ), 1.14
2
1
1
1
3.9 (CH
3
), 33.6 (C
q
-1), 35.0 (C-2), 79.4 (C-1ЈЈЈ), 111.3 (C
q
-1ЈЈ),
2
2
1
18.3, 119.5, 119.6, 120.7, 125.6, 125.6, 2 ϫ 125.8, 126.2, 126.6,
27.8, 2 ϫ 128.4 (13 ϫ Ar-C), 143.5 (C-2ЈЈ), 139.4, 140.0, 143.5,
R
f
R
3
(300 MHz, CDCl
(m, 2 H, H-3Ј), 1.44 (m, 2 H, H-4Ј), 1.47 (dd, JH,H ϭ 7.4, JH,H ϭ
3
3
2
3
44.8, 148.5 (5 ϫ Ar-C
q
) ppm. MS (70 eV): m/z (%) ϭ 352 (5)
ϩ
ϩ
ϩ
3
2
[M ], 247 (80) [M Ϫ C
8
H
H
9
O], 229 (30) [M Ϫ C
8
H11O], 165 (100)
4.9 Hz, 1 H, H-3cis), 1.65 (dd, JH,H ϭ 9.2, JH,H ϭ 4.9 Hz, 1 H,
ϩ
ϩ
9
3
3
13 9 8
[C H ], 105 (65) [C
]. HR-MS: calcd. 352.1827, found H-3trans), 2.30 (dd, JH,H ϭ 7.4, JH,H ϭ 9.2 Hz, 1 H, H-2), 3.51
ϩ
3
2
3
3
52.1833 for [M ].
(dt, JH,H ϭ 5.6, JH,H ϭ 10.7 Hz, 1 H, H-2Јa), 3.62 (dt, JH,H ϭ
.0, JH,H ϭ 10.7 Hz, 1 H, H-2Јb), 3.98 (q, JH,H ϭ 7.1 Hz, 1 H,
), 4.04 (q, JH,H ϭ 7.1 Hz, 1 H, OCH ), 6.14 (s, 1 H, H-
2 2
Ј), 7.15Ϫ7.40 (m, 4 H, Ar-H), 7.66 (d, JH,H ϭ 7.4 Hz, 1 H, Ar-
2
3
5
General Procedure for the Chromium Complex Catalysed Reactions
of Ethyl α-diazophenylacetate (3) with 1-Alkoxy-1,3-butadienes: A
solution of ethyl α-diazophenylacetate (3) in CH Cl (20 mL) was
2 2
added over a period of 4 h at 5 °C to a stirred solution containing
the corresponding 1-alkoxy-1,3-butadiene (2 equiv.) and chro-
2 2 2
mium(0) complex 1 (5 mol %) in CH Cl (5 mL). Evolution of N
was accompanied by a colour change of the reaction mixture from
yellow to dark red. After stirring for a further 8 h followed by re-
moval of the solvent under reduced pressure, work-up was per-
formed by column chromatography.
3
OϪCH
3
6
1
3
H) ppm. C NMR (75 MHz, CDCl
3
): δ ϭ 14.2 (CH
ЈЈ), 22.1 (C-3), 22.9 (C-4ЈЈ), 32.0 (C-2), 34.0 (C-1), 61.0 (OCH
5.4 (C-2ЈЈ), 108.2 (C-5ЈЈ), 125.7, 2 ϫ 128.4, 2 ϫ 131.0 (5 ϫ Ar-
), 142.7 (C-6ЈЈ), 174.4 (CϭO) ppm. MS (70 eV):
3
), 17.1 (C-
3
6
2
),
C), 136.4 (Ar-C
m/z (%) ϭ 272 (30) [M ], 199 (75) [M Ϫ C
q
ϩ
ϩ
ϩ
3
5 2
H O ], 155 (25) [M
ϩ
ϩ
Ϫ C
3 5 2 3 8 7 5 7 7
H O Ϫ C H ], 105 (100) [C H O ], 91 (45) [C H ]. HR-
ϩ
MS: calcd. 272.1412, found 272.1413 for [M ].
Ethyl (1ЈЈR,2ЈЈS,5ЈЈR)-trans-2-[(E)-2Ј-(2ЈЈ-Isopropyl-5ЈЈ-methyl-
cyclohexanoxy)-1Ј-methylvinyl]-1-phenylcyclopropanecarboxylate
19): Reaction of 3 (0.57 g, 3 mmol) with 7 (1.34 g, 6 mmol) in the
presence of 1 (0.05 g, 0.15 mmol, 5 mol %) gave 19 (0.77 g, 67%)
as a 1:1 mixture of diastereomers after work-up (eluent: CH Cl
petroleum ether, 1:1, R ϭ 0.43) as a colourless oil. The dia-
Ethyl
boxylate (16): Reaction of 3 (0.57 g, 3 mmol) with 4 (0.50 g,
mmol) in the presence of 1 (0.05 g, 0.15 mmol, 5 mol %) gave 16
0.58 g, 78%) after work-up (eluent: CH Cl /petroleum ether, 2:1,
ϭ 8.21 min. H NMR
): δ ϭ 0.81 (t, JH,H ϭ 7.0 Hz, 3 H, CH ), 1.10
trans-2-[(E)-2Ј-Methoxyvinyl]-1-phenylcyclopropanecar-
(
6
(
R
(
2
2
2
2
/
1
f R
ϭ 0.38) as a colourless oil. GC-MS: t
3
f
500 MHz, C
6
D
6
3
3
stereomers could not be separated by column chromatography.
Their NMR spectrum was recorded as a mixture of diastereomers.
3
2
(
9
dd, JH,H ϭ 6.7, JH,H ϭ 4.3 Hz, 1 H, H-3a), 1.99 (dd, JH,H
ϭ
2
3
3
.1, JH,H ϭ 4.3 Hz, 1 H, H-3b), 2.57 (ddd, JH,H ϭ 6.7, JH,H
ϭ
9
.1, 3
J
J
H,H ϭ 9.2 Hz, 1 H, H-2), 2.85 (s, 3 H, OCH
3
), 3.80 (dd,
Diastereomer I: GC-MS: t
R
ϭ 12.13 min. 1H NMR (300 MHz,
3
H,H ϭ 9.2, 3JH,H ϭ 12.7 Hz, 1 H, H-1Ј), 3.93 (m, 1 H, OCH
3
3
2
), CDCl
3
): δ ϭ 0.74 (d, JH,H ϭ 5.7 Hz, 3 H, CH
), 0.90 (d, 3
H,H ϭ 6.2 Hz, 3 H, CH
H,H ϭ 6.8 Hz, 3 H, CH ), 0.6Ϫ1.55 (m, 8 H, H-4
ЈЈЈ, H-2 ЈЈЈ, H-5 ЈЈЈ, H-3 ЈЈЈ, H-4 ЈЈЈ, H-6 ЈЈЈ), 1.58 (s, 3 H, CH
3
), 0.84 (d, JH,H
ϭ
3
6
.27 (d, 3JH,H ϭ 12.7 Hz, 1 H, H-2Ј), 7.11 (t, JH,H ϭ 7.4 Hz, 1 H, 6.0 Hz, 3 H, CH
3
J
3
), 1.14 (t,
3
3
Ar-H
p
), 7.20 (dd, 3JH,H ϭ 7.4, JH,H ϭ 7.2 Hz, 2 H, Ar-H
m
), 7.31
):
J
3
a a
ЈЈЈ, H-6
ЈЈЈ, H-
),
3
) ppm. 13C NMR (125 MHz, C
(
d, JH,H ϭ 7.1 Hz, 2 H, Ar-H
o
6
D
6
3
a
a
a
e
e
e
3
1054
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1049Ϫ1056

Chromium(0)-Catalysed Cyclopropanation of 1-Alkoxy-1,3-dienes with Diazo Compounds
FULL PAPER
1
.74 (dd, 3JH,H ϭ 9.6, JH,H ϭ 4.7 Hz, 1 H, H-3trans), 1.90 (m, 1 H,
2
3
J
H,H ϭ 7.3, 2JH,H ϭ 4.8 Hz, 1 H, H-3cis), 1.58 (dd, JH,H ϭ 9.2,
3
H-7ЈЈЈ), 2.01 (dd, JH,H ϭ 8.1, JH,H ϭ 4.7 Hz, 1 H, H-3cis), 2.40 2JH,H ϭ 4.8 Hz, 1 H, H-3trans), 2.30 (dd,
3
2
3
J
H,H ϭ 7.3, 3JH,H
ϭ
dd, 3
J
J
H,H ϭ 9.6, 3JH,H ϭ 8.1 Hz, 1 H, H-2), 3.30 (ddd, 1 H, 9.2 Hz, 1 H, H-2), 3.98 (m, 2 H, OCH
), 4.48 (q, JH,H ϭ 6.5 Hz,
3
(
2
3
H,H ϭ 9.6, 3JH,H ϭ 9.4, JH,H ϭ 4.2 Hz, H-1ЈЈЈ), 4.08 (q, JH,H
.3 Hz, 2 H, OCH ), 5.81 (s, 1 H, H-2ЈЈ), 7.10Ϫ7.41 (m, 5 H, Ar-
H) ppm. C NMR (75.5 MHz, CDCl ): δ ϭ 13.4 (CH ), 14.1 (CH
), 17.5 (C-3), 20.6 (CH ), 22.1 (CH ), 23.6 (C- 79.0 (OCH), 110.2 (C
ЈЈЈ), 25.8 (C-7ЈЈЈ), 31.5 (C-2), 33.0 (C-5ЈЈЈ), 34.3 (C -1), 35.1 (C- 128.3, 2 ϫ 131.1 (10 ϫ Ar-C), 135.9, 143.2 (2 ϫ Ar-C
ЈЈЈ), 41.4 (C-6ЈЈЈ), 47.6 (C-2ЈЈЈ), 60.8 (OCH ), 81.4 (C-1ЈЈЈ), 108.4 2Ј), 174.0 (CϭO) ppm. MS (70 eV): m/z (%) ϭ 350 (10) [M ], 246
-1ЈЈ), 126.8, 2 ϫ 127.4, 2 ϫ 131.2 (5 ϫ Ar-C), 135.9 (Ar-C
43.4 (C-2ЈЈ), 174.1 (CϭO) ppm. MS (70 eV): m/z (%) ϭ 384 (40)
3
3
4
ϭ
1 H, OCH), 5.72 (q, JH,H ϭ 1.1 Hz, 1 H, H-2Ј), 6.95Ϫ7.1 (m, 10
1
3
6
2
H, Ar-H) ppm. C NMR (75 MHz, CDCl
), 17.8 (C-3), 23.4 (CH ), 32.8 (C-2), 34.6 (C-1), 60.8 (OCH
-1Ј), 2 ϫ 125.8, 126.7, 127.2, 2 ϫ 127.5, 2 ϫ
), 143.2 (C-
3
): δ ϭ 12.6 (CH
3
), 14.1
13
3
3
3
3
2
),
(CH
3
), 16.5 (CH
3
3
3
q
3
4
q
q
ϩ
2
ϩ
ϩ
ϩ
(C
q
q
), (5) [M Ϫ C
Ϫ C Ϫ C
(10) [C
8
H
8
], 177 (5) [M Ϫ C
O Ϫ C ], 105 (100) [C
6 5
H ]. HR-MS: calcd. 350.1882, found 350.1888 for [M ].
8 8 4 5
H Ϫ C H O], 149 (15) [M
ϩ
ϩ
1
[
8
H
8
4
H
5
2
H
4
8 9 7 7
H ], 91 (5) [C H ], 77
ϩ
ϩ
ϩ
ϩ
ϩ
M ], 246 (50) [M Ϫ C10
H
18], 200 (40) [M Ϫ C10
18 Ϫ C ], 139 (50) [C10
18 Ϫ C ]. HR-MS: calcd.
H
18 Ϫ C
2
H
6
O],
ϩ
ϩ
173 (80) [M Ϫ C10
H
3
H
5
O
2
H19 ], 105 (30)
ϩ
9
ϩ
[C
8
H
], 83 (100) [M Ϫ C10
H
4 6 2
H O
Acknowledgments
ϩ
384.2664, found 384.2668 for M .
ϭ 12.13 min. 1H NMR (300 MHz,
Financial support from the Fonds der Chemischen Industrie and
the Ministry of Science and Research NRW is gratefully acknowl-
edged.
Diastereomer II: GC-MS: t
R
3
3
CDCl
3
): δ ϭ 0.57 (d, JH,H ϭ 5.8 Hz, 3 H, CH
), 0.84 (d, 3JH,H ϭ 6.0 Hz, 3 H, CH
H,H ϭ 6.9 Hz, 3 H, CH ), 0.6Ϫ1.55 (m, 8 H, H-4
ЈЈЈ, H-2 ЈЈЈ, H-5 ЈЈЈ, H-3 ЈЈЈ, H-4 ЈЈЈ, H-6 ЈЈЈ), 1.58 (s, 3 H, CH
.74 (dd, JH,H ϭ 9.6, JH,H ϭ 4.7 Hz, 1 H, H-3trans), 1.86 (m, 1 H,
3
), 0.76 (d, JH,H
ϭ
6
J
.8 Hz, 3 H, CH
3
3
), 1.19 (t,
3
3
a
ЈЈЈ, H-6
a
ЈЈЈ, H-
),
3
1
a
a
3
a
e
e
e
3
[1]
A. Loose, J. Prakt. Chem. 1909, 79, 507Ϫ510.
2
[2]
L. Wolff, Justus Liebigs Ann. Chem. 1912, 394, 23Ϫ59.
3
2
[3] [3a]
H-7ЈЈЈ), 2.01 (dd, JH,H ϭ 8.1, JH,H ϭ 4.7 Hz, 1 H, H-3cis), 2.40
M. P. Doyle, M. A. McKervey, T. Ye, Modern Catalytic
3
3
3
Methods for Organic Synthesis with Diazo Compounds, John
Wiley & Sons, New York, 1998. [ C. A. Merlic, A. L. Zech-
man, Synthesis 2003, 8, 1137Ϫ1156. [ G. Maas, Top. Curr.
Chem. 1987, 137, 75Ϫ253.
(
9
dd, JH,H ϭ 9.6, JH,H ϭ 8.1 Hz, 1 H, H-2), 3.30 (ddd, JH,H
ϭ
3b]
3
3
3
.6, JH,H ϭ 9.4, JH,H ϭ 4.2 Hz, 1 H, H-1ЈЈЈ), 4.08 (q, JH,H
.3 Hz, 2 H, OϪCH
ϭ
3c]
6
2
), 5.72 (s, 1 H, H-2ЈЈ), 7.10Ϫ7.41 (m, 5 H, Ar-
): δ ϭ 13.1 (CH ), 14.1
), 17.5 (C-3), 20.5 (CH ), 22.0 (CH ), 23.6 (C-
ЈЈЈ), 25.9 (C-7ЈЈЈ), 31.4 (C-2), 32.9 (C-5ЈЈЈ), 34.3 (C -1), 34.8 (C-
ЈЈЈ), 41.0 (C-6ЈЈЈ), 47.5 (C-2ЈЈЈ), 60.8 (OCH ), 81.3 (C-1ЈЈЈ), 108.0
-1ЈЈ), 126.7, 2 ϫ 127.4, 2 ϫ 131.2 (5 ϫ Ar-C), 135.8 (Ar-C ),
13
H) ppm. C NMR (75.5 MHz, CDCl
3
3
[4]
[4a]
Reviews:
H. Lebel, J.-F. Marcoux, C. Molinaro, A. B. Char-
(CH
3
), 16.4 (CH
3
3
3
[4b]
ette, Chem. Rev. 2003, 103, 977Ϫ1050.
A. Pfaltz, in Tran-
3
4
q
sition Metals For Organic Chemistry: Building Blocks and Fine
Chemicals (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim,
1998, chapter 2.6. [ A. Pfaltz, in Contemporary Asymmetric
2
4c]
(C
q
q
ϩ
1
2
43.2 (C-2ЈЈ), 174.1 (CϭO) ppm. MS (70 eV): m/z ϭ 384 (40) [M ],
Catalysis I-III (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
ϩ
ϩ
Springer, Berlin, Heidelberg, 2000, chapter 16.1. [4d] K. M. Ly-
46 (50) [M Ϫ C10
H
18], 200 (40) [M Ϫ C10
], 139 (50) [C10
18 Ϫ C ]. HR-MS: calcd.
H
18 Ϫ C
2
H
6
O], 173
ϩ
ϩ
don, M. A. McKervey, in Contemporary Asymmetric Catalysis
IϪIII (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
Springer, Berlin, Heidelberg, 2000, chapter 16.2. [ A. B. Char-
ette, H. Lebel, in Contemporary Asymmetric Catalysis IϪIII
(Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer,
Berlin, Heidelberg, 2000, chapter 16.3. [ M. P. Doyle, in Cata-
lytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima), VCH Pub-
(80) [M Ϫ C10
H18 Ϫ C
3
H
5
O
2
H19 ], 105 (30)
ϩ
ϩ
[C
8
H
9
], 83 (100) [M Ϫ C10
84.2664, found 384.2668 for M .
H
4 6 2
H O
4e]
ϩ
3
Ethyl (1ЈЈR)-trans-2-[(E)-2Ј-(1ЈЈ-Phenylethoxy]-1Ј-methylvinyl)-1-
phenylcyclopropanecarboxylate (20): Reaction of 3 (0.57 g, 3 mmol)
with 8 (1.12 g, 6 mmol) in the presence of 1 (0.05 g, 0.15 mmol, 5
mol %) gave 20 (0.62 g, 59%) as an 1:1 mixture of diastereomers
4f]
lishers, New York, 1993, chapter 5.
[5]
[5a]
Reviews:
Methoden Org. Chem. (Houben-Weyl) 4th ed.
after work-up (eluent: CH
2
Cl
2
/petroleum ether, 2:1, R
f
ϭ 0.43) as a
[5b]
1
952, vol. VI/3 (Ed.: E. Müller), Thieme, Stuttgart, 1971.
colourless oil. The diastereomers could not be separated by column
chromatography. Their NMR spectrum was recorded as a mixture
of diastereomers.
Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952, vol.
[5c]
E17aϪc (Ed.: A. de Meijere), Thieme, Stuttgart, 1997. J. R.
[5d]
Y. Salaün, Top. Curr. Chem. 1988, 144, 1Ϫ71.
H.-U. Reissig,
Top. Curr. Chem. 1988, 144, 73Ϫ135. [ H. N. C. Wong, M.-
5e]
Diastereomer I: GC-MS: t
R
ϭ 11.58 min. 1H NMR (300 MHz,
Y. Hon, C.-W. Tse, Y.-C. Yip, J. Tanko, T. Hudlicky, Chem. Rev.
3
4
CDCl
3
): δ ϭ 1.02 (t, JH,H ϭ 7.0 Hz, 3 H, CH
3
), 1.07 (d, JH,H
ϭ
1989, 89, 165Ϫ198.
[6] [6a]
1
J
.2 Hz, 3 H, CH
3
), 1.31 (d, 3JH,H ϭ 6.4 Hz, 3 H, CH
3
3
), 1.45 (dd,
T. Hudlicky, F. Rulin, T. C. Lovelace, J. W. Reed, in Studies
3
2
H,H ϭ 7.4, JH,H ϭ 4.8 Hz, 1 H, H-3cis), 1.64 (dd, JH,H ϭ 9.2,
in Natural Product Chemistry, Stereoselective Synthesis (Ed.:
Attaur-Rahman), Elsevier, Amsterdam, 1989, vol. 3, Part B.
2JH,H ϭ 4.8 Hz, 1 H, H-3trans), 2.30 (dd, 3
J
H,H ϭ 7.4, 3JH,H
ϭ
3
[6b]
9
1
.2 Hz, 1 H, H-2), 3.95 (m, 2 H, OCH
2
), 4.54 (q, JH,H ϭ 6.4 Hz,
C. A. Henrick, Pyrethroids in Agrochemicals from natural
4
Products (Ed.: C. R. A. Godfrey), Marcel Dekker, New York
H, OCH), 5.74 (q, JH,H ϭ 1.2 Hz, 1 H, H-2Ј), 6.95Ϫ7.1 (m, 10
1995, p. 147Ϫ213. [ R. Faust, Angew. Chem. 2001, 113,
6c]
13
H, Ar-H) ppm. C NMR (75 MHz, CDCl
3
): δ ϭ 12.9 (CH
), 32.5 (C-2), 34.4 (C-1), 60.8
-1Ј), 2 ϫ 125.6, 126.7, 127.4, 2 ϫ
27.5, 2 ϫ 128.3, 2 ϫ 131.2 (10 ϫ Ar-C), 135.7, 143.0 (2 ϫ Ar-
), 143.0 (C-2Ј), 174.1 (CϭO) ppm. MS (70 eV): m/z (%) ϭ 350
3
), 14.0
2
312Ϫ2314; R. Faust, Angew. Chem. Int. Ed. 2001, 40,
251Ϫ2253.
(
CH
3
), 17.4 (C-3), 23.5 (CH
), 79.2 (OCH), 109.6 (C
3
2
(
OϪCH
2
q
[
7] [7a]
B. M. Trost, T. Yasukata, J. Am. Chem. Soc. 2001, 123,
1
[7b]
7162Ϫ7163.
P. A. Wender, C. M. Barziay, A. Dyckman, J.
C
q
[7c]
Am. Chem. Soc. 2001, 123, 179Ϫ180.
T. Hudlicky, J. W.
ϩ
ϩ
ϩ
(10) [M ], 246 (5) [M Ϫ C
8
H
8
], 177 (5) [M Ϫ C
8 8 4 5
H Ϫ C H O],
Reed, in Comprehensive Organic Synthesis (Eds.: B. M. Trost,
I. Fleming), Pergamon Press, Oxford, 1991, vol. 5, p. 899Ϫ970.
T. Hudlicky, F. J. Koszyk, D. M. Dochwat, G. L. Cantrell, J.
Org. Chem. 1981, 46, 2911Ϫ2915.
9] [9a]
ϩ
ϩ
149 (15) [M Ϫ C
8
H
8
Ϫ C
4
H
5
O Ϫ C ], 105 (100) [C H ], 91
2
H
4
8 9
ϩ
7
ϩ
[8]
(5) [C
7
H
], 77 (10) [C
6
H
5
]. HR-MS: calcd. 350.1882, found
ϩ
350.1888 for [M ].
[
J. Pfeiffer, K. H. Dötz, Angew. Chem. 1997, 109,
Diastereomer II: GC-MS: t
R
ϭ 11.58 min. 1H NMR (300 MHz,
2
948Ϫ2950; Angew. Chem. Int. Ed. Engl. 1997, 36, 2828Ϫ2830.
3
4
[9b]
CDCl
3
): δ ϭ 1.04 (t, JH,H ϭ 6.9 Hz, 3 H, CH
3
), 1.14 (d, JH,H
ϭ
J. Pfeiffer, M. Nieger, K. H. Dötz, Eur. J. Org. Chem.
1.1 Hz, 3 H, CH
3
), 1.21 (d, 3JH,H ϭ 6.5 Hz, 3 H, CH
3
), 1.40 (dd,
1998, 1011Ϫ1022.
Eur. J. Org. Chem. 2004, 1049Ϫ1056
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1055

N. D. Hahn, M. Nieger, K. H. Dötz
FULL PAPER
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1056
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1049Ϫ1056