Reaction of α,β-unsaturated Fischer carbene complexes with allyl alkoxide

Article abstract of DOI:10.1016/j.tet.2005.10.036

Optically enriched homo-binuclear Fischer chromium carbene complexes with planar chiral arene chromium complexes gave α-allyl β-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-bin

Full text of DOI:10.1016/j.tet.2005.10.036

Tetrahedron 62 (2006) 922–930
Reaction of a,b-unsaturated Fischer carbene complexes
with allyl alkoxide
a
a
a
Ken Kamikawa,a, Atsushi Tachibana, Yasunori Shimizu, Kazuya Uchida,
*
Masaru Furusyob and Motokazu Uemurac,
*
aDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
bAnalysis Technology Research Center, 1-1-1, Koyakita, Itami, Hyogo 664-0016, Japan
cKyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 640-8412, Japan
Received 26 August 2005; revised 9 September 2005; accepted 13 October 2005
Available online 7 November 2005
Abstract—Optically enriched homo-binuclear Fischer chromium carbene complexes with planar chiral arene chromium complexes gave
a-allyl b-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-
binuclear tungsten carbene complexes afforded anti a-allyl b-hydroxy b-arylpropionates as a major product up to 92/8 dr by the same
reaction sequence. High diastereoselectivity in these reactions is contributed to the planar chirality of the arene chromium complex, even
though the reaction was carried out under vigorous basic media. The reaction products, a-allyl b-arylpropionates were derived by 1,3-
M(CO)5 shift and subsequent [3,3]-sigmatropic rearrangement. Also, the corresponding chromium-uncomplexed a,b-unsaturated Fischer
carbene complexes afforded a-allyl b-arylpropionates under the same conditions. Formation of b-allyl b-arylpropionates via 1,2-M(CO)5
shift followed by [3,4]-sigmatropic rearrangement was not observed in both reactions of chromium-coordinated and the corresponding
chromium-uncoordinated a,b-unsaturated Fischer carbene complexes with allyl alkoxide in the presence of base.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
complexes, we have investigated asymmetric reaction of
optically pure a,b-unsaturated Fischer carbene complexes
with planar chirality (Type II, R*ZArCr(CO)3). We
expected that these type of chiral Fischer carbene
complexes would become promising chiral reagents, since
a reactive site is located closely to the chiral auxiliary.
Moreover, these binuclear chiral complexes would be
expected to develop interesting asymmetric reactions
based on the combined nature of two metallic moieties.
However, to best of our knowledge, there is no report on
asymmetric reactions utilizing a,b-unsaturated binuclear
Fischer carbene complexes8 with a planar chiral transition
metal p-complex. Herein, we wish to report asymmetric
reaction utilizing planar chiral binuclear Fischer carbene
complexes with allyl alkoxides.9
Fischer carbene complexes are one of the most versatile
organometallic reagents for organic synthesis,1 and a
number of novel reactions using Fischer carbene complexes
have been reported.2 For instance, a,b-unsaturated Fischer
carbene complexes are significant for organic synthesis such
as Michael addition reaction,3 [3C2]-, [4C2]- and [3C2C1]-
cycloaddition reactions.4–6 Furthermore, optically active
Fischer carbene complexes have attracted increasing
attention as powerful tool of asymmetric reaction, and
various chiral carbene complexes have been developed to
date. Most of these chiral a,b-unsaturated Fischer carbene
complexes have chiral alcohols or amines at the carbene
carbon atom as a stabilizing substituent (type I) due to their
easy preparation (Fig. 1). On the other hand, there are few
examples of the other type of chiral a,b-unsaturated Fischer
carbene complexes, in which a chiral auxiliary is directly
attached to the a,b-unsaturated bond.7 As a synthetic
development of the planar chiral arene chromium
[M]
[M]
X*, R* = Chiral Auxiliary
R
X
R*
X*
Type I
Type II
Keywords: Fischer carbene complexes; Binuclear carbene complexes;
Planar chirality; 1,3-Metal shift; 3,4-Sigmatropic rearrangement;
Enantiomeric excess.
Figure 1. Chiral a,b-unsaturated Fischer carbene complexes.
2. Results and discussion
*
Corresponding authors. Tel.: C81 72 254 9721; fax: C81 72 254
9931 (K.K.); Tel.: C81 75 595 4666; fax: C81 75 595 4763 (M.U.);
e-mail addresses: kamikawa@c.s.osakafu-u.ac.jp;
Barluenga et al. reported10 that aryl a,b-unsaturated Fischer
carbene complexes 1 were treated with allyl alcohol in the
muemura@mb.kyoto-phu.ac.jp
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.10.036

K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
923
presence of a base to give b-allyl b-arylpropionate 4 via
concerted 1,2-M(CO)5 shift followed by [3,4]-sigmatropic
rearrangement (Scheme 1). The allyl group was introduced
at the b-carbon to the ester carbonyl group. Therefore,
b-allyl b-arylpropionates 4 would be expected to obtained
as optically active compounds by utilizing a,b-unsaturated
binuclear Fischer carbene complexes with planar chiral
arene chromium complex as a chiral auxiliary.
version of [3,4]-sigmatropic rearrangement reaction of these
chiral binuclear a,b-unsaturated Fischer carbene complexes
with allyl alkoxides. Initially, we studied the synthesis of
b-allyl b-phenyl propionate 4 (RZPh) by using nonchiral
binuclear Fischer carbene complex 7a according to
Barluenga’s conditions. A reaction was carried out by
stirring a solution of the binuclear carbene complex 7a and
allyl alcohol in the presence of NaH under inert gas in
a balloon, and subsequently exposed to sunlight. Surpris-
ingly, a-allyl b-phenyl propionate 8a was obtained in 75%
yield without formation of b-allyl b-phenyl propionate 4
(RZPh) (Table 2, entry 1). Thus, the allyl group was
regioselectively introduced at the a position to the ester
group. The structure of a-allyl b-phenyl propionate 8a was
absolutely confirmed by comparison with both authentic
samples 8a and 4 (RZPh).12 Both compounds 4 and 8a
OH
1,2- M(CO) shift
5
M(CO)
5
O
OMe
O
–
R
R
[3,4]-sigmatropic
rearrangement
NaH
1
[M]
R = Ph, Furyl M = Cr, W
2
1
could be cleanly distinguished by H NMR spectra. The
–[M]
O
formation of a-allyl b-phenyl propionate 8a is in sharp
contrast to Barluenga’s report, in which the allyl group was
introduced at the b-position.
O
O
R
–
O
R
[M]
3
4
We initially imagined that the distinct difference of two
reaction pathways of a,b-unsaturated Fischer carbene
complexes with allyl alkoxide might be attributed to the
strong electron-withdrawing ability of the tricarbonyl-
chromium fragment. Hence, we examined the reaction of
a,b-unsaturated chromium carbene complex 11 having
p-nitrophenyl group with allyl alkoxide. However, only
ester exchange product 12 was obtained (Scheme 2). Thus,
the electronic effect of the arene ring of a,b-unsaturated
binuclear Fischer carbene complexes does not seem to
control the two reaction pathways. Surprisingly, the
tricarbonylchromium-uncomplexed a,b-unsaturated Fischer
carbene complex 1 (RZPh, MZCr) gave only a-allyl
b-phenyl propionate 8a in 68% yield without detection of
b-allyl b-phenyl propionate 4 (RZPh) by the reaction with
allyl alkoxide under identical conditions with Barluenga’s
report. In this way, we obtained only a-allyl b-phenyl
propionate by reaction with allyl alkoxide in both cases
of a,b-unsaturated Fischer carbene complex 1 and
the corresponding tricarbonylchromium coordinated
a,b-unsaturated Fischer carbene complex 7. Consequently,
we concluded that the structural assignment of the reaction
products is wrong in Barluenga’s report.10
Scheme 1. [3,4]-Sigmatropic rearrangement promoted by [1,2]-metal shift
reported by Barluenga.
2.1. Synthesis of a,b-unsaturated binuclear Fischer
carbene complexes
Chiral binuclear a,b-unsaturated Fischer carbene complexes
7 as starting materials were easily prepared by aldol
condensation of planar chiral o-substituted benzaldehyde
chromium complexes 5 with methylmethoxycarbene
complexes 6 in the presence of triethylamine and
trimethylsilyl chloride in reasonable yields (Table 1).11
The geometry of the double bond of complexes 7 was
1
determined as (E)-configuration by H NMR.
Table 1. Preparation of chiral a,b-unsaturated binuclear Fischer carbene
complexesa
1
1
R
R
M(CO)
5
2
CHO
+
TMSCl, Et N
3
M(CO)
5
OMe
1
3
Et O, 25 ˚C, 24 h
2
Me
OMe
Cr(CO)
Cr(CO)
3
5
6
7
We next extended this interesting reaction to the asym-
metric synthesis of a-allyl b-phenyl propionate by using
planar chiral binuclear carbene complexes. When enantio-
merically pure binuclear Fischer carbene complex 7b ([a]D24
K3400 (c 0.001, CHCl3)), derived from a planar chiral
(K)-(R)-o-methoxybenzaldehyde chromium complex, was
reacted with allyl alkoxide at 25 8C, a-allyl b-(o-methoxy-
phenyl)propionate (8b) ([a]2D3 K25.2 (c 0.09, CHCl3)) was
obtained in 68% yield with 95% ee13 (entry 2). Expectedly,
the a-allyl phenyl propionate 8b was obtained with high ee
despite severe basic conditions.
Entry
Compound
M
R1
Yield 7 (%)
1
2
3
4
5
6
7
8
7a
7b
7c
7d
7e
7f
Cr
Cr
Cr
Cr
W
W
W
W
H
OMe
Me
OPr-i
H
OMe
Me
OPr-i
55
74
60
31
40
59
65
30
7g
7h
a Planar chiral (1R,2S)-enantiomer was used as starting materials in this
study.
The absolute stereochemistry of the compound 8b was
determined as (R)-configuration by comparison of an
optical rotation of authentic (S)-configurated allyl 2-allyl
o-methoxyphenylpropionate (15) ([a]2D3 C27.1 (c 0.38,
CHCl3)) prepared from Evans’ oxazolidone derivative
13 (Scheme 3).14
2.2. Reactions of binuclear Fischer carbene complexes
with allyl alkoxides
Since we have chiral binuclear a,b-unsaturated Fischer
carbene complexes in hand, we examined an asymmetric

924
K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
Table 2. Reaction of binuclear carbene complexes 7 with allyl alcoholsa
Entry
Complex
Temperature (8C)b
Yield 8 (%)
Yield 9 (%)
Yield 10 (%)
ee (%) of 8 or 9c
anti/syn Ratio of 10d
1
2
3
4
5
6
7
8
7a
7b
7b
7b
7b
7c
7c
7c
7d
7e
7e
7f
25
25
0
25
0
25
0
K30
0
25
K30
K30
K30
K30
8a (75)
8b (68)
—
8c (85)
—
8d (83)
—
—
—
—
—
—
9b (40)
—
—
—
—
10b (40)
—
10c (45)
—
10d (40)
10d (30)
10e (51)
10a (71)
10a (75)
10b (65)
10d (70)
10e (31)
—
95
97
72
—
77
93
97
—
—
—
—
—
—
—
—
78/22
—
83/17
—
83/17
80/20
85/15
63/37
92/8
92/8
92/8
75/25
—
9d (55)
9d (33)
9e (10)
9a (10)
—
—
—
—
9
10
11
12
13
14
—
—
—
—
7g
7h
R2
a Reagents and conditions: (a)
, NaH, THF, under inert gas in ballon; (b) hn air, ether
OH
b Reaction time; 30 min for the reaction at 25 8C: 1.5 h for the reaction at 0 or K30 8C.
c Determined by chiral HPLC.
d Determined by integration of representative signals by 1H NMR of the crude product.
When the reaction was performed at 0 8C, the corresponding
a-allyl methyl ester 9b was obtained in 40% yield with 97%
ee along with formation of a-allyl b-hydroxy ester 10b as an
easily separable diastereomeric mixture in 40% yield (entry
3). The stereochemistry of the major a-allyl b-hydroxy ester
10b ([a]3D0 K36.0 (c 0.23, CHCl3)) was determined to
possess the anti (2R,3S)-configuration by comparison with
authentic compound. The authentic methyl 2(R)-allyl-3(S)-
hydroxy-3(o-methoxyphenyl)propionate (18) was prepared
by anti selective aldol reaction of chiral oxazoline
derivative 16 according to the reported procedure15
(Scheme 4).
Cr(CO)
5
Cr(CO)
5
OH
OMe
O
NaH, THF, rt
40 %
O N
2
O N
2
12
11
Scheme 2. Reaction of electron deficient mononuclear carbene complex
with allyl alkoxide.
O
O
OMe
O
OMe
O
S
1) LDA, THF, –78˚C
O
N
O
N
O
OMe OH
O
O
2) CH2=CHCH2Br
40%
O
1) o-anisaldehyde, MgCl ,
2
Et N, TMSCl, EtOAc, rt
3
Bn
R
Bn
O
O
N
N
S
13
14
2) TFA, MeOH
75%
[α]D28 +127.2 (c, 1.78, CHCl3)
Bn
Bn
16
17
30
[α ]
D
–13.8 (c, 0.38, CHCl )
OMe
O
3
1) LiOH, H2O2, THF, H2O
S
O
OMe OH
O
2) SOCl2, toluene
3) allyl alcohol, Et3N, DMAP
54%
R
1) LiOH, H O , THF, H O
2
2
2
S
OMe
[α ]
2) MeOH, p-TsOH
15
[α]D27 +27.1 (c, 0.38, CHCl3)
26
–38.2 (c, 0.22, CHCl )
D
3
18
Scheme 3. Absolute configuration of a-allyl b-(2-methoxyphenyl)
propionate.
Scheme 4. Absolute configuration of a-allyl-b-hydroxy ester.

K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
925
Similarly, with 2-methyl-2-propen-1-ol at 25 8C, the
corresponding b-allyl b-arylpropionate 8c was obtained in
85% yield with 72% ee (Table 2, entry 4). On reaction of 7b
with 2-methyl-2-propen-1-ol at 0 8C, the corresponding
a-allyl-b-hydroxy ester 10c was only obtained with 83/17 dr
(entry 5). Similarly, with o-methyl substituted-arene
chromium complex 7c, the reaction products were con-
trolled by reaction temperature. Thus, a-allyl-b-hydroxy
ester 8d was obtained at 25 8C (entry 6), while the
corresponding a-allyl methyl ester 9d and diastereomeric
a-allyl-b-hydroxy ester 10d were obtained at lower reaction
temperature (entries 7 and 8). The optical yield of 9d
increased to 97% ee in the reaction at K30 8C (entry 8).
When the ortho substituent of the arene chromium complex
was changed to an isopropoxy group, aldol type product 10e
was obtained as a major product in 51% yield with 85/15 dr
(entry 9). In this way, binuclear a,b-unsaturated chromium
carbene complexes with planar chiral arene chromium
complex were reacted with allyl alcohols in the presence of
a base to give [3,3]-sigmatropic rearrangement products,
a-allyl o-substituted phenyl propionate esters, with high ee
without formation of b-allyl b-arylpropionates. Further-
more, when the reaction was performed at lower tempera-
ture under longer reaction time, methyl a-allyl b-hydroxy-
b-arylpropionates 10, were obtained with high anti
selectivity in moderate yield. Thus, the coordination of the
tricarbonylchromium fragment to the arene ring of a,b-
unsaturated Fischer carbene complexes gave optically active
a-allyl b-arylpropionates and a-allyl b-aryl b-hydroxy-
propionates, respectively, with high selectivity by
reaction with allyl alkoxides depending on the reaction
temperature.
high selectivity in spite of vigorous basic conditions. With a
sterically bulky ortho isopropoxy substituent of the arene
chromium complex, diastereomeric ratio decreased to 75/25
(entry 14).
A clarification of origin of the benzylic oxygen of a-allyl-
b-hydroxy-b-arylpropionates 10 in the reaction of the
binuclear carbene complexes 7 is significant for the
reaction mechanism. Although the reaction was carried
out under an inert atmosphere in a balloon, trace amounts
of oxygen might be present in the solvent and/or inert gas.
Therefore, the reaction mixture of 7g, allyl alcohol and
NaH in dry THF was carefully degassed by an inert gas/
freeze/vacuum technique, and the reaction was carried out
in a well-degassed glove box. Consequently, it was found
that the aldol-type product 10d decreased to 15% yield,
and the a-allyl product 9d was obtained in 50% yield. This
result indicates obviously that the benzylic hydroxy group
was introduced from oxygen in the solvent and/or inert
gas. The oxygenated product 10 in the reaction with
hetero-binuclear tungsten carbene complexes was obtained
with higher yield than the reaction with chromium
complexes.
3. Reaction mechanism
On the basis of these results, we propose the reaction
mechanism of a,b-unsaturated binuclear Fischer carbene
complexes with allyl alkoxide in Scheme 5. Nucleophilc
addition of allyl alkoxide at the metal carbene fragment of
–
[M]
–
To further pursue this unique reaction, we next turned our
attention to the reaction of hetero-binuclear tungsten
carbene complexes having planar chiral arene chromium
complexes with allyl alkoxides. A hetero-binuclear tungsten
carbene complex 7e was reacted with allyl alkoxide to give
[3,3]-sigmatropic rearranged products, 9a and 10a. In
analogy with a,b-unsaturated chromium carbene complex
1 (MZCr), the corresponding tungsten carbene complex 1
(RZPh, MZW) gave still a-allyl b-phenyl propionate in
55% yield without detection of b-allyl b-phenyl propionate
reported by Barluenga.10 Thus, a,b-unsaturated chromium
or tungsten carbene complexes afforded always a-allyl
propionates via metal 1,3-shift and subsequent [3,3]-
sigmatropic rearrangement by reaction with allyl alkoxides,
regardless of the coordination of the tricarbonylchromium
fragment to the arene ring. In the case of binuclear tungsten
carbene complex, methyl a-allyl-b-hydroxy-b-aryl propio-
nate 10a was predominantly obtained even at room
temperature (entry 10). The aldol type product 10a was
obtained as sole product with higher diastereoselectivity at
lower reaction temperature (entry 11). Similarly, optically
active tungsten carbene complexes with planar chiral arene
chromium complexes 7f, 7g gave the corresponding a-allyl-
b-aryl-b-hydroxypropionates 10b, 10d in good yields with
high diastereoselectivity by reaction with allyl alkoxide at
K30 8C (entries 12 and 13). Compared with homo-
binuclear chromium complexes, the hetero-binuclear tung-
sten carbene complexes having planar chiral arene
chromium complex gave predominantly anti a-allyl-b-
hydroxy-b-arylpropionates as major reaction product with
Ar(Cr)
H
R
[M]
R
O
H
OMe
O
O
S
–
[M]
Cr(CO)
3
H
Cr(CO)
3
H
[1,3]-M(CO)
shift
OMe
5
OMe
21A
19A
[3,3]-sigmatropic
rearrangement
[1,2]-M(CO) shift
5
X
–
R
–
[M]
[M]
R
–
OMe
O
H
S
+
CO Me
Cr(CO)
H
2
3
20
Cr(CO)
3
22
M = Cr
R
M = W
O
O
R
R
OH
R
OMe
S
OMe
Cr(CO)
3
Cr(CO)
3
24
23
–
[M]
R
R
OMe
H
–
O
[M]
H
OMe
O
S
O
OMe
Cr(CO)
H
3
Cr(CO)
3
H
–
Ar(Cr)
[M]
19B
21B
Scheme 5. Proposed mechanism.

926
K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
–
–
Cr(CO)
5
Cr(CO)
5
OMe
OMe
28
[M]
26
O
E
rel
O
[M]
28B
28A
+34.6
+34.4
26A
+27.7
+15.2
–
26B
Cr(CO)
5
+4.3
27A
[M]
CO Me
2
0.0
–2.3
27B
29
–
Cr(CO)
–
5
29A
OMe
–26.8
–29.5
O
Cr(CO)
5
[M]
O
OMe
29B
[M]
27
A: without Cr(CO)
25
3
B: [M] = Cr(CO)
3
Figure 2. Ab initio calculation.
a,b-unsaturated Fischer carbene complex 7 is initiated to
give tetrahedral intermediates 19A and 19B. A tetrahedral
intermediate 19A would be formed by the addition to
s-transoid configurated carbene carbon of the complex 7,
and another intermediate 19B is formed from s-cisoid
conformer of the complex 7. Generally, [1,2]-M(CO)5
shift16 in a,b-unsaturated Fischer carbene complexes is a
concerted process accompanied with sigmatropic rearrange-
ment. The products derived from this process were not
observed in the reaction of a,b-unsaturated carbene
complexes 1 and 7 with allyl alkoxides. The formation
of (R)-configurated a-allyl arylpropionates 8, 9 and 10
would be explained by 1,3-metal shift17 followed by
[3,3]-sigmatropic rearrangement reaction. 1,3-Metal shift
from the tetrahedral intermediate 19A generates an
intermediate 21 with anti conformation between the
tricarbonylchromium fragment and the pentacarbonylmetal
group due to steric repulsion. Consequently, benzylic
position of the resulting s-allyl chromium complex
21 is S-configuration. Subsequent [3,3]-sigmatropic
rearrangement produces a-allyl b-aryl propionate complex
22 with (R)-configuration at the a-position via 6-membered
chair form 21A. Furthermore, in the case of the chromium
carbene complexes, protonation and the following reductive
elimination of the intermediate 22 occur to give complex
23 as the major product. On the other hand, with tungsten
carbene complexes, the anionic tungsten species is easily
trapped with oxygen followed by reductive elimination to
give anti aldol type products 24. Similarly, the intermediate
19B affords a-allyl b-aryl propionate complex 22 via [3,3]-
sigmatropic rearrangement from the transition state 21B.
Fischer carbene complex (Fig. 2).18,19 The complex
26A and 26B were transition states for the 1,3-metal shift
step of tetrahedral non-chromium coordinated intermediate
25A and the corresponding Cr(CO)3-complexed
intermediate 25B. Activation energies for the 1,3-metal
shift step are 27.7 and 15.2 kcal molK1, respectively.20 On
the other hand, the structures 27A and 27B are the 1,3-metal
shifted stable intermediate of 25A and 25B. The
corresponding chromium-coordinated intermediate 27B is
6.6 kcal molK1 more stable than non-chromium complexed
intermediate 27A. Following [3,3]-sigmatropic rearrange-
ment takes place with exothermicity of almost same
energy in both Cr(CO)3-complexed and non-complexed
intermediates to give rearranged products 29A and 29B.
In contrast, we could not find out the transition state
structures for concerted 1,2-metal shift and 3,4 sigmatropic
rearrangemet giving b-allyl arylpropionate. Theoretical
study also supports that 1,3-metal shift process in
the reaction of a,b-unsaturated Fischer carbene complexes
with allyl alkoxides is favorable reaction path than
1,2-metal shift.
5. Conclusions
The binuclear a,b-unsaturated carbene complexes with
arene chromium complex afforded a-allyl b-arylpropionates
and anti a-allyl-b-hydroxy-b-arylpropionates as optically
enriched compounds via 1,3-M(CO)5 shift and [3,3]-
sigmatropic rearrangement. The corresponding a,b-
unsaturated carbene complexes without tricarbonylchromium
coordination gave also a-allyl b-aryl propionate without
detection of b-allyl b-aryl propionate under the same
reaction conditions.
4. Computational studies
We, furthermore, studied ab initio calculation in this unique
1,3-metal shift process of a,b-unsaturated unsaturated

K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
927
6. Experimental
d 1.42–1.48 (6H, m), 4.72–4.75 (1H, m), 4.81 (3H, s), 5.29
(1H, t, JZ6.4 Hz), 5.69 (1H, d, JZ6.9 Hz), 6.13 (1H, t, JZ
6.4 Hz), 6.48 (1H, d, JZ6.9 Hz), 7.41 (1H, d, JZ15.6 Hz),
7.97 (1H, d, JZ15.6 Hz); 13C NMR (125 MHz, CDCl3) d
21.78, 22.41, 66.38, 72.93, 74.94, 84.43, 94.42, 94.60,
125.26, 138.78, 142.87, 216.67, 232.15, 245.56, 332.18; IR
6.1. General
All manipulations involving organometallics were carried
out under an atmosphere of nitrogen or argon and using inert
gas/vacuum double manifold techniques. All NMR spectra
were recorded in CDCl3 or acetone-d6 solvent with
tetramethylsilane as an internal reference. Mass spectra
were determined with EI or FAB mode. Optical rotations
were obtained at wavelength 589 nm (sodium D line) using
a 1.0-dm cell with a total volume of 5 mL. Diethyl ether and
tetrahydrofuran were distilled from sodium/benzophenone
ketyl immediately before use.
(CHCl3) 2986, 2056, 2000, 1580, 1454, 1252, 992 cmK1
.
Anal. Calcd for C21H16O10Cr2: C, 47.38; H, 3.03. Found: C,
47.57; H, 2.86.
6.2.5. Binuclear carbene complex 7e. Mp 117 8C; 1H
NMR (500 MHz, CDCl3) d 4.72 (3H, s), 5.68 (2H, t, JZ
6.3 Hz), 5.90 (1H, t, JZ6.3 Hz), 6.21 (2H, d, JZ6.3 Hz),
6.97 (1H, d, JZ15.5 Hz), 7.95 (1H, d, JZ15.5 Hz); 13C
NMR (126 MHz, CDCl3) d 59.87, 90.24, 93.24, 93.90,
98.08, 113.36, 148.91, 197.22, 231.53, 233.37, 305.15; IR
6.2. General procedure for preparation of binuclear
a,b-unsaturated Fischer carbene complexes
(CHCl3) 2953, 2067, 2000, 1586, 1451, 1215, 988 cmK1
.
Anal. Calcd for C18H10O9CrW: C, 35.67; H, 1.66. Found: C,
35.71; H, 1.88.
Binuclear Fischer carbene complexes were prepared by
reported procedure.8a,11 To an equimolar solution of
pentacarbonyl[(methoxy)(methyl)carbene]chromium(0)
(1 mmol) and the corresponding benzaldehyde chromium
complex in anhydrous Et2O (0.1 M) was added Et3N
(4 mmol) at room temperature. Then, TMSCl (3 mmol)
was added dropwise at the same temperature, and the
reaction mixture was stirred until disappearance of the
starting material. The solvent was removed in vacuo and the
residue was purified by silica gel chromatography.
6.2.6. Binuclear carbene complex 7f. [a]2D4 K4000 (c
0.001, CHCl3); mp 148 8C; H NMR (500 MHz, CDCl3) d
1
2.34 (3H, s), 4.64 (3H, s), 5.14 (1H, d, JZ6.6 Hz), 5.24 (1H,
t, JZ6.2 Hz), 5.59 (1H, t, JZ6.2 Hz), 5.80 (1H, d, JZ
6.6 Hz), 7.07 (1H, d, JZ15.3 Hz), 7.58 (1H, d, JZ15.3 Hz);
13C NMR (125 MHz, CDCl3) d 56.09, 69.09, 73.23, 84.89,
88.62, 93.28, 94.00, 127.49, 142.65, 143.49, 197.43, 203.93,
231.90, 305.60; IR (CHCl3) 3032, 2951, 2066, 2000, 1580,
1464, 1252, 995 cmK1. Anal. Calcd for C19H12O10CrW: C,
35.87; H, 1.90. Found: C, 35.82; H, 1.93.
6.2.1. Binuclear carbene complex 7a. Mp 116 8C; 1H
NMR (500 MHz, CDCl3) d 4.87 (3H, s), 5.69 (2H, t, JZ
6.0 Hz), 5.89 (1H, t, JZ6.0 Hz), 6.20 (2H, d, JZ6.0 Hz),
6.79 (1H, d, JZ15.6 Hz), 7.98 (1H, d, JZ15.6 Hz); 13C
NMR (125 MHz, CDCl3) d 66.68, 90.74, 93.43, 94.08,
98.33, 125.36, 138.67, 216.39, 224.28, 231.58, 332.02; IR
(CHCl3) 3034, 2957, 2058, 2000, 1586, 1453, 1225,
986 cmK1. Anal. Calcd for C18H10O9Cr2: C, 45.59; H,
2.13. Found: C, 45.64; H, 2.41.
6.2.7. Binuclear carbene complex 7g. [a]2D4 K3800 (c
0.001, CHCl3); mp 145 8C; H NMR (500 MHz, CDCl3) d
1
2.34 (3H, s), 4.64 (3H, s), 5.14 (1H, d, JZ6.6 Hz), 5.24 (1H,
t, JZ6.3 Hz), 5.59 (1H, t, JZ6.3 Hz), 5.80 (1H, d, JZ
6.6 Hz), 7.07 (1H, d, JZ15.3 Hz), 7.58 (1H, d, JZ15.3 Hz);
13C NMR (125 MHz, CDCl3) d 19.45, 69.19, 88.84, 92.04,
92.57, 94.49, 97.74, 111.11, 129.64, 143.69, 197.31, 203.67,
231.97, 305.87; IR (CHCl3) 3032, 2953, 2073, 2000, 1580,
1449, 1219, 995 cmK1. Anal. Calcd for C19H12O9CrW: C,
36.80; H, 1.95. Found: C, 36.70; H, 2.03.
6.2.2. Binuclear carbene complex 7b. [a]2D4 K3400 (c
0.001, CHCl3); mp 88 8C; H NMR (500 MHz, CDCl3) d
1
3.84 (3H, s), 4.82 (3H, s), 4.99 (1H, t, JZ6.3 Hz), 5.10 (1H,
d, JZ6.3 Hz), 5.72 (1H, t, JZ6.3 Hz), 5.94 (1H, d, JZ
6.3 Hz), 6.94 (1H, d, JZ15.3 Hz), 7.78 (1H, d, JZ15.3 Hz);
13C NMR (125 MHz, CDCl3) d 56.06, 66.56, 73.22, 84.87,
88.73, 93.39, 93.97, 122.39, 138.73, 143.65, 211.55, 216.60,
231.93, 331.83; IR (CHCl3) 2957, 2058, 2000, 1580, 1464,
1213, 992 cmK1. Anal. Calcd for C19H12O10Cr2: C, 45.25;
H, 2.40. Found: C, 45.51; H, 2.41.
6.2.8. Binuclear carbene complex 7h. [a]2D3 K2600 (c
0.001, CHCl3); mp 129 8C; H NMR (400 MHz, CDCl3) d
1
1.39 (3H, d, JZ6.0 Hz), 1.49 (3H, d, JZ6.0 Hz), 4.48 (1H,
sep, JZ6.0 Hz), 4.63 (3H, s), 4.94 (1H, t, JZ6.5 Hz), 5.10
(1H, d, JZ6.5 Hz), 5.74 (1H, t, JZ6.5 Hz), 5.92 (1H, d, JZ
6.5 Hz), 7.28 (1H, d, JZ15.6 Hz), 7.66 (1H, d, JZ15.6 Hz);
13C NMR (125 MHz, CDCl3) d 21.80, 22.43, 69.02, 72.98,
74.89, 84.43, 88.06, 94.26, 130.85, 142.56, 142.73, 197.48,
203.88, 232.12, 306.23; IR (CHCl3) 3025, 2988, 2066,
1971, 1941, 1578, 1452, 1219 cmK1; MS (relative intensity)
m/z, 664 (MC, 5), 167 (30), 149 (100), 81 (41); HRMS calcd
for C21H16O10CrW 663.9658, found 663.9651.
6.2.3. Binuclear carbene complex 7c. [a]2D4 K5600 (c
0.001, CHCl3); mp 95 8C; H NMR (500 MHz, CDCl3) d
1
2.34 (3H, s), 4.83 (3H, s), 5.14 (1H, d, JZ6.3 Hz), 5.25 (1H,
t, JZ6.3 Hz), 5.58 (1H, t, JZ6.3 Hz), 5.79 (1H, d, JZ
6.3 Hz), 6.79 (1H, d, JZ15.2 Hz), 7.68 (1H, d, JZ15.2 Hz);
13C NMR (125 MHz, CDCl3) d 19.39, 66.56, 88.92, 92.19,
92.63, 94.46, 98.00, 111.28, 124.60, 139.66, 216.49, 224.27,
232.05, 332.38; IR (CHCl3) 3032, 2959, 2058, 2000, 1580,
1451, 1225, 992 cmK1. Anal. Calcd for C19H12O9Cr2: C,
46.74; H, 2.48. Found: C, 46.48; H, 2.43.
6.3. General procedure for stereoselective [3,3]-sigma-
tropic reactions utilizing binuclear Fischer carbene
complexes
A solution of complex 7 (0.082 mmol) in dry THF (2.0 mL)
was added dropwise to a solution of NaH (66 mg, 60% in
oil, 1.6 mmol) in allyl alcohol (2.0 mL) under argon. The
solution immediately turned from dark purple to yellow.
6.2.4. Binuclear carbene complex 7d. [a]2D4 K2400 (c
0.001, CHCl3); mp 112 8C; 1H NMR (500 MHz, acetone-d6)

928
K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
The reaction mixture was stirred and quenched with
aqueous NH4Cl. The resulting mixture was extracted with
EtOAc and washed with brine. The organic layer was dried
over anhydrous MgSO4 and filtered and concentrated under
reduced pressure. The yellow residue was pushed a plug of
silica gel with EtOAc, and all yellow bands were collected.
Without further purification, the crude reaction mixture was
diluted with ether (5.0 mL) and was exposed to sunlight
until yellow solution became colorless. The precipitate was
filtered off, and the solution was evaporated under reduced
pressure and purified by silica gel chromatography to give a
demetallated product.
5.04–5.22 (4H, m), 5.73–5.83 (2H, m), 7.10–7.13 (4H, m);
13C NMR (126 MHz, CDCl3) d 19.41, 35.32, 45.89,
64.96, 117.20, 118.05, 125.85, 126.50, 129.58, 130.34,
132.16, 135.11, 136.18, 137.29, 174.67; IR (CHCl3) 3013,
2930, 1730, 1495, 1456, 1229, 1165, 924, 741 cmK1; MS
(relative intensity) m/z, 244 (MC, 4), 203 (20), 157 (53), 105
(100), 121 (100), 91 (14); HRMS calcd for C16H20O2
244.1463, found 244.1459. HPLC conditions; Chiralcel OD;
hexane/2-propanolZ20:1; flow rate 1.0 mL/min; column
temperature 40 8C; UV detector 254 nm, retention time,
racemate, 4.1 min, 4.7 min: 8d, 4.1 min.
6.3.5. Methyl 2-allyl-3-phenylpropionate (9a). (Lit. Ref.
22) 1H NMR (500 MHz, CDCl3) d 2.26–2.40 (2H, m), 2.73–
2.81 (2H, m), 2.91–2.99 (1H, m), 3.59 (s, 3H), 5.01–5.09
(2H, m), 5.70–5.80 (1H, m), 7.13–7.29 (5H, m); IR (neat)
3018, 2961, 1722, 1212.
6.3.1. Allyl 2-allyl-3-phenylpropionate (8a). (Lit. Ref. 21)
1H NMR (500 MHz, CDCl3) d 2.26–2.42 (2H, m), 2.76–
2.81 (2H, m), 2.93–2.98 (1H, m), 4.50 (2H, dd, JZ6.0,
1.4 Hz), 5.03–5.09 (2H, m), 5.15–5.22 (2H, m), 5.72–5.83
(2H, m), 7.15–7.28 (5H, m); 13C NMR (126 MHz, CDCl3) d
36.01, 37.75, 47.23, 64.95, 117.18, 118.08, 126.35, 128.37,
128.93, 132.13, 135.05, 139.06, 174.49.
6.3.6. (K)-(R)-Methyl 2-allyl-3-(2-methoxyphenyl)-
1
propionate (9b). [a]D27 K53.6 (c 0.056, CHCl3); H NMR
(500 MHz, CDCl3) d 2.24–2.40 (2H, m), 2.82–2.88 (3H, m),
3.58 (3H, s), 3.82 (3H, s), 5.00–5.08 (2H, m), 5.72–5.80
(1H, m), 6.82–6.87 (2H, m), 7.08 (1H, dd, JZ7.8, 1.4 Hz),
7.19 (1H, dt, JZ7.8, 1.4 Hz); 13C NMR (126 MHz, CDCl3)
d 32.85, 36.31, 45.26, 51.25, 55,20, 110.12, 116.54, 120.15,
127.58, 130.56, 135.35, 157.42, 175.48; IR (CHCl3) 3013,
2953, 1728, 1601, 1494, 1466, 1439 cmK1; MS (relative
intensity) m/z, 234 (MC, 25), 116 (37), 121 (100), 91 (68);
HRMS calcd for C14H18O3 234.1256, found 234.1256.
HPLC conditions; Chiralcel OD; hexane/2-propanolZ9:1;
flow rate 1.0 mL/min; column temperature 40 8C; UV
detector 254 nm, retention time, racemate, 6.4 min,
7.2 min: 9b, 7.2 min.
6.3.2. (K)-(R)-Allyl2-allyl-3-(2-methoxyphenyl)propionate
1
(8b). [a]2D3 K25.2 (c 0.09, CHCl3); H NMR (500 MHz,
CDCl3) d 2.25–2.30 (1H, m), 2.36–2.42 (1H, m), 2.86–
2.91(3H, m), 3.82 (3H, s), 4.49 (2H, ddd, JZ4.6, 3.3,
1.4 Hz), 5.02–5.09 (2H, m), 5.14–5.22 (2H, m), 5.73–5.83
(2H, m), 6.82–6.86 (2H, m), 7.09 (1H, dd, JZ7.3, 1.8 Hz),
7.19 (1H, dt, JZ7.3, 1.8 Hz); 13C NMR (126 MHz, CDCl3)
d 32.84, 36.29, 45.17, 55.16, 64.77, 110.19, 116.75, 117.81,
120.24, 127.44, 127.71, 130.79, 132.33, 135.42, 157.59,
174.89; IR (CHCl3) 3013, 2942, 1728, 1495, 1466, 1246,
1163, 922, 742 cmK1; MS (relative intensity) (FAB) m/z,
260 (MC, 44), 203 (32), 121 (100), 91 (31); HRMS calcd
for C16H20O3 260.1412, found 260.1416. HPLC conditions;
Chiralcel OD; hexane/2-propanolZ100:1; flow rate
1.0 mL/min; column temperature 40 8C; UV detector
254 nm, retention time, racemate, 14.3 min, 16.9 min: 8b,
16.9 min.
6.3.7. (C)-(R)-Methyl 2-(2-methylpropenyl)-3-(2-
methoxyphenyl)propionate (9c). [a]3D0 C24.0 (c 0.05,
CHCl3); H NMR (400 MHz, CDCl3) 1.72 (3H, s), 2.14–
1
2.21(1H, m), 2.35–2.44 (1H, m), 2.73–2.93 (2H, m), 2.96–
3.02 (1H, m), 3.54 (3H, s), 3.81 (3H, s), 4.74 (2H, d, JZ
7.2 Hz), 6.82 (1H, d, JZ7.8 Hz), 6.84 (1H, t, JZ7.8 Hz),
7.07 (1H, dd, JZ7.8, 1.7 Hz), 7.18 (1H, dt, JZ7.8, 1.8 Hz);
13C NMR (100 MHz, CDCl3) 22.17, 33.27, 40.72, 43.99,
51.27, 55.20, 110.14, 111.99, 120.20, 127.52, 127.62,
130.56, 143.00, 157.44, 175.89; IR (CHCl3) 3379, 2928,
1728, 1601, 1464, 1217 cmK1; MS (relative intensity) m/z,
248 (MC, 18), 217 (13), 192 (96), 161 (100), 121 (86), 91
(65); HRMS calcd for C15H20O3 248.1413, found 248.1417.
HPLC conditions; Chiralcel OD; hexane/2-propanolZ20:1;
flow rate 1.0 mL/min; column temperature 40 8C; UV
detector 254 nm, retention time, racemate, 6.7 min,
12.0 min: 9c, 12.0 min.
6.3.3. (K)-(R)-2-Methylpropenyl 2-(2-methylpropenyl)-
3-(2-methoxyphenyl)propionate (8c). [a]2D7 K50.0 (c 0.02,
CHCl3); H NMR (500 MHz, CDCl3) d 1.62 (3H, s), 1.74
1
(3H, s), 2.21 (1H, dd, JZ14.2, 6.4 Hz), 2.43 (1H, dd, JZ
14.2, 8.7 Hz), 2.81 (1H, dd, JZ13.3, 8.7 Hz), 2.89 (1H, dd,
JZ13.3, 6.4 Hz), 3.01–3.07 (1H, m), 3.82 (3H, s), 4.37 (2H,
s), 4.76 (2H, d, JZ6.0 Hz), 4.84 (2H, s), 6.82–6.85 (2H, m),
7.09 (1H, d, JZ7.3 Hz), 7.18 (1H, t, JZ7.3 Hz); 13C NMR
(126 MHz, CDCl3) d 19.40, 22.16, 33.32, 40.75, 43.96,
55.19, 67.50, 110.19, 112.17, 112.82, 120.31, 127.56,
127.70, 130.73, 140.06, 143.02, 157.59, 175.30; IR
(CHCl3) 3000, 2920, 1724, 1648, 1491, 1460, 1240, 1160,
899, 739 cmK1; MS (relative intensity) m/z, 288 (MC, 25),
232 (38), 187 (36), 161 (48), 121 (100), 91 (64), 55 (12);
HRMS calcd for C18H24O3 288.1726, found 288.1723.
HPLC conditions; Chiralcel OD; hexane/2-propanolZ20:1;
flow rate 1.0 mL/min; column temperature 40 8C; UV
detector 254 nm, retention time, racemate, 5.2 min,
6.3 min: 8c, 6.3 min.
6.3.8. (K)-(R)-Methyl 2-allyl-3-(2-methylphenyl)propionate
(9d). [a]2D0 K62.5 (c 0.01, CHCl3); H NMR (500 MHz,
1
CDCl3) d 2.23–2.31 (1H, m), 2.31 (3H, s), 2.34–2.46 (1H,
m), 2.70–2.80 (1H, m), 2.78 (1H, dd, JZ7.9, 20.4 Hz), 2.94
(1H, dd, JZ7.9, 13.3 Hz), 3.59 (3H, s), 5.02–5.10 (2H, m),
5.70–5.80 (1H, m), 7.08–7.14 (4H, m); 13C NMR
(126 MHz, CDCl3) d 19.45, 29.76, 35.23, 36.36,
45.95, 51.46, 117.06, 125.80, 126.45, 129.43, 130.28,
135.08, 137.26, 175.37; IR (CHCl3) 3027, 3013, 2928,
1730, 1213 cmK1; MS (relative intensity) m/z, 218 (MC,
28), 177 (32), 159 (25), 158 (89), 145 (54), 113 (48), 106
6.3.4. (K)-(R)-Allyl 2-allyl-3-(2-methylphenyl)propionate
(8d). [a]2D6 K17.7 (c 0.26, CHCl3); H NMR (500 MHz,
1
CDCl3) d 2.27–2.32 (4H, m), 2.41–2.47 (1H, m), 2.74–2.82
(2H, m), 2.92–2.97 (1H, m), 4.50 (2H, d, JZ5.5 Hz),

K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
929
(28), 105 (100); HRMS calcd for C14H18O2 218.1310, found
218.1310. HPLC conditions; Chiralcel OD; hexane/
2-propanolZ100:1; flow rate 1.0 mL/min; column tempera-
ture 40 8C; UV detector 254 nm, retention time, racemate,
7.5 min, 9.1 min: 9d, 7.5 min.
intensity) m/z, 234 (MC, 2), 157 (10), 121 (100), 114 (91),
93 (66); HRMS calcd for C14H18O3 234.1256, found
234.1251.
6.3.14. (K)-(2R,3S)-Methyl 2-allyl-3-hydroxy-3-(2-iso-
propoxyphenyl)propionate (10e). [a]2D7 K34.8 (c 0.48,
1
6.3.9. (K)-(R)-Methyl 2-allyl-3-(2-isopropoxyphenyl)-
CHCl3); H NMR (500 MHz, CDCl3) d 1.36 (3H, d, JZ
1
propionate (9e). [a]D26 K29.6 (c 0.054, CHCl3); H NMR
6.1 Hz), 1.39 (3H, d, JZ6.1 Hz), 2.12 (1H, quin, JZ
7.2 Hz), 2.34 (1H, quin, JZ7.2 Hz), 3.06 (1H, ddd, JZ9.2,
7.2, 6.1 Hz), 3.44–3.54 (1H, m), 3.65 (3H, s), 4.64 (1H, sep,
JZ6.1 Hz), 4.94–5.05 (3H, m), 5.65–5.75 (1H, m), 6.87
(1H, d, JZ7.9 Hz), 6.91 (1H, t, JZ7.9 Hz), 7.20–7.26 (2H,
m); 13C NMR (126 MHz, CDCl3) d 22.07, 22.29, 34.17,
51.56, 69.84, 72.27, 112.33, 116.74, 120.28, 128.11, 128.59,
129.99, 134.81, 154.52, 174.94; IR (CHCl3) 3366, 3025,
3013, 1730, 1601, 1238 cmK1; MS (relative intensity) m/z,
278 (MC, 2), 165 (43), 149 (8), 123 (100), 121 (15); HRMS
calcd for C16H22O4 278.1518, found 278.1514. HPLC
conditions; Chiralcel OD; hexane/2-propanolZ9:1; flow
rate 1.0 mL/min; column temperature 40 8C; UV detector
254 nm, retention time, racemate, 6.1 min, 7.5 min: 10e,
6.1 min.
(270 MHz, CDCl3) d 1.25–1.30 (6H, m), 2.17–2.32 (2H, m),
2.77–2.80 (2H, m), 3.51 (3H, s), 4.44–4.52 (1H, m), 4.92–
5.19 (3H, m), 5.13–5.68 (1H, m), 6.73–7.10 (4H, m); IR
(CHCl3) 3373, 2983, 1728, 1601, 1454 cmK1; MS (relative
intensity) m/z, 262 (MC, 18), 188 (24), 147 (29), 146 (100),
107 (40); HRMS calcd for C16H22O3 262.1569, found
262.1570.
6.3.10. Methyl 2-allyl-3-hydroxy-3-phenylpropionate
(10a). (Lit. Ref. 23) H NMR (500 MHz, CDCl3) d 2.11–
1
2.17 (1H, m), 2.25–2.31 (1H, m), 2.84–2.88 (2H, m), 3.69
(3H, s), 4.83 (1H, dd, JZ7.8, 5.0 Hz), 5.00–5.04 (2H, m),
5.64–5.72 (1H, m), 7.29–7.38 (5H, m); 13C NMR
(126 MHz, CDCl3) d 33.75, 51.71, 52.77, 74.85, 117.33,
126.41, 128.13, 128.57, 134.30, 141.63, 174.96.
6.3.11. (K)-(2R,3S)-Methyl 2-allyl-3-hydroxy-3-
(2-methoxyphenyl)propionate (10b). [a]3D0 K36.0 (c 0.23,
CHCl3); 1H NMR (270 MHz, CDCl3) d 2.09–2.14 (1H, m),
2.32–2.38 (1H, m), 3.04 (1H, ddd, JZ12.8, 7.3, 5.0 Hz),
3.34 (1H, d, JZ9.2 Hz), 3.66 (3H, s), 3.86 (3H, s), 4.97–
5.04 (3H, m), 5.65–5.73 (1H, m), 6.89 (1H, d, JZ8.7 Hz),
6.96 (1H, t, JZ7.3 Hz), 7.26–7.28 (2H, m); IR (CHCl3)
3555, 2953, 1730, 1641, 1215 cmK1; MS (relative intensity)
m/z, 250 (MC, 2), 138 (10), 137 (100), 135 (19), 107 (21);
HRMS calcd for C14H18O4 250.1205, found 250.1171.
HPLC conditions; Chiralcel OD; hexane/2-propanolZ9:1;
flow rate 1.0 mL/min; column temperature 40 8C; UV
detector 254 nm, retention time, racemate, 10.2 min,
11.1 min: 10b, 10.2 min.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific
Research from Ministry of Education, Culture, Sports,
Science and Technology, Japan. We thank Dr. Jieping Zhu
for helpful discussion.
References and notes
1. Some selected reviews: (a) Doyle, M. P. In Abel, E. W., Stone,
F. G. A., Wilkinson, G., Eds.; Comprehensive Organometallic
Chemistry II; Pergamon: New York, 1995; Vol. 12,
pp 387–420. (b) Wulff, W. D. In Abel, E. W., Stone, F. G. A.,
Wilkinson, G., Eds.; Comprehensive Organometallic Chem-
istry II; Pergamon: New York, 1995; Vol. 12, pp 469–547. (c)
Hegedus, L. S. In Abel, E. W., Stone, F. G. A., Wilkinson, G.,
Eds.; Comprehensive Organometallic Chemistry II; Pergamon:
New York, 1995; Vol. 12, pp 549–600. (d) Metal Carbons in
6.3.12. (K)-(2R,3S)-Methyl 2-(2-methylpropenyl)-3-
hydroxy-3-(2-methoxyphenyl)propionate (10c). [a]D30
K34.3 (c 0.07, CHCl3); H NMR (270 MHz, CDCl3) d
1
1.61 (3H, s), 1.95–2.01 (1H, m), 2.29–2.37 (1H, m), 3.01–
3.16 (1H, m), 3.32 (1H, d, JZ9.1 Hz), 3.55 (3H, s), 3.79
(3H, s), 4.66 (2H, d, JZ1.0 Hz), 4.91 (1H, dd, JZ9.1,
7.0 Hz), 6.79–6.91 (2H, m), 7.17–7.22 (2H, m); IR (CHCl3)
3013, 2957, 1730, 1240, 1215 cmK1; MS (relative intensity)
m/z, 264 (MC, 1), 208 (22), 137 (100), 135 (23), 107 (41);
HRMS calcd for C15H20O4 264.1361, found 264.1360.
HPLC conditions; Chiralcel OD; hexane/2-propanolZ9:1;
flow rate 1.0 mL/min; column temperature 40 8C; UV
detector 254 nm, retention time, racemate, 6.3 min,
7.0 min: 10c, 6.3 min.
¨
Organic Synthesis; Dotz, K.-H., Ed.; Topics in Organometallic
Chemistry; Springer: Berlin, 2004; Vol. 13. (e) Bertrand, G.
(Guest Ed.); J. Organomet. Chem. 2001, 617/618, 3–754.
2. Some selected references: (a) Miura, T.; Iwasawa, N. J. Am.
Chem. Soc. 2002, 124, 518–519. (b) Iwasawa, N.; Shido, M.;
Kusama, H. J. Am. Chem. Soc. 2001, 123, 5814–5815. (c)
´ ´
Barluenga, J.; Lopez, L. A.; Lober, O.; Tomas, M.;
¨
´
´
Garcıa-Granda, S.; Alvarez-Rua, C.; Borge, J. Angew. Chem.,
Int. Ed. 2001, 40, 3392–3394. (d) Barluenga, J.; Aznar, F.;
Palomero, M. A. Angew. Chem., Int. Ed. 2000, 39, 4346–4348.
´ ´
(e) Barluenga, J.; Aznar, F.; Gutierrez, I.; Martın, A.;
´
Garcıa-Granda, S.; Llorca-Baragan˜o, M. A. J. Am. Chem. Soc.
2000, 122, 1314–1324. (f) Barluenga, J.; Ballesteros, A.;
6.3.13. (K)-(2R,3S)-Methyl 2-allyl-3-hydroxy-3-(2-
methylphenyl)propionate (10d). [a]2D7 K40.2 (c 0.48,
CHCl3); 1H NMR (500 MHz, CDCl3) d 2.09–2.15 (1H, m),
2.32–2.37 (4H, m), 2.82 (1H, d, JZ5.5 Hz), 2.87–2.92 (1H,
m), 3.68 (3H, s), 4.99–5.10 (3H, m), 5.63–5.71 (1H, m),
7.14–7.38 (4H, m); 13C NMR (126 MHz, CDCl3) d 19.33,
33.61, 51.68, 52.24, 71.08, 117.29, 125.85, 126.39, 127.77,
130.59, 134.37, 135.22, 139.67, 175.07; IR (CHCl3) 3470,
3081, 3013, 2953, 1723, 1644, 1441 cmK1; MS (relative
´ ´
´
Santamarıa, J.; Bernardo de la Rua, R.; Rubio, E.; Tomas, M.
J. Am. Chem. Soc. 2000, 122, 12874–12875. (g) Barluenga, J.;
´ ´
Rodrıguez, F.; Fan˜anas, F. J.; Rubio, E. Angew. Chem., Int. Ed.
1999, 38, 3084–3086.
3. Some selected references for Michael reactions: (a) Barluenga,
´ ´
J.; Montserrat, J. M.; Florez, J.; Garcıa-Granda, S.; Martin, E.

930
K. Kamikawa et al. / Tetrahedron 62 (2006) 922–930
Chem. Eur. J. 1995, 1, 236–242. (b) Barluenga, J.; Montserrat, hex-5-enoic acid; Majetich, G.; Casares, A. M.; Chapman, D.;
´ ´ ´
J. M.; Florez, J.; Garcıa-Granda, S.; Martın, E. Angew. Chem.,
Behnke, M. Tetrahedron Lett. 1983, 24, 1909–1912.
13. Enantiomeric excess was determined by chiral HPLC with
Chiralcel OD; hexane/2-propanolZ100:1; flow rate 1.0 mL/
min; column temperature 40 8C; UV detector 254 nm,
retention time, racemate, 14.3 min, 16.9 min: 8b, 16.9 min.
14. Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc.
1982, 104, 1737–1739.
Int. Ed. Engl. 1994, 23, 1392–1394. (c) Barluenga, J.; Bernad,
´ ´ ´
P. L., Jr.,; Concellon, J. M.; Pin˜era-Nicolas, A.; Garcıa-Granda,
S. J. Org. Chem. 1997, 62, 6870–6875. (d) Ezquerra, J.; Pedregal,
´
´
C.; Merino, I.; Florez, J.; Barluenga, J.; Garcıa-Granda, S.;
Llorca, M.-A. J. Org. Chem. 1999, 64, 6554–6565. (e) Shi, Y.;
Wulff, W. D.; Yap, G. P. A.; Rheingold, A. L. Chem. Commun.
1996, 2601–2602.
15. Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am.
Chem. Soc. 2002, 124, 392–393.
¨
16. (a) Dotz, K. H.; Christoffers, C.; Knochel, P. J. Organomet.
4. Some selected references for [3C2]-cycloaddition: (a)
´ ´
Barluenga, J.; Fernandez-Marı, F.; Viado, A. L.; Aguilar, E.;
´
Olano, B.; Garcıa-Granda, S.; Moya-Rubiera, C. Chem. Eur. J.
1999, 5, 883–896. (b) Kagoshima, H.; Okamura, T.; Akiyama,
T. J. Am. Chem. Soc. 2001, 123, 7182–7183. (c) Merino, I.;
´
Laxmi, Y. R. S.; Florez, J.; Barluenga, J. J. Org. Chem. 2002,
67, 648–655.
Chem. 1995, 489, C84–C86. (b) Iwasawa, N.; Ochiai, T.;
Maeyama, K. J. Org. Chem. 1998, 63, 3164–3165. (c)
Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc.
1997, 119, 1486–1487. (d) Iwasawa, N.; Ochiai, T.; Maeyama,
K. Organometallics 1997, 16, 5137–5139. (e) Barluenga, J.;
´ ´
Trabanco, A. A.; Florez, J.; Gracıa-Granda, S.; LLlorca, M.-A.
J. Am. Chem. Soc. 1998, 120, 12129–12130. (f) Barluenga, J.;
5. Some selected references for [4C2]-cycloaddition: (a)
Powers, T. S.; Jiang, W.; Su, J.; Wulff, W. D.; Waltermire,
B. E.; Rheingold, A. L. J. Am. Chem. Soc. 1997, 119,
6438–6439. (b) Wulff, W. D.; Bauta, W. E.; Kaesler, R. W.;
Lankford, P. J.; Miller, R. A.; Murray, C. K.; Yang, D. C.
J. Am. Chem. Soc. 1990, 112, 3642–3659. (c) Hsung, R. P.;
Wulff, W. D.; Rheingold, A. L. J. Am. Chem. Soc. 1994, 116,
6449–6450. (d) Beddoes, R. L.; King, J. D.; Quayle, P.
Tetrahedron Lett. 1995, 36, 3027–3028. (e) Hsung, R. P.;
Wulff, W. D.; Challener, C. A. Synthesis 1996, 773–789.
6. Some selected references for [3C2C1]-cycloaddition: (a)
Quinn, J. F.; Powers, T. S.; Wulff, W. D.; YAP, G. P. A.;
Rheingold, A. L. Organometallics 1997, 16, 4945–4947. (b)
´
´
´
´
Tomas, M.; Rubio, E.; Lopez-Pelegrın, J. L.; Garcıa-Granda,
S.; Priede, M. P. J. Am. Chem. Soc. 1999, 121, 3065–3071.
17. (a) Hegedus, L. S.; Lundmark, B. R. J. Am. Chem. Soc.
1989, 111, 9194–9198. (b) Sleiman, H. F.; McElwee-White,
L. J. Am. Chem. Soc. 1988, 110, 8700–8701. (c) Maxey,
C. T.; Sleiman, H. F.; Massey, S. T.; McElwee-White, L.
J. Am. Chem. Soc. 1992, 114, 5153–5160. (d) Fischer, H.;
Schlageter, A.; Bidell, W.; Fru¨h, A. Organometallics 1991,
10, 389–391.
18. All calculations were performed with Gaussian 98: Frisch,
M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.;
Montgomery, Jr., J. A.; Stratmann, R. E.; Burant, J. C.;
Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.;
Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.;
Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.;
Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J.
V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.;
Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.;
Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;
Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.;
Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J.
A. Gaussian 98, Revision A. 5; Gaussian, Inc.: Pittsburgh,
PA, 1998.
¨
Dotz, K. H.; Stinner, C.; Nieger, M. J. Chem. Soc., Chem.
Commun. 1995, 2535–2536. (c) Bao, J.; Wulff, W. D.; Fumo,
M. J.; Grant, E. B.; Heller, D. P.; Whitcomb, M. C.; Yeung, S.-M.
J. Am. Chem. Soc. 1996, 118, 2166–2181.
7. (a) Vorogushin, A. V.; Wulff, W. D.; Hansen, H.-J. J. Am.
¨ ¨
Chem. Soc. 2002, 124, 6512–6513. (b) Dotz, K. H.; Jakel, C.;
Hasse, W.-C. J. Organomet. Chem. 2001, 617–618, 119–132.
¨
(c) Janes, E.; Dotz, K. H. J. Organomet. Chem. 2001, 622,
251–258.
8. Some selected a,b-unsaturated binuclear Fischer carbene
complexes with arene tricarbonylchromium complex or
ferrocene: (a) Sierra, M. A.; del Amo, J. C.; Manchen˜o,
´
M. J.; Gomez-Gallego, M. J. Am. Chem. Soc. 2001, 123,
´
851–861. (b) Barluenga, J.; Lopez, S.; Trabanco, A. A.;
´
Fernandez-Acebes, A.; Florez, J. J. Am. Chem. Soc. 2000, 122,
´
´
8145–8154. (c) Barluenga, J.; Fernandez-Acebes, A.;
´
Trabanco, A. A.; Florez, J. J. Am. Chem. Soc. 1997, 119,
19. Geometry optimizations for Cr complexes 25–29 were carried
out with RHF level theory on using 3-21G(d) basis sets.
20. Total energies of compounds 25A and 25B were K2245.7650
H and K3620.2431 H, respectively. Relative energies were
including zero point energy correction.
7591–7592.
9. A preliminary report:
Kamikawa, K.; Tachibana, A.;
Shimizu, Y.; Uchida, K.; Furusyo, M.; Uemura, M. Org.
Lett. 2004, 6, 4307–4310.
´ ´ ´
10. Barluenga, J.; Rubio, E.; Lopez-Pelegrın, J. A.; Tomas, M.
21. Zou, X.-W.; Lu, T.-M.; Song, J.; Wu, F.-H.; Shen, Y.-J.
Huadong Ligong Daxue Xuebao 2003, 29, 210–213.
Angew. Chem., Int. Ed. 1999, 38, 1091–1093.
11. Aumann, R.; Heinen, H. Chem. Ber. 1987, 120, 537–540 and
Ref. 8a.
22. Kim, D. H.; Li, Z.-H.; Lee, S. S.; Park, J.-Il.; Chung, S. J.
Bioorg. Med. Chem. 1998, 6, 239–249.
12. Authentic samples 4 (RZPh) and 8a were prepared by allyl
esterification of 3-phenyl-hex-5-enoic acid and LDA-mediated
a-allylation of b-phenyl propionate, respectively. 3-Phenyl-
23. (a) Hart, D. J.; Krishnamurthy, R. J. Org. Chem. 1992, 57,
4457–4470. (b) Urabe, H.; Takeda, T.; Hideura, D.; Sato, F.
J. Am. Chem. Soc. 1997, 119, 11295–11305.