Ring-opening reaction of vinylidenecyclopropanediesters catalyzed by Re2(CO)10 or Yb(OTf)3

Article abstract of DOI:10.1002/ejoc.201001398

Ring-opening reaction of vinylidenecyclopropanediesters catalyzed by Re₂(CO)₁₀ or Yb(OTf)₃ afforded 2H-pyran-2-one derivatives or α,β-unsaturated ketones in moderate to good yields through a highly regioselective carbon-ca

Full text of DOI:10.1002/ejoc.201001398

FULL PAPER
DOI: 10.1002/ejoc.201001398
Ring-Opening Reaction of Vinylidenecyclopropanediesters Catalyzed by
Re2(CO)10 or Yb(OTf)3
Lei Wu[a] and Min Shi*[a]
Keywords: Regioselectivity / Cleavage reactions / Small ring systems / Rhenium / Ytterbium
Ring-opening reaction of vinylidenecyclopropanediesters
catalyzed by Re2(CO)10 or Yb(OTf)3 afforded 2H-pyran-2-one
derivatives or α,β-unsaturated ketones in moderate to good
yields through a highly regioselective carbon–carbon bond
cleavage pathway. The substituents at the cyclopropane
mainly determine the regioselectivity of the carbon–carbon
bond cleavage, providing different products of tandem ring-
opening and rearrangement reactions.
nium has very special catalytic properties. Most rhenium
complexes are stable with different oxidation states and are
moisture- and air-tolerant, resulting in their diverse applica-
tion in catalytic organic reactions as homogeneous cata-
lysts.[11] Herein, we wish to report an interesting intramolec-
ular ring-opening reaction of VDCP-diesters through a re-
gioselective carbon–carbon bond cleavage catalyzed by
Re2(CO)10 or Yb(OTf)3 to produce the corresponding 2H-
pyran-2-one derivatives or α,β-unsaturated ketones, sub-
stantially enriching the chemistry of highly strained small
rings as well as rhenium-catalyzed reactions.
Introduction
Vinylidenecyclopropanes (VDCPs),[1] containing an al-
lene moiety and a connected cyclopropane ring in their
structural motif, are one of the most fascinating organic
compounds in the chemistry of highly strained small rings.
It is already known that these highly strained cyclopropanes
are easily available, thermally stable, and yet reactive sub-
stances, which can easily undergo a variety of novel intra-
molecular rearrangements or intermolecular reactions with
many electrophiles either upon heating and photoirradia-
tion[2] or catalyzed by a variety of Lewis or Brønsted ac-
ids.[3–5] It is quite clear that the release of the highly strained
energy associated with the ring opening of a cyclopropane
moiety in an organic molecule can lead to novel tandem
transformations, and the reaction pathway highly depends
on the electronic properties of the substituents on the cyclo-
propane ring as well as the functional groups connected to
the cyclopropane.[6,7] We anticipated that the geminal instal-
lation of two electron-withdrawing groups (EWGs) at the
cyclopropane ring connected with an allene moiety might
further promote carbon–carbon bond cleavage of cyclopro-
pane, leading to a highly regioselective ring-opening reac-
tion.[8] In our previous work on the reactivity of VDCP-
diesters, we found that they could undergo interesting cy-
cloaddition reactions with 1,3-dipoles to afford the corre-
sponding cycloadducts in good yields under mild condi-
tions.[9,10] These results have stimulated us to further ex-
plore other novel reactions of VDCP-diesters in the pres-
ence of Lewis acids or transition metals. During our ongo-
ing investigations, we realized that the transition metal rhe-
Results and Discussion
Initial experiments were carried out by using VDCP-dies-
ter 1a as the substrate in the presence of a series of catalysts
at 110 °C in toluene to determine the most effective catalyst.
We found that the reaction was complete within 3 d, giving
2H-pyran-2-one 2a in 40% yield in the presence of Re2-
(CO)10 (5 mol-%) (Table 1, Entry 1). Adding LiOH·H2O
(1.2 equiv.) to assist the hydrolysis of the ester groups of 1a
afforded complex product mixtures (Table 1, Entry 2).
Other commonly used transition metals such as Ru3(CO)12
and Ru(PPh3)2Cp*Cl as well as Lewis acids such as PtCl2,
Ph3PAuI, Yb(OTf)3, In(OTf)3, Sc(OTf)3, BF3·OEt2,
Fe(OTf)2·2CH3CN, Cu(OTf)2, Zn(OTf)2 and the Brønsted
acid trifluoromethanesulfonic acid TfOH were not effective
catalysts in this reaction, leading to either complex product
mixtures or no reaction. On the basis of catalyst screening,
it was found that only Re2(CO)10 was a suitable catalyst in
this reaction and this is the first example of a Re2(CO)10-
catalyzed intramolecular cyclization of VDCP-diesters as
far as we know. The carbonyl complex Ru3(CO)12 has no
catalytic activity for this reaction.
[a] State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, China
Fax: +86-21-64166128
We next examined solvent effects of this reaction by
using Re2(CO)10 as the catalyst, and the results of these
experiments are summarized in Table 1. Examination of the
E-mail: Mshi@mail.sioc.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201001398.
Eur. J. Org. Chem. 2011, 1099–1105
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1099

L. Wu, M. Shi
FULL PAPER
Table 1. Optimization of the reaction conditions.
Entry[a]
Additive
Solvent
Temperature
[°C]
Time
[d]
Yield
[%][b]
1
2
3
4
5
6
7
8
9
–
toluene
toluene
xylene
DMF
dioxane
110
110
130
110
110
110
130
130
130
110
110
3
3
3
3
3
3
1
1
1
1
1
40
complex
trace
nr
trace
36
LiOH·H2O (1.2 equiv.)
–
–
–
–
TCE
–
chlorobenzene
chlorobenzene
chlorobenzene
ortho-dichlorobenzene
ortho-dichlorobenzene
45
64
70
78
H2O (10 equiv.)
H2O (20 equiv.)
H2O (10 equiv.)
MeOH (10 equiv.)
10
11
56
[a] All reactions were carried out with VDCP-diester 1a (0.2 mmol), Re2(CO)10 (5 mol-%), and the additives upon heating in the solvent
(2.0 mL), and the reaction was monitored by TLC unless otherwise specified. [b] Isolated yield.
reaction temperature indicated that the ring-opening reac- Table 2. Re2(CO)10-catalyzed intramolecular reactions of VDCP-
diesters 1.[a]
tion could only take place at Ͼ100 °C, perhaps due to the
high energy required for carbon–carbon bond cleavage.
Screening of several solvents with high boiling points re-
vealed that the use of chlorobenzene afforded 2a in 45%
yield at 130 °C within 1 d, and other solvents such as xy-
lene, N,N-dimethylformamide (DMF), dioxane, and 1,1,2,2-
tetrachloroethane (TCE) were not suitable for this reaction
(Table 1, Entries 3–7). In the presence of 10 and 20 equiv. of
H2O, 2a could be formed in 64 and 70% yield, respectively
(Table 1, Entries 8 and 9). These results suggest that the ex-
tra proton source can accelerate the reaction, giving the cy-
clized product in higher yield. Moreover, in ortho-dichloro-
benzene with the addition of 10 equiv. of H2O at 110 °C,
the reaction proceeded more smoothly, affording 2a in 78%
yield within 1 d (Table 1, Entry 10). The use of MeOH as
the proton source gave no improvement (Table 1, Entry 11).
Therefore, the best reaction conditions involve the use of
chlorobenzene as the solvent at 130 °C with the addition of
20 equiv. of H2O (conditions A) or the use of ortho-dichlo-
robenzene as the solvent at 110 °C with the addition of
10 equiv. of H2O (conditions B) both in the presence of
Re2(CO)10 (5 mol-%).
Entry[b]
Substrate R1
R2
Product, Yield [%][c]
1
2
3
4
1b
1c
1d
1e
1f
Bn
Me
Me
Me
Me
Me
H
nPr
Bn
iPr
nC5H11
Ph
2b, 70 (74)
2c, 68 (70)
2d, 61 (55)
2e, 62 (62)
2f, 70 (73)
2g, 51 (46)
5
6[d]
1g
[a] Conditions A: At 130 °C in chlorobenzene (2.0 mL) with the ad-
dition of H2O (20 equiv.). Conditions B: At 110 °C in ortho-dichlo-
robenzene (2.0 mL) with the addition of H2O (10 equiv.). [b] All
reactions were carried out with VDCP-diester 1 (0.2 mmol) and
Re2(CO)10 (5 mol-%) under conditions A or B, and the reaction
was monitored by TLC unless otherwise specified. [c] Isolated
yield. Yield of the product obtained under conditions B is given in
parentheses. [d] The reaction was carried out with VDCP-diester
1g (0.2 mmol) in the presence of Re2(CO)10 (5 mol-%) in chloroben-
zene (2.0 mL) at 130 °C or in ortho-dichlorobenzene (2.0 mL) at
110 °C without the addition of H2O.
With these optimal reaction conditions in hand, we fur-
ther investigated the scope of this interesting intramolecular
cyclization reaction with respect to various VDCP-diesters
The structure of compound 2e was further established by
1, and the results are summarized in Table 2. As for VDCP- a single-crystal X-ray diffraction (Figure 1).[12]
diesters 1 in which R2 = H or alkyl, the reactions proceeded
To identify the effect of H2O in the reaction, we carried
smoothly to afford desired products 2 in moderate to good out an isotopic labeling control experiment (Scheme 1). Un-
yields under conditions A or B (Table 2, Entries 1–5). In the der the standard reaction conditions (conditions A), using
case of VDCP-diester 1g in which R2 = phenyl, we found D2O to replace H2O, desired product 2b-d was obtained in
that this substrate was sensitive to the extra proton source, 67% yield along with 76%D incorporation, indicating that
leading to nucleophilic attack of H2O at the cyclopropane. H2O did play an important role in this reaction.
The corresponding cyclized product could be obtained in
51 and 46% yield under conditions A and B, respectively, sensitive to H2O, it was found that it could easily undergo
without the addition of H2O (Table 2, Entry 6). nucleophilic attack by H2O (20 equiv.) in chlorobenzene at
As mentioned above, because VDCP-diester 1g was quite
1100
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Eur. J. Org. Chem. 2011, 1099–1105

Ring-Opening Reaction of Vinylidenecyclopropanediesters
Table 3. Reaction of VDCP-diesters 1 with H2O.
Entry[a]
1, Ar
Cat. (x mol-%)
3
Yield of 3 [%][b]
1
2
3
4
5
6
7
8
1g, Ph
Re2(CO)10 (5)
Yb(OTf)3 (10)
Re2(CO)10 (5)
Yb(OTf)3 (10)
Re2(CO)10 (5)
Yb(OTf)3 (10)
Re2(CO)10 (5)
Yb(OTf)3 (10)
3g
3g
3h
3h
3i
51
88 (92)[c]
46
1g, Ph
1h, p-MeC6H4
1h, p-MeC6H4
1i, p-ClC6H4
1i, p-ClC6H4
1j, p-BrC6H4
1j, p-BrC6H4
85 (86)[c]
30
Figure 1. ORTEP drawing of 2e.
3i
78 (72)[c]
30
3j
3j
81 (85)[c]
[a] All reactions were carried out with VDCP-diesters 1 (0.2 mmol),
the catalyst Re2(CO)10 (5 mol-%) or Yb(OTf)3 (10 mol-%), and
H2O (10 equiv.) in chlorobenzene or toluene (2.0 mL) at 110 °C,
and the reaction was monitored by TLC unless otherwise specified.
[b] Isolated yield. [c] Yield of the product obtained for the reaction
conducted in toluene is given in parentheses.
Scheme 1. Isotopic labeling control experiment.
130 °C to give the corresponding α,β-unsaturated ketone 3g
in 50% yield in the presence of Re2(CO)10, disfavoring the
formation of 2H-pyran-2-one 2g (Scheme 2). Decreasing
the amount of H2O to 10 equiv. and lowering the reaction
temperature to 110 °C produced 3g in 51% yield (Table 3,
Entry 1). the use of VDCP-diesters 1h–j having an aromatic
ring at the terminus of the allene moiety gave similar results
in the presence of Re2(CO)10 (5 mol-%) and H2O (10 equiv.)
in chlorobenzene at 110 °C, affording 3h–j in 30–46% yield
(Table 3, Entries 3, 5, and 7). Similar results were obtained
with the addition of 4 Å molecular sieves (MS), suggesting
that their use as an additive did not devoid the reaction
system of water. Furthermore, we found that by using
Yb(OTf)3 (10 mol-%) as the catalyst in this reaction, the
corresponding α,β-unsaturated ketones 3g–j could be
formed in higher yields in chlorobenzene or toluene
(Table 3, Entries 2, 4, 6, and 8).
come of the above reaction, plausible mechanisms for the
formation of these ring-opening products are tentatively
outlined in Schemes 4–6. As for VDCP-diester 1, in which
R2 = H or alkyl, we believe that the rhenium catalyst can
coordinate with the carbonyl group and the allene moiety
simultaneously, although the active rhenium species is not
clear. Cleavage of the C1–C2 bond takes place to give inter-
mediate A, in which the oxygen anion is bonded to the rhe-
nium catalyst, and then intermediate A undergoes 1,2-H
shift to afford intermediate B and its resonance-stabilized
intermediate C along with the regeneration of the rhenium
catalyst. Cyclization of intermediate C gives intermediate D,
which undergoes nucleophilic attack with H2O to provide
intermediates E and F. Then, elimination of R1OH affords
final product 2 (Scheme 4).
Cyclopropane has significant π character,[13] providing
the kinetic opportunity to initiate the release of strain. In
1,1-cyclopropanediesters, this ring bond can be polarized
and further weakened by coordination of a Lewis acid to
one or both of the ester moieties.[14] As for VDCP-diester 1
having an aromatic ring at the terminus of the allene moi-
ety, the C–C cyclopropane bond is initially activated by
Yb(OTf)3 through coordination with the ester moieties; it
can then easily undergo nucleophilic attack by H2O to give
intermediate G through C1–C2 bond cleavage, indicating
that this vinylidenecyclopropane substrate is more sensitive
to H2O. Intermediate G can tautomerize to corresponding
Scheme 2. Re2(CO)10-catalyzed reaction of VDCP-diesters 1g with
H2O.
In the case of VDCP-diester 1k, the intramolecular ring- product 3 through intermediate H (Scheme 5).
opening reaction took place in a different way, affording In the case of VDCP-diester 1k having an iPr group at
products 4k, 5k, and 6k in 86% total yield under the stan- the cyclopropane ring, its reaction mechanism is partially
dard conditions, probably because the iPr substituent at the similar to the cyclopropane ring opening of VDCP-diester
cyclopropane ring activates the C1–C3 bond to make it 1a as described in Scheme 4. The carbonyl group and allene
more sensitive to cleavage than the C1–C2 bond under these moiety coordinate with the rhenium catalyst at the same
reaction conditions (Scheme 3).
time, but the ring opening takes place through a different
The mechanism of this unprecedented reaction has not path involving nucleophilic attack of H2O at the middle
been unequivocally established, but on the basis of the out- carbon atom of the allene moiety along with C1–C3 bond
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1101

L. Wu, M. Shi
FULL PAPER
Scheme 3. Re2(CO)10-catalyzed reaction of VDCP-diester 1k.
Scheme 4. A plausible reaction mechanism for the formation of 2H-pyran-2-one 2.
Scheme 5. A plausible reaction mechanism for the formation of α,β-unsaturated ketone 3.
cleavage to afford intermediate I. Intermediate I can pro-
duce intermediate J, leading to corresponding product 6k
Conclusions
along with the regeneration of the rhenium catalyst. De-
In summary, we have reported an interesting ring-open-
carboxylation of 6k under the reaction conditions produces ing reaction of vinylidenecyclopropanediesters through a
product 4k. Proton transfer of 6k can give intermediate L highly regioselective carbon–carbon bond cleavage pathway
via intermediate K, which undergoes tautomerization to catalyzed by Re2(CO)10 or Yb(OTf)3 to produce 2H-pyran-
give product 5k (Scheme 6).
2-one derivatives or α,β-unsaturated ketones in moderate to
Scheme 6. A plausible reaction mechanism for the ring-opening reaction of VDCP-diester 1k.
1102
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Ring-Opening Reaction of Vinylidenecyclopropanediesters
ν = 3083, 2956, 2923, 2852, 1753, 1626, 1562, 1430, 1364, 1266,
˜
good yields. The geminal installation of two EWGs at the
cyclopropane ring significantly facilitates C–C bond cleav-
age, which exclusively takes place at C1–C2, leading to the
tandem ring-opening reaction. However, introduction of
another substituent at the cyclopropane ring causes exclus-
ive C1–C3 bond cleavage, affording different reaction prod-
ucts. The outcome of the reactions is mainly dependent on
the electronic properties of the substituents at the cyclopro-
pane ring as well as at the terminus of allene moiety. Clarifi-
cation of the reaction mechanism and further application
of this chemistry are in progress.
1096, 792 cm–1. MS (EI): m/z (%) = 168 (70) [M]+, 140 (75), 137
(58), 109 (100), 85 (54), 84 (72), 49 (85). HRMS: calcd. for C8H8O4
168.0423; found 168.0425.
Compound 2b: Yield: 36 mg, 74%; yellow oil. 1H NMR (400 MHz,
CDCl3, TMS): δ = 2.32 (s, 3 H, CH3), 5.33 (s, 2 H, OCH2), 6.12
(dd, J = 7.2, 0.8 Hz, 1 H, CH =), 7.30–7.39 (m, 3 H, Ar), 7.43–
7.45 (m, 2 H, Ar), 8.15 (d, J = 7.2 Hz, 1 H, CH=) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 20.6, 67.0, 103,5, 113.6, 128.15,
128.24, 128.5, 135.6, 149.9, 158.1, 163.1, 169.1 ppm. IR (NaCl): ν
˜
= 3064, 3034, 2955, 2926, 1756, 1628, 1556, 1278, 1109, 788, 739,
698 cm–1. MS (EI): m/z (%) = 244 (6) [M]+, 226 (6), 138 (39), 110
(62), 91 (100), 71 (5), 65 (18), 43 (15). HRMS: calcd. for C14H12O4
244.0736; found 244.0733.
Experimental Section
Compound 2c: Yield: 29 mg, 70%; colorless oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 0.94 (t, J = 7.6 Hz, 3 H, CH3), 1.36–
1.41 (m, 2 H, CH2), 1.64–1.72 (m, 2 H, CH2), 2.56 (t, J = 7.6 Hz,
2 H, CH2), 3.90 (s, 3 H, OCH3), 6.14 (d, J = 7.2 Hz, 1 H, CH=),
8.18 (d, J = 7.2 Hz, 1 H, CH=) ppm. 13C NMR (100 MHz, CDCl3,
TMS): δ = 13.6, 22.1, 28.8, 34.0, 52.6, 102.9, 113.8, 150.1, 158.4,
General Remarks: Melting points were determined with a digital
1
melting point apparatus. H and 13C NMR spectra were recorded
at 400 and 100 MHz, respectively. LRMS and HRMS were re-
corded by the EI method. Employed solvents were dried by stan-
dard procedures. Commercially obtained reagents were used with-
out further purification. All reactions were monitored by TLC with
silica gel coated plates. Flash column chromatography was carried
out by using 300–400 mesh silica gel at increased pressure. Because
VDCP-diesters and some products are unstable and quite labile,
the obtainment of elemental analytic data was difficult and only
HRMS data are given.
164.2, 172.9 ppm. IR (NaCl): ν = 2956, 2919, 2852, 1745, 1619,
˜
1553, 1272, 1109, 1002, 784 cm–1. MS (EI): m/z (%) = 210 (8)
[M]+, 197 (3), 169 (6), 153 (22), 127 (14), 113 (19), 99 (24), 85 (78),
71 (78), 57 (100). HRMS: calcd. for C11H14O4 210.0892; found
210.0895.
Compound 2d: Yield: 31 mg, 61%; light yellow oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 2.86 (t, J = 7.2 Hz, 2 H, CH2), 3.02
(t, J = 7.2 Hz, 2 H, CH2), 3.89 (s, 3 H, OCH3), 6.04 (d, J = 7.2 Hz,
1 H, CH=), 7.15–7.31 (m, 5 H, Ar), 8.12 (d, J = 7.2 Hz, 1 H, CH=)
ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 32.8, 36.0, 52.6,
103.5, 114.0, 126.6, 128.2, 128.6, 139.3, 150.0, 158.2, 164.0,
General Procedure for the Reaction of VDCP-diesters under Stan-
dard Reaction Conditions: Under an Ar atmosphere, VDCP-diester
1
(0.2 mmol, 1.0 equiv.), Re2(CO)10 (5 mol-%) or Yb(OTf)3
(10 mol-%), H2O (10 or 20 equiv.), and chlorobenzene or ortho-
dichlorobenzene (2.0 mL) were added into a Schlenk tube. The re-
action mixture was stirred at 110 or 130 °C for 1–3 d and moni-
tored by TLC until the reaction was complete. Then, the reaction
mixture was directly applied to a silica gel column to give the corre-
sponding product.
171.2 ppm. IR (NaCl): ν = 3027, 2953, 2926, 2854, 1753, 1627,
˜
1556, 1435, 1287, 1113, 1009, 791, 700 cm–1. MS (EI): m/z (%) =
258 (11) [M]+, 153 (5), 139 (2), 115 (2), 104 (2), 91 (100), 71 (4), 65
(6), 49 (9). HRMS: calcd. for C15H14O4 258.0892; found 258.0896.
VDCP-diesters 1a–d,[9] 1g–k,[9] and product 3g[9] are known com-
pounds.
VDCP-Diester 1e: Yield: 29 mg, 65%. 1H NMR (400 MHz, CDCl3,
TMS): δ = 1.03 (d, J = 6.8 Hz, 6 H, 2CH3), 2.40–2.48 (m, 3 H,
CH, CH2), 3.75 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 5.66–5.70
(m, 1 H, CH=) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ =
19.4, 21.78, 21.83, 28.6, 34.6, 52.5, 52.6, 85.7, 107.7, 167.6, 167.7,
1
Compound 2e: Yield: 26 mg, 62%; yellow solid; m.p. 95–96 °C. H
NMR (400 MHz, CDCl3, TMS): δ = 0.97 (d, J = 6.8 Hz, 6 H, 2
CH3), 2.09–2.19 (m, 1 H, CH), 2.42 (d, J = 6.8 Hz, 2 H, CH2), 3.90
(s, 3 H, OCH3), 6.15 (d, J = 6.8 Hz, 1 H, CH=), 8.19 (d, J = 6.8 Hz,
1 H, CH=) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 22.1,
27.0, 43.2, 52.5, 103.9, 113.7, 149.9, 158.4, 164.1, 172.0 ppm. IR
(NaCl): ν = 2958, 2928, 1766, 1714, 1626, 1557, 1435, 1291, 1111,
˜
1007, 789 cm–1. MS (EI): m/z (%) = 210 (34) [M]+, 182 (10), 168
(17), 153 (75), 136 (100), 125 (16), 111 (13), 85 (65), 71 (47), 57
(78). HRMS: calcd. for C11H14O4 210.0892; found 210.0894.
186.9 ppm. IR (NaCl): ν = 2959, 2870, 1738, 1436, 1313, 1275,
˜
1235, 1193, 1108 cm–1. MS (EI): m/z (%) = 224 (14) [M]+, 177 (11),
165 (51), 149 (15), 133 (37), 105 (56), 86 (66), 84 (100), 59 (33).
HRMS: calcd. for C12H16O4 224.1049; found 224.1050.
Compound 2f: Yield: 35 mg, 73%; light yellow oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 0.89 (t, J = 6.8 Hz, 3 H, CH3), 1.26–
1.36 (m, 6 H, 3CH2), 1.65–1.73 (m, 2 H, CH2), 2.56 (t, J = 7.6 Hz,
2 H, CH2), 3.90 (s, 3 H, OCH3), 6.15 (d, J = 7.2 Hz, 1 H, CH=),
8.18 (d, J = 7.2 Hz, 1 H, CH=) ppm. 13C NMR (100 MHz, CDCl3,
TMS): δ = 13.9, 22.4, 26.7, 28.6, 31.3, 34.2, 52.5, 102.9, 113.7,
VDCP-Diester 1f: Yield: 34 mg, 68%. 1H NMR (400 MHz, CDCl3,
TMS): δ = 0.89 (t, J = 6.8 Hz, 3 H, CH3), 1.29–1.33 (m, 4 H,
2CH2), 1.39–1.46 (m, 2 H, CH2), 2.09–2.14 (m, 2 H, CH2), 2.42–
2.43 (m, 2 H, CH2), 3.75 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3),
5.64–5.69 (m, 1 H, CH) ppm. 13C NMR (100 MHz, CDCl3, TMS):
δ = 13.8, 19.3, 22.2, 28.0, 28.8, 31.0, 34.5, 52.5, 52.6, 84.6, 100.5,
150.1, 158.4, 164.1, 172.9 ppm. IR (NaCl): ν = 2955, 2929, 2858,
˜
1759, 1626, 1556, 1436, 1287, 1113, 1009, 791 cm–1. MS (EI): m/z
(%) = 238 (26) [M]+, 207 (14), 188 (15), 168 (23), 153 (100), 136
(73), 125 (9), 108 (8), 84 (41), 59 (17). HRMS: calcd. for C13H18O4
238.1205; found 238.1207.
167.61, 167.66, 188.0 ppm. IR (NaCl): ν = 2955, 2929, 2858, 1736,
˜
1436, 1276, 1241, 1107 cm–1. MS (EI): m/z (%) = 252 (2) [M]+, 196
(71), 164 (100), 137 (41), 121 (51), 105 (57), 91 (36), 79 (24), 59 (36),
55 (22). HRMS: calcd. for C14H20O4 252.1362; found 252.1364.
1
Compound 2a: Yield: 26 mg, 78%; yellow solid; m.p. 90–91 °C. H
Compound 2g: Yield: 25 mg, 51%; light yellow oil. 1H NMR
NMR (400 MHz, CDCl3, TMS): δ = 2.34 (s, 3 H, CH3), 3.90 (s, 3 (400 MHz, CDCl3, TMS): δ = 3.86 (s, 2 H, CH2), 3.89 (s, 3 H,
H, OCH3), 6.16 (dd, J = 7.2, 0.8 Hz, 1 H, CH=), 8.18 (d, J =
7.2 Hz, 1 H, CH=) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ =
20.6, 52.6, 103.7, 113.7, 150.2, 158.3, 164.1, 169.1 ppm. IR (NaCl):
OCH3), 6.00 (dd, J = 7.2, 1.2 Hz, 1 H, CH=), 7.25–7.38 (m, 5 H,
Ar), 8.14 (d, J = 7.2 Hz, 1 H, CH=) ppm. 13C NMR (100 MHz,
CDCl3, TMS): δ = 40.4, 52.6, 103.4, 114.1, 127.7, 129.0, 129.3,
Eur. J. Org. Chem. 2011, 1099–1105
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1103

L. Wu, M. Shi
FULL PAPER
134.0, 150.0, 158.0, 164.0, 171.0 ppm. IR (NaCl): ν = 3030, 2954,
Supporting Information (see footnote on the first page of this arti-
˜
1
2925, 2854, 1755, 1627, 1556, 1277, 1111, 789, 700 cm–1. MS (EI):
cle): H NMR and 13C NMR spectra of VDCP-diesters 1e and 1f
m/z (%) = 244 (25) [M]+, 213 (5), 153 (100), 128 (6), 125 (4), 85 and compounds 2, 3, 4k, 5k and 6k and crystallographic data of
(34), 84 (10), 65 (10), 49 (14). HRMS: calcd. for C14H12O4
244.0736; found 244.0731.
2e.
Compound 3h: Yield: 50 mg, 86%; light yellow oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 2.38 (s, 3 H, CH3), 3.34 (d, J =
6.8 Hz, 2 H, CH2), 3.78 (s, 6 H, 2OCH3), 4.02 (t, J = 6.8 Hz, 1 H,
CH), 6.71 (d, J = 16.4 Hz, 1 H, CH=), 7.21 (d, J = 8.0 Hz, 2 H,
Ar), 7.45 (d, J = 8.0 Hz, 2 H, Ar), 7.59 (d, J = 16.4 Hz, 1 H, CH=)
ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 21.5, 39.3, 46.6,
52.8, 124.3, 128.4, 129.7, 131.4, 141.3, 143.8, 169.4, 196.2 ppm. IR
Acknowledgments
We thank the Shanghai Municipal Committee of Science and Tech-
nology (08dj1400100–2), the National Basic Research Program of
China (973)-2009CB825300, and the National Natural Science
Foundation of China for financial support (20872162, 20672127,
20732008, 20821002 and 20702013). Mr. Jie Sun in the State Key
Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry is also thanked for performing the X-ray dif-
fraction experiments.
(NaCl): ν = 3003, 2954, 2925, 2854, 1738, 1691, 1665, 1613, 1513,
˜
1436, 1281, 978, 802, 543 cm–1. MS (EI): m/z (%) = 210 (6) [M]+,
275 (11), 259 (5), 227 (5), 158 (18), 145 (100), 115 (30), 91 (14), 71
(7), 55 (6). HRMS: calcd. for C16H18O5 290.1154; found 290.1151.
Compound 3i: Yield: 49 mg, 78%; light yellow oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 3.34 (d, J = 6.8 Hz, 2 H, CH2), 3.78
(s, 6 H, 2OCH3), 4.02 (t, J = 6.8 Hz, 1 H, CH), 6.72 (d, J = 16.4 Hz,
1 H, CH=), 7.38 (d, J = 8.4 Hz, 2 H, Ar), 7.48 (d, J = 8.4 Hz, 2
H, Ar), 7.56 (d, J = 16.4 Hz, 1 H, CH=) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 39.5, 46.6, 52.9, 125.6, 129.3, 129.5,
[1] For the synthesis of VDCPs, see: a) K. Isagawa, K. Mizuno,
H. Sugita, Y. Otsuji, J. Chem. Soc. Perkin Trans. 1. 1991, 2283–
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132.6, 136.7, 142.2, 169.3, 196.0 ppm. IR (NaCl): ν = 2955, 2925,
˜
2854, 1744, 1696, 1613, 1489, 1435, 1012, 962 cm–1. MS (EI): m/z
(%) = 244 (16), 165 (47), 152 (23), 139 (57), 105 (100), 91 (19), 77
(42). HRMS: calcd. for C15H15ClO5 310.0608; found 310.0606.
Compound 3j: Yield: 60 mg, 85%; yellow solid; m.p. 120–122 °C.
1H NMR (400 MHz, CDCl3, TMS): δ = 3.33 (d, J = 6.8 Hz, 2 H,
CH2), 3.78 (s, 6 H, 2 OCH3), 4.02 (t, J = 6.8 Hz, 1 H, CH), 6.73
(d, J = 16.4 Hz, 1 H, CH=), 7.41 (d, J = 8.4 Hz, 2 H, Ar), 7.53 (d,
J = 8.4 Hz, 2 H, Ar), 7.54 (d, J = 16.4 Hz, 1 H, CH=) ppm. 13C
NMR (100 MHz, CDCl3, TMS): δ = 39.5, 46.6, 52.8, 125.0, 125.7,
[2] a) K. Mizuno, H. Sugita, T. Hirai, H. Maeda, Y. Otsuji, M.
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129.7, 132.2, 133.1, 142.2, 169.3, 195.9 ppm. IR (NaCl): ν = 2954,
˜
2925, 2853, 1732, 1689, 1611, 1585, 1487, 1434, 1262, 1160, 1009,
973, 802 cm–1. MS (EI): m/z (%) = 211 (41), 209 (40), 181 (8), 155
(6), 113 (16), 102 (64), 85 (42), 71 (55), 57 (100), 43 (91). HRMS:
calcd. for C15H15BrO5 354.0103; found 354.0101.
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Compounds 4k/5k: Ratio = 1.0:0.6. Yield: 20 mg, 47%; light yellow
1
oil. H NMR (400 MHz, CDCl3, TMS): δ = 1.08 (d, J = 6.8 Hz, 6
H, 2 CH3, 4k), 2.34 (s, 3 H, CH3, 4k), 2.59–2.71 (m, 1 H, CH, 4k),
3.34 (s, 2 H, CH2, 4k), 3.66 (s, 3 H, OCH3, 4k), 6.58 (d, J = 10.0 Hz,
1 H, CH=, 4k), 1.74 (s, 1.8 H, CH3, 5k), 1.80 (s, 1.8 H, CH3, 5k),
2.19 (s, 1.8 H, CH3, 5k), 3.67 (s, 1.8 H, OCH3, 5k), 3.71 (s, 1.8 H,
OCH3, 5k), 3.90 (d, J = 10.4 Hz, 0.6 H, CH=, 5k), 4.14 (t, J =
10.4 Hz, 0.6 H, CH=, 5k), 4.85 (d, J = 10.4 Hz, 0.6 H, CH=, 5k)
ppm. 13C NMR (100 MHz, CDCl3, TMS, 4k/5k): δ = 18.2, 22.0,
25.1, 25.9, 28.8, 28.9, 30.8, 51.9, 52.7, 53.0, 117.8, 139.8, 152.9,
168.5, 168.7, 206.4 ppm. IR (NaCl): ν = 2955, 2931, 2859, 1737,
˜
1717, 1434, 1347, 1149, 1029 cm–1. MS (GC–EI, 4k): m/z = 152
[M – CH3OH]+, 125, 109, 99, 81, 67, 59. MS (GC–EI, 5k): m/z =
242 [M]+, 200, 179, 167, 140, 125, 109, 99, 81, 67, 59.
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Compound 6k: Yield: 19 mg, 39%; light yellow oil. 1H NMR
(400 MHz, CDCl3, TMS): δ = 1.08 (d, J = 6.4 Hz, 6 H, 2 CH3),
2.37 (s, 3 H, CH3), 2.64–2.70 (m, 1 H, CH), 3.74 (s, 6 H, 2 OCH3),
4.82 (s, 1 H, CH), 6.65 (d, J = 10.4 Hz, 1 H, CH=) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 21.6, 25.1, 29.4, 48.2, 52.7, 132.8,
155.0, 168.5, 197.4 ppm. IR (NaCl): ν = 2957, 2924, 2853, 1738,
˜
1670, 1641, 1435, 1193, 758 cm–1. MS (EI): m/z (%) = 242 (12)
[M]+, 210 (6), 178 (19), 155 (8), 141 (10), 127 (7), 113 (18), 99 (24),
71 (73), 57 (100), 43 (96). HRMS: calcd. for C12H18O5 242.1154;
found 242.1150.
1104
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Eur. J. Org. Chem. 2011, 1099–1105

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[12] CCDC-783105 (for 2e) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Empirical formula:
C11H14O4; formula weight: 210.22; crystal color, habit: color-
less, prismatic; crystal system: triclinic; lattice type: primitive;
crystal size: 0.413ϫ0.369ϫ0.307; lattice parameters: a =
9.0256(9) Å, b = 11.2232(12) Å, c = 11.7436(12) Å, α =
102.157(2)o, β = 107.425(2)o, γ = 90.063(2)o, V = 1106.9(2) Å3;
space group: P1; Z = 4; Dcalcd. = 1.261 g/cm3; F(000) = 448;
¯
diffractometer: Rigaku AFC7R; residuals: R; Rw: 0.0543,
0.1435.
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Received: October 13, 2010
Published Online: December 30, 2010
Eur. J. Org. Chem. 2011, 1099–1105
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1105