Synthesis of trans -Cycloalkenes via Enantioselective Cyclopropanation and Skeletal Rearrangement

Article abstract of DOI:10.1021/ja5096045

An efficient one-pot two-step procedure for asymmetric synthesis of piperidine-fused trans-cycloalkenes is reported. The method comprises the initial enantioselective installation of another cyclopropane ring onto methylenecyclopropanes and the subsequent thermal skeletal rearrangement in which the installed and inherent cyclopropane rings are both opened. A concerted mechanism is proposed for the latter thermal rearrangement reaction together with a closed transition state model.

Full text of DOI:10.1021/ja5096045

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Communication
Synthesis of trans-Cycloalkenes via Enantioselective
Cyclopropanation and Skeletal Rearrangement
Tomoya Miura, Takayuki Nakamuro, Chia-Jung Liang, and Masahiro Murakami
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja5096045 • Publication Date (Web): 22 Oct 2014
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Synthesis of trans-Cycloalkenes via Enantioselective
Cyclopropanation and Skeletal Rearrangement
Tomoya Miura,* Takayuki Nakamuro, Chia-Jung Liang,† Masahiro Murakami*
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Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan
Supporting Information Placeholder
N-sulfonyl-1,2,3-triazoles.11 Our previous study12 on the reac-
tion of spiropentanes led us to examine the use of methylene-
ABSTRACT: An efficient one-pot two-step procedure for
asymmetric synthesis of piperidine-fused trans-cycloalkenes is
reported. The method comprises the initial enantioselective
installation of another cyclopropane ring onto methylenecy-
cyclopropanes, hoping that enantioenriched spiropentanes be-
came accessible.13,14 Thus, we treated methylenecyclopropane
2a (1.5 equiv), which was synthesized from cis-cyclooctene
simply according to a literature procedure,15 with 1-mesyl-4-
clopropanes and the subsequent thermal skeletal rearrangement
phenyl-1,2,3-triazole (1a, 1.0 equiv) in the presence of (tBu-
in which the installed as well as inherent cyclopropane rings
are both opened. A concerted mechanism is proposed for the
CO2)4Rh2 (1.0 mol %) and 4 Å molecular sieves (MS) in
latter thermal rearrangement reaction together with a closed
CHCl3 (0.2 M) at 40 °C (eq 1). The cyclopropanation reaction
transition state model.
was complete in 5 h, and after chromatographic purification,
α-imino spiropentane 3a was obtained as a single diastereomer
Both cis and trans isomers are synthetically accessible for
cyclic alkenes consisting of more than 7 carbon atoms. Unlike
acyclic alkenes, trans isomers of cyclic alkenes from seven- to
ten-membered ring are less stable than their cis counterparts.1
Seven-membered trans-cycloheptene is too distorted to retain
its trans geometry at temperatures higher than –78 °C.2 The
torsion strain is alleviated by increment of the ring-size, and
eight-membered trans-cyclooctene is stable at room tempera-
ture. Medium-sized cyclic trans-alkenes take twisted forms,
and are characterized by planar chirality. The properties inher-
ent to their unique structures have found a wide variety of ap-
plications in organic synthesis3 and chemical biology.4 There-
fore, the development of stereoselective preparative methods
of medium-sized cyclic trans-alkenes has been a subject of
considerable investigation.5 Yet, synthetic methods available
for optically active ones are limited. There are only a few ex-
amples of enantioselective syntheses,6 and the other precedents
are based on either resolution of racemates7 or multi-step deri-
vatization of chiral pool molecules.8 Now, we report a one-pot
two-step procedure for the synthesis of enantioenriched piperi-
dine-fused trans-cycloalkenes from achiral methylenecyclo-
propanes and triazoles. The procedure can be modified even to
directly start from terminal alkynes in place of triazoles (Fig-
ure 1).
in 85% yield. The stereochemistry is explained by assuming
that the carbenoid species has added onto the exocyclic C–C
double bond of 2a from its less-hindered side.
(tBuCO2)4Rh2
Ms
Ms
N
(1.0 mol %)
N
H
(1)
+
8
N
CHCl3, MS
40 °C, 5 h
8
N
Ph
Ph
2a (1.5 equiv)
1a
3a 85%
Next, the thermal reactivities16 of 3a were investigated, and
an unprecedented rearrangement reaction was identified; when
3a in CHCl3 (0.2 M) was heated at 120 °C under microwave
irradiation (MW) in a sealed microwave vial for 2 h, the piper-
idine-fused cyclononene 4a was cleanly formed in a stereo-
chemically pure form (85% isolated yield), and its nOe study
1
in H-NMR proved the trans geometry for its bridgehead dou-
ble bond (eq 2). The C(1)–C(1’) σ-bond, C(2’)–C(3’) σ-bond,
and C(2)–N(3) π-bond of 3a are cleaved, and instead the N(3)–
C(3’) σ-bond, C(1)–C(2) π-bond, and C(1’)–C(2’) π-bond are
newly formed with 4a with installation of a trans geometry for
the C(1’)–C(2’) double bond. These bond cleavages and for-
mations result in a structural reorganization of the tricyclic
skeleton into the twisted bicyclic skeleton.
Ms
N3
Ms
R
N 3
2
1
H
Ms
2
1
3'
Ms
N
+
MsN3
+
cat. cat.
CuI RhII
H
N
3'
2'
9
(2)
H
R
∆
*
1'
H
CHCl3, 120 °C/MW, 2 h
n
Ph
8
1'
n
2'
Ph
n
3a
4a 85%
R
This thermal rearrangement reaction is generalized as de-
picted in Figure 2. If we focus on the cleavage of the C(1)–
Figure 1. Construction of piperidine-fused trans-cycloalkenes
C(1’) σ-bond occurring with A and the formation of the N(3)–
C(3’) σ-bond occurring with B, the former σ-bond migrates to
the new position between the N(3) and C(3’) atoms which are
both two atoms removed from the bonded loci. In this sense,
the present skeletal rearrangement can be described as a [3,3]
sigmatropic rearrangement. In the case of the retro process17 of
the Claisen rearrangement from C to D, which would serve as
a prototype for [3,3] sigmatropic rearrangement, the C(1)–
C(1’) σ-bond being cleaved with C is flanked by two
from terminal alkynes, mesyl azide, and methylenecyclopropanes.
N-Sulfonyl-1,2,3-triazoles are readily prepared from termi-
nal alkynes and N-sulfonyl azides using copper(I) catalyst.9
Upon treatment with rhodium(II) or nickel(0) complexes, they
generate metal complexes of α-imino carbenes, which subse-
quently react with various electron-rich compounds.10 Fokin
and co-workers reported a rhodium(II)-catalyzed, highly enan-
tioselective cyclopropanation reaction of simple alkenes with
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(The present skeletal rearrangement)
(retro-Claisen rearrangement)
97% ee to assure the integrity of chirality transfer within an
experimental accuracy during the skeletal rearrangement. In
2
2
2
1
2
3
4
3
2
3
1
1
O3
1
1
O3
N
order to determine the absolute stereochemistry of 4a, we fol-
lowed a procedure in literature19 to treat it with trans-
PtCl2(2,4,6-collidine)(η2-ethylene). The resulting platinum(II)
complex 5 was obtained as a crystalline solid and its single-
crystal X-ray analysis proved the absolute stereochemistry.20
N
1'
3'
1'
2'
1'
3'
3'
3'
1'
2'
2'
2'
A
C
D
B
5
Figure 2. The general diagram of thermal rearrangement.
6
7
8
9
[(S)-NTTL]4Rh2
π-electron systems. Terminal sp2 atoms [O(3) and C(3’)]
change into sp3 atoms by losing a π-bond and gaining a new σ-
bond between themselves. The structural deviation of A from
(2.5 mol %)
1a
2a
+
3a
4a
CHCl3
CHCl3, MS
40 °C, 8 h
(1.5 equiv)
86%
83% (97% ee)
120 °C/MW
2 h
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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41
42
43
44
45
46
47
48
49
50
51
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53
54
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56
57
58
59
60
(96% ee)
C is that a cyclopropane ring replaces one π-electron system of
C. With A, the σ-bond being cleaved is flanked by one π-
electron system and one cyclopropane ring. The sp3 C(3’) loses
the σ-bond to C(2’) gaining a new σ-bond to N(3). The major
driving force of the present skeletal rearrangement is presuma-
bly attributed to the release of the ring strain of the spirocyclic
structure (ca. 61 kcal/mol), which is considerably larger than
the double of the ring strain of a simple cyclopropane ring (ca.
28 kcal/mol).18
Cl
Pt
Cl
Ms
(3)
N
N
(1.0 equiv)
Ph
4a
Cl
Pt
CH2Cl2
rt, 13 d
Cl
N
5 80%
The transition state model F is proposed for the skeletal rear-
rangement of 3a in analogy with that of the retro process of the
Claisen rearrangement reaction (Scheme 1).17 The sigmatropic
interconversion between γ,δ-unsaturated aldehydes and allyl
vinyl ethers is assumed to proceed via a closed six-membered
chair-like transition state model E. The α-imino spiropentane
3a can be considered as the cyclopropane homolog of γ,δ-
unsaturated aldehydes, and therefore, the transition state model
F which is conformationally analogous to E can be expected
on the mechanistic pathway from 3a to 4a. The transition state
model F reasonably depicts how the stereochemistry at the
C(2’) position dictates the geometry of the resulting bridge-
head double bond. The substituent at C(2’) orients downward
in parallel to the methylene bridge of the adjacent cyclopro-
pane ring, and upon skeletal rearrangement, the π-bond devel-
ops in between with these orientations retained. Further sup-
port was lent to the transition state model F by additional ex-
perimental results (vide infra).
The two-step transformation of 1a and 2a into the enantioen-
riched 4a was successfully integrated into a one-pot procedure
(Table 1).21 The trans-cyclononene 4a was prepared in 88%
yield with 97% ee by applying the two reaction conditions to
the mixture of 1a and 2a in sequence (entry 1). Various other
4-aryl-substituted triazoles 1b–e were subjected to the one-pot
procedure, and similar results were obtained when a mixed
solvent of chloroform/methanol was used; trans-cyclononenes
4b–e were produced in good yield with enantioselectivities
ranging from 93% ee to 98% ee (entries 2–5). 4-(1-
Cyclohexenyl)triazole 1f was also a suitable triazole (entry 6).
On the other hand, a complex mixture arose from alkyl-
substituted triazoles, because the latter thermal skeletal process
was more sluggish.
Table 1. One-Pot Transformation of Triazoles 1 and 2aa
Ms
N
1) [(S)-NTTL]4Rh2 (2.5 mol %)
Ms
Scheme 1. The Proposed Transition State Model
CHCl3, MS, 40 °C, 8 h
N
+
N
(retro-Claisen rearrangement)
2) CHCl3, 120 °C/MW, 2 h
R1
R1
N
‡
R1
3'R2
2a (1.5 equiv)
R1
R1
1
4
3
O
3
2
3'
3
3'
2
2
O
R2
R3
O
R2
yield (%)b
1
R1
4
entry
ee (%)
1
1
1'
1'
1
1'
2'
2'
R3
2'
R3
1
2
3
4
5
6
4a
4b
4c
4d
4e
4f
88
97
98
97
96
93
98
1a
1b
1c
1d
1e
1f
Ph
E
(this work)
82c
91c
88c
93c
83
4-MeO-C6H4
4-CF3-C6H4
2-naphthyl
3-thienyl
‡
H
nOe
H
H
Ms
Ms
3
Ms
3
N3
3'
3'
3'
2
2
2
N
H
H
H
N
1
1
1
1'
2'
1'
2'
Ph
Ph
Ph
1'
2'
4a
3a
F
Thus, the piperidine-fused trans-cyclononene 4a was stere-
oselectively constructed from 2a through the cyclopropanation
with 1a and subsequent thermal skeletal rearrangement. Next,
we challenged the asymmetric synthesis of 4a by using chiral
rhodium(II) catalysts in the first cyclopropanation reaction. As
with the case of cyclopropanation of simple alkenes,11 an ex-
cellent enantioselectivity of 96% ee was observed with 3a
when [(S)-NTTL]4Rh2 (2.5 mol %, NTTL = N-naphthoyl-tert-
leucinate) was used as the catalyst (eq 3). Of note was that
three new chiral centers were stereoselectively installed in a
single step. Then, the enantioenriched spiropentane 3a was
subjected to the second skeletal rearrangement reaction. The
resulting trans-cyclononene 4a exhibited an enantiopurity of
1-cyclohexenyl
aA 0.2 mmol scale. bYield of isolated product (average of two
runs). cThe second step [CHCl3/MeOH (1/1), 100 °C/MW, 3 h].
Exemplified in Scheme 2 is an ultimate one-pot procedure
starting directly from terminal alkynes. An arylethyne, mesyl
azide, 2a, CuTC, [(S)-NTTL]4Rh2, MS, and CHCl3 were all
placed in a reaction vessel, and the reaction mixture was stirred
from 0 °C to 25 °C for 10–16 h, and subsequently at 100 °C
under MW irradiation for additional 3 h. Finally, the cooled
reaction mixture was subjected to chromatographic purifica-
tion. The products 4a, 4b, and 4f were isolated in 60–67 %
overall yields with excellent enantioselectivities (97–99% ee)
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according to this all-in-one-pot procedure. It is notable that the oriented away from the other propyl group (eq 7). The first
1
2
3
4
5
6
7
8
molecular complexities including the absolute stereochemistry
have dramatically increased through this one-pot process, dur-
ing which a work-up procedure is executed only once.
cyclopropanation reaction would have occurred selectively
from the less-hindered side of 2c to form the intermediary spi-
ropentane 3c diastereoselectively as with the case of 2a.
Granting this stereoselectivity, the double bond stereochemis-
try of 6 is in accordance with the proposed transition state
model I with the two propyl groups oriented downward, one is
in a pseudoaxial position and the other is in a pseudoequatorial
position, which is also virtually similar to the model F.
Scheme 2. One-Pot Synthesis Starting from Terminal Al-
kynes
1) 10 mol % CuTC
R1
Ms
N
2.5 mol % [(S)-NTTL]4Rh2
+
1) (tBuCO2)4Rh2 (1.0 mol %)
CHCl3, MS, 0 °C–rt, 10–16 h
Ms
nPr
9
nPr
MsN3
CHCl3, MS, 40 °C, 8 h
N
2) CHCl3/MeOH (1/1)
100 °C/MW, 3 h
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
R1
+
1a
+
2a (1.5 equiv)
2) CHCl3, 120 °C/MW, 2 h
Ph
nPr
2c (1.5 equiv)
nPr
R1 = Ph
R1 = 4-MeO-C6H4
R1 = 1-cyclohexenyl
4a 67% (97% ee)
4b 60% (99% ee)
4f 63% (97% ee)
3c
(7)
Ms
N
‡
nPr
H
Ms
nPr
N
H
H
In order to corroborate the transition state model F proposed
above, the two-step transformation was examined in more de-
tail using a pair of symmetrically disubstituted methylenecy-
clopropanes 2b and 2c prepared from trans- and cis-oct-4-ene,
respectively. The cyclopropanation reaction of the racemic 2b
with the triazole 1a using (tBuCO2)4Rh2 as the catalyst yielded
a 5:2 mixture of diastereomers 3b1 and 3b2 (eq 4). The dia-
stereomers were separated by HPLC, and their structures were
determined by a set of NMR analyses (DEPT, COSY, HMQC,
HMBC, and nOe).
Ph
Ph
nPr
nPr
I
6 85%
Methylenecyclopropanes derived from cycloalkenes of other
ring-sizes than eight were also employed in the sequential
transformation. When 10-methylenebicyclo[7.1.0]decene (2d),
derived from cis-cyclononene, was subjected to the cyclopro-
panation reaction with 1a using [(S)-NTTL]4Rh2 as the catalyst
at 40 °C, the second skeletal rearrangement reaction occurred
concurrently with the first cyclopropanation to directly furnish
trans-cyclodecene 8 in 94% yield with 97% ee (eq 8). We sup-
pose that the faster reaction may be ascribed to the confor-
mation of the intermediate spiropentane derived from 2d; the
intermediate spiropentane would be conformationally closer to
the transition state of the skeletal rearrangement than in the
case of 3a so that a smaller structural change is required to
reach the transition state.
(tBuCO2)4Rh2
Ms
Ms
nPr
nPr
nPr
(2.0 mol %)
N
N
(4)
1a
+
+
CHCl3, MS
40 °C, 4 h
Ph
nPr
Ph
nPr
nPr
(rac)
3b1 67% NMR
3b2 26% NMR
2b (1.5 equiv)
The subsequent skeletal rearrangement of the major dia-
stereomer 3b1 under the standard thermal conditions
(120 °C/MW) was slower than that of 3a to afford piperidine
derivative 6 in 44% yield after 14 h (eq 5). Noteworthy was the
exclusive stereochemistry of the exocyclic double bond; the
propyl substituent is oriented away from the other propyl
group. In contrast, the rearrangement of the minor diastere-
omer 3b2 was much faster than that of 3b1 to selectively pro-
duce the geometrical isomer 7 with its propyl substituent ori-
ented in the opposite direction in 85% yield (eq 6). The stereo-
specificity observed with the reaction using the pair of the
diastereomers 3b1 and 3b2 is well accounted for by assuming
the transition state models G and H, which are similar to the
model F in Scheme 1. Moreover, the transition state models G
and H explain the slower reaction of 3b1; the transition state
model G having the two propyl substituents in pseudoaxial
positions would be energetically higher than H having the two
propyl substituents in pseudoequatorial positions.
Ms
[(S)-NTTL]4Rh2
Ms
N
(2.5 mol %)
N
+
9
(8)
10
N
CHCl3, MS
40 °C, 14 h
Ph
N
Ph
8
2d (1.5 equiv)
1a
93% (97% ee)
The stability of planar chirality of medium-sized trans-
cycloalkenes generally decreases with increment in ring size,
and trans-cyclononene racemizes considerably faster (t1/2 = 6 s
at 30 °C) than trans-cyclooctene (t1/2 = ~105 years at 30 °C)
through swiveling of the twisted double bond.22 Nonetheless,
double bond swiveling was not observed with both 4a and 8 up
to 120 °C. We suppose that the twisted conformation is locked
by the central chirality at the bridgehead position,8a which has
been originally set in the achiral molecules upon the enantiose-
lective cyclopropanation.
On the other hand, the eight-membered trans-cyclooctene
derivative 9 (eq 9) was expected to be more strained than the
cyclononene and cyclodecene counterparts 4a and 8.1 We next
tried to synthesize 9 by using 8-methylenebicyclo[5.1.0]octane
(2e), derived from cis-cycloheptene. When the standard condi-
tions of the one-pot two-step transformation (2.5 mol % of
[(S)-NTTL]4Rh2 at 40 °C for 8 h, then at 120 °C/MW for 2 h)
were applied to a mixture of 1a and 2e, the major product was
the corresponding α-imino spiropentane because the second
rearrangement reaction was considerably slower than that of
3a. Then, the duration of time of heating (120 °C/MW) for the
second skeletal rearrangement was extended to 12 h, and a
mixture of trans-cyclooctene 9 (18% NMR yield, 98% ee), cis-
cyclooctene 10 (40% NMR yield, 98% ee), and 1,3-diene 1123
(37% NMR yield, 6% ee) was generated. Although it was pos-
Ms
‡
Ms
nPr
nPr
Ms
nPr
N
N
N
(5)
H
H
H
CHCl3
Ph
Ph
Ph
nPr
nPr 120 °C/MW
nPr
6 44%
G
3b1
14 h
‡
Ms
N
Ms
nPr
H
Ms
nPr
N
nPr
N
(6)
nPr
nPr
CHCl3
Ph
Ph
Ph
nPr
H
120 °C/MW
14 h
3b2
H
H
7 85%
On the other hand, the one-pot, two-step transformation of
2c, prepared from cis-oct-4-ene, using 1a and (tBuCO2)4Rh2
yielded the piperidine derivative 6 with the propyl substituent
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Journal of the American Chemical Society
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sible to separate them by HPLC, a mixture of 9 and 10 (5:2)24
resulted again even when the purified trans-cyclooctene 9 was
left in vacuo at room temperature for 9 h. Thus, decrease in
ring size from nine to eight brought about a significant in-
crease in the structural strain.
K.; Nishikawa, R.; Suzuki, M.; Igawa, K. J. Am. Chem. Soc. 2010,
132, 9232 and references therein.
1
2
3
4
5
6
7
8
(7)
(a) Tomooka, K.; Komine, N.; Fujiki, D.; Nakai, T.;
Yanagitsuru, S. J. Am. Chem. Soc. 2005, 127, 12182. (b) Tomooka,
K.; Suzuki, M.; Shimada, M.; Yanagitsuru, S.; Uehara, K. Org.
Lett. 2006, 8, 963.
Ms
1) [(S)-NTTL]4Rh2, (2.5 mol %)
(8)
(a) Nakazaki, M.; Naemura, K.; Nakahara, S. J. Org.
CHCl3, MS, 40 °C, 8 h
N
+
Chem. 1979, 44, 2438. (b) Sudau, A.; Münch, W.; Nubbemeyer,
U.; Bats, J. W. J. Org. Chem. 2000, 65, 1710. (c) Larionov, O. V.;
Corey, E. J. J. Am. Chem. Soc. 2008, 130, 2954. (d) Prévost, M.;
Woerpel, K. A. J. Am. Chem. Soc. 2009, 131, 14182.
7
N
2) CHCl3, 120 °C/MW, 12 h
N
Ph
2e (1.5 equiv)
1a
(9)
9
Ms
N
Ms
N
(9)
Raushel, J.; Fokin, V. V. Org. Lett. 2010, 12, 4952.
Ms
N
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(10)
Davies, H. M. L.; Alford, J. S. Chem. Soc. Rev. 2014, 43,
+
+
8
5151 and references therein.
8
8
Ph
Ph
(11)
Chuprakov, S.; Kwok, S. W.; Zhang, L.; Lercher, L.;
Ph
9
10
11
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Soc. 2007, 129, 12596.
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A.; de Meijere, A.; Dzhemilev, U. M. Chem. Rev. 2014, 114, 5775.
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18% NMR (98% ee) 40% NMR (98% ee)
37% NMR (6% ee)
Matsuda, T.; Tsuboi, T.; Murakami, M. J. Am. Chem.
In summary, we have developed a new method for the
asymmetric synthesis of piperidine-fused trans-cycloalkenes,
which comprises the enantioselective construction of a cyclo-
propane ring and the thermal skeletal rearrangement opening
the two cyclopropane rings.
For a review: (a) D’yakonov, V. A.; Trapeznikova, O.
(14)
A singular example of related intramolecular cyclopro-
ASSOCIATED CONTENT
panation of a methylenecyclopropane moiety is reported: Chen,
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Supporting Information. Experimental procedures, spectral data
for the new compounds, and details of the X-ray analysis. This
material is available free of charge via Internet at
http://pubs.acs.org.
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For a review: (a) de Meijere, A.; Kozhushkov, S. I.
AUTHOR INFORMATION
Corresponding Author
tmiura@sbchem.kyoto-u.ac.jp; murakami@sbchem.kyoto-u.ac.jp
Notes
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For reviews: (a) Carpenter, N. E.; Overman, L. E. Org.
The authors declare no competing financial interest.
†C.L. is on leave from Department of Chemistry, National Taiwan
Normal University, Taipei, Republic of China.
React. 2005, 66, 1. (b) Majumdar, K. C.; Bhattacharyya, T.; Chat-
topadhyay, B.; Sinha, B. Synthesis 2009, 2117. For recent exam-
ples: (c) Boeckman, R. K.; Genung, N. E.; Chen, K.; Ryder, T. R.
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ACKNOWLEDGMENT
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Beckhaus, H.-D.; Rüchardt, C.; Kozhushkov, S. I.; Be-
The paper is dedicated to Prof. A. B. Smith, III on the occasion of
his 70th birthday. We thank Dr. Y. Nagata (Kyoto University) for
kind help in an X-ray analysis and Prof. K. Tomooka and Dr. K.
Igawa (Kyushu University) for useful advice. This work was sup-
ported in part by a Grant-in-Aid for Scientific Research (B) from
MEXT and the ACT-C program of the JST.
lov, V. N.; Verevkin, S. P.; de Meijere A. J. Am. Chem. Soc. 1995,
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ometallics 2010, 29, 6632.
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signed by analogy.
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Whang, J. J.; Winkler, H. J. S. J. Am. Chem. Soc. 1965, 87, 3644.
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tion is under way.
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see reference 2.
Tomooka, K.; Shimada, M.; Uehara, K.; Ito, M. Organ-
The absolute configurations of other products were as-
Jones, A. C.; May, J. A.; Sarpong, R.; Stoltz, B. M. An-
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