Control of regioselectivity in Pd(0)-catalyzed coupling-cyclization reaction of 2-(2′,3′-allenyl)malonates with organic halides

Article abstract of DOI:10.1021/jo0108616

The regioselectivity in the Pd(0)-catalyzed coupling-cyclization of 2-(2′,3′-allenyl)malonates with organic halides is determined by the steric and electronic effects of both substrates. By deliberate control of the reaction conditions, the regioselectivity of this reaction can be tuned. With conditions A and B, the reaction afforded vinylic cyclopropane derivatives, while with conditions C and D, the reaction afforded cyclopentene derivatives in a highly selective manner. Under similar conditions, 1-alkenyl halides tend to form more three-membered cyclic products. The increased steric hindrance at the 2′-positon of the allene moiety and aryl halides favors the formation of five-membered cyclic products. The regioselectivity of the reaction may be explained by the comparison of the relative stabilities of syn- and anti-type π-allyl palladium intermediates.

Full text of DOI:10.1021/jo0108616

J . Org. Chem. 2002, 67, 2837-2847
2837
Con tr ol of Regioselectivity in P d (0)-Ca ta lyzed
Cou p lin g-Cycliza tion Rea ction of 2-(2′,3′-Allen yl)m a lon a tes w ith
Or ga n ic Ha lid es
Shengming Ma,* Ning J iao, Shimin Zhao, and Hairong Hou
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China
masm@pub.sioc.ac.cn
Received August 23, 2001
The regioselectivity in the Pd(0)-catalyzed coupling-cyclization of 2-(2′,3′-allenyl)malonates with
organic halides is determined by the steric and electronic effects of both substrates. By deliberate
control of the reaction conditions, the regioselectivity of this reaction can be tuned. With conditions
A and B, the reaction afforded vinylic cyclopropane derivatives, while with conditions C and D, the
reaction afforded cyclopentene derivatives in a highly selective manner. Under similar conditions,
1-alkenyl halides tend to form more three-membered cyclic products. The increased steric hindrance
at the 2′-positon of the allene moiety and aryl halides favors the formation of five-membered cyclic
products. The regioselectivity of the reaction may be explained by the comparison of the relative
stabilities of syn- and anti-type π-allyl palladium intermediates.
The carbopalladation reaction of allenes1 was reported
Sch em e 1
to afford a π-allyl palladium intermediate,2 which can be
further trapped by either a â-H elimination reaction or
a nucleophilic substitution reaction (Scheme 1).3
Here a major concern is the control of the regioselec-
tivity of the nucleophilic substitution process.4 Recently,
during the course of our study of coupling-cyclization
reaction of functionalized allenes,5 we have developed a
set of reaction conditions under which the coupling-
cyclization reactions afforded the pathyway a-type prod-
ucts (n ) 1), i.e., cyclopropane derivatives, in a highly
selective manner starting from dimethyl 2-(2′,3′-allenyl)-
malonate and organic halides.6 These results are quite
contrary to those reported by Cazes et al.7 In this paper,
we wish to report the details of this reaction. Interest-
ingly, the regioselectivity can be tuned by the deliberate
selection of solvents, bases, catalysts, and substrates.
High ly Regioselective F or m a tion of Vin ylic Cy-
clop r op a n e Der iva tives. The Pd(PPh3)4-catalyzed cou-
pling-cyclization reaction of dimethyl 2-(2′,3′-butadienyl)-
malonate (1a ) and PhI was studied in different solvents
(Scheme 1 and Table 1). The reactions in DMF and
DMSO afforded a mixture of cyclopropane derivative 2a
and cyclopentene derivative 3a in good combined yields
(entries 1 and 2, Table 1). However, it is interesting to
observe that the corresponding reaction in toluene,
benzene, and CH3CN afforded 2a with an excellent
selectivity, albeit in low yields (entries 3-5, Table 1). To
our surprise, with the addition of a catalytic amount (10
mol %) of n-Bu4NBr, the reaction in CH3CN afforded 2a
as the sole product in 80% yield (entry 6, Table 1)!
Furthermore, the reaction in THF afforded 2a in 85%
yield even in the absence of n-Bu4NBr (entry 7, Table 1).
Two sets of reaction conditions (A and B) were defined
in Scheme 2.
(1) Schuster, H. F.; Coppola, G. M. Allenes in Organic Synthesis;
J ohn Wiley & Sons: New York, 1984. The Chemistry of Ketenes,
Allenes, and Related Compounds; Patai, S., Ed.; J ohn Wiley & Sons:
New York, 1980; Part I.
(2) Shimizu, I.; Tsuji, J . Chem. Lett. 1984, 233. Ahmar, M.; Cazes,
B.; Gore, J . Tetrahedron Lett. 1984, 25, 4505.
(3) (a) Larock, R. C.; Berrios-Pena, N. G.; Fried, C. A. J . Org. Chem.
1991, 56, 2615. (b) Larock, R. C.; Zenner, J . M. J . Org. Chem. 1995,
60, 482. (c) Okuro, K.; Alper, H. J . Org. Chem. 1997, 62, 1566. (d)
Walkup, R. D.; Guan, L.; Mosher, M. D.; Kim, S. W.; Kim, Y. S. Synlett
1993, 88. (e) Ohno, H.; Toda, A.; Miwa, Y.; Taga, T.; Osawa, E.;
Yamaoka, Y.; Fujii, N.; Ibuka, T. J . Org. Chem. 1999, 64, 2992. (f)
Ma, S.; Negishi, E. J . Org. Chem. 1994, 59, 4730. (g) Grigg, R.; Xu, L.
Tetrahedron Lett. 1996, 37, 4251. (h) Nemoto, H,; Yoshida, M.;
Fukumoto, K. J . Org. Chem. 1997, 62, 6450. J eong, I.;-Y.; Nagao, Y.
Tetrahedron Lett. 1998, 39, 8677. (i) Grigg, R.; Rasul, R.; Redpath, J .;
Wilson, D. Tetrahedron Lett. 1996, 37, 4609. Oppolzer, W.; Pimm, A.;
Stammen, B.; Hume, W. E. Helv. Chim. Acta 1997, 80, 623.
(4) (a) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
(b) Trost, B. M. J . Organomet. Chem. 1986, 300, 263.
(5) For some of our most recent results, see: Ma, S.; Shi, Z. J . Org.
Chem. 1998, 63, 6387. Ma, S.; Duan, D.; Shi, Z. Org. Lett. 2000, 2,
1419. Ma, S.; Shi, Z.; Wu, S. Tetrahedron: Astmmetry 2001, 12, 193.
Ma, S.; Wu, S. J . Org. Chem. 1999, 64, 9314; Ma, S.; WU, S. Chem.
Commun. 2001, 441. Ma, S.; Zhang, J . Chem. Commun. 2000, 117.
Ma, S.; Li, L. Org. Lett. 2000, 2, 941. Ma, S.; Xie, H. Org. Lett. 2000,
2, 3801. Ma, S.; Zhao, S. J . Am. Chem. Soc. 1999, 121, 7943.
(6) Ma, S.; Zhao, S. Org. Lett. 2000, 2, 2495.
The results of the Pd(PPh3)4-catalyzed coupling-cy-
clization reactions of 1a with different organic halides
obtained by applying both conditions A and B to afford
cyclopropane derivatives as the sole products are sum-
marized in Table 2.
(7) (a) Ahmar, M.; Cazes, B.; Gore, J . Tetrahedron Lett. 1985, 26,
3795. (b) Ahmar, M.; Cazes, B.; Gore, J . Tetrahedron 1987, 43, 3453.
(c) Cazes, B. Pure Appl. Chem. 1990, 62, 1867. (d) Besson, L.; Bazin,
J .; Gore, J .; Cazes, B. Tetrahedron Lett. 1994, 35, 2881. (e) Gamez, P.;
Ariente, C.; Gore, J .; Cazes, B. Tetrahedron 1998, 54, 14835.
10.1021/jo0108616 CCC: $22.00 © 2002 American Chemical Society
Published on Web 04/10/2002

2838 J . Org. Chem., Vol. 67, No. 9, 2002
Ma et al.
Ta ble 1. P d (P P h 3)4-Ca ta lyzed Cou p lin g-Cycliza tion of
Sch em e 3
1a w ith P h I u n d er Differ en t Rea ction Con d ition sa
entry solvent
additive
T (°C) time (h) 2a (%) 3a (%)
1
2
3
4
5
6
7
DMF
-
60
62
82
80
25
22
15.5
15
19.5
15
65
49
30
40
32
80
85
8
21
0
0
0
DMSO
toluene
benzene
CH3CN
CH3CN n -Bu 4NBr r eflu x
THF r eflu x
-
-
-
-
Ta ble 3. P d (0)-Ca ta lyzed Cou p lin g-Cycliza tion
Rea ction of 2′-Su bstitu ted 2-(2′,3′-Allen yl)m a lon a tes w ith
Differ en tly Str u ctu r ed Or ga n ic Ha lid es u n d er
Con d ition s Aa
reflux
0
0
-
15.5
a
PhI (1.2 equiv) was used.
Sch em e 2
Ta ble 2. P d (P P h 3)4-Ca ta lyzed Cou p lin g-Cycliza tion of
Dim eth yl 2-(2′,3′-P r op a d ien yl)m a lon a te w ith Or ga n ic
Ha lid es u n d er Con d ition s A a n d Ba
a
RI (1.2 equiv) was used.
conditions A, while under conditions B, the corresponding
reaction did not afford either cyclopropane derivative 2i
or five-membered cyclic product 3i in decent yields
(Scheme 3), implying that conditions A afforded the
cyclopropane derivative 2i even with the increased steric
hindrance at the 2-position of the allene moiety.
a
1.2 equiv of RI was used for Conditions A, and 1.3 equiv of RI
b
was used for Conditions B. See text.
The results of the Pd(0)-catalyzed reaction of differ-
ently 2′-substituted 2-(2′,3′-allenyl)malonates with or-
ganic halides are summarized in Table 3. From Table 3,
it should be noted that (1) the regioselectivity for the
formation of the three-membered cyclic products is high
and (2) the configuration of the CdC bond in 1-alkenyl
Furthermore, it is interesting to observe that the Pd-
(PPh3)4-catalyzed reaction of dimethyl 2-(2′-benzyl-2′,3′-
butadienyl)malonate (1b) (a benzyl group was introduced
at the 2-position of the allenyl moiety) with PhI afforded
the three-membered cyclic product 2i in 80% yield under

Control of Regioselectivity
J . Org. Chem., Vol. 67, No. 9, 2002 2839
Ta ble 4. P d (0)-Ca ta lyzed Cou p lin g-Cycliza tion
Rea ction of 4′-Su bstitu ted 2-(2′,3′-Allen yl)m a lon a tes w ith
Or ga n ic Ha lid es u n d er Con d ition s Aa
Sch em e 4
Ta ble 5. P d (0)-Ca ta lyzed Cou p lin g-Cycliza tion
Rea ction of 1 w ith Or ga n ic Ha lid es u n d er Con d ition s Ca
a
b
R3I (1.2 equiv) was used. Determined by 300 MHz 1H NMR
spectra.
F igu r e 1.
iodide remained unchanged during the reaction (entries
4-6 and 11-13, Table 3).
Further introduction of a substitutent at the 4-position
of the allene moiety gave high ratios of cyclopropane/
cyclopentene derivatives, although the formation of five-
membered cyclic products were also observed (Table 4).
The configurations of the CdC bond in 2 were determined
1
by the H-1H NOESY spectra (Figure 1).
High ly Regioselective Syn th esis of Cyclop en ten e
Der iva tives. To investigate the possibility of developing
a set of general reaction conditions for the exclusive
formation of cyclopentene derivatives, an enormous
number of reaction conditions were screened and the
results are shown in Tables 1 and 2 in Supporting
Information. In both CH3CN and THF, the effect of a base
on the regioselectivity is obvious: with LiOH, NaOH,
KOH, LDA, n-BuLi, or NaH, the reaction afforded five-
membered cyclic product 3i with an excellent regioselec-
tivity. With the observation that the reaction using NaH
as the readily available base afforded 3i in 53% yield (see
Table 2 in Supporting Information), we developed a set
of reaction conditions, i.e., 5 mol % Pd(PPh3)4, NaH (1.1
equiv), DMSO, 85 °C (Conditions C), for the highly
regioselective and high-yielding preparation of cyclopen-
tene derivative 3i (Scheme 4). Here the solvent (DMSO)
and the catalyst (Pd(PPh3)4) are the keys for a good yield
of 3i. The corresponding results are summarized in Table
5. The conversion of 2i to 3i under Conditions C was not
observed (Scheme 5).
a
b
R3I (1.2 equiv) was used. THF was used as the solvent. c E-
2/Z-2 ratio determined by 300 MHz 1H NMR spectra.
are the only products formed. However, even under
Conditions C, the corresponding reactions with 1-alkenyl
iodide afforded a mixture of both cyclopropane and
cyclopentene derivatives with low selectivities, favoring
In most cases involving aryl iodides except entries 6,
7, 10, and 11 (Table 5), the cyclopentene derivatives 3

2840 J . Org. Chem., Vol. 67, No. 9, 2002
Ma et al.
Ta ble 7. Effect of Ba se on th e P d (0)-Ca ta lyzed Rea ction
of 1a w ith P h I in DMF a
Sch em e 5
yield of
(2a + 3a ) (%)
entry
baseb
time (h)
2a :3a c
1
2
3
4
5
n-BuLi (1.1)
KOH (2.0)
NaOH (1.2)
NaOH (1.5)
Na OH (2.0)
10.5
10.5
12
12
10.5
46
31
75
40
66
0:100
0:100
13:87
0:100
0:100
Ta ble 6. P d (0)-Ca ta lyzed Rea ction of 1a w ith P h I in
Differ en t Solven ts Usin g Na H a s th e Ba sea
a
b
PhI (1.2 equiv) was used. Numbers in parentheses are the
equivalents of the base used in the reaction. c Determined by 300
MHz 1H NMR spectra.
Ta ble 8. P d (0)-Ca ta lyzed Cou p lin g-Cycliza tion
Rea ction of 2′-Su bstitu ted 2-(2′,3′-Allen yl)m a lon a tes w ith
Differ en tly Str u ctu r ed Or ga n ic Ha lid es u n d er
Con d ition s Da
T
(°C)
time
yield
yield
entry solvent
1c DMSO NaH (1.1)
baseb
(h) of 2a (%) of 3a (%)
85
12
12
12
10
10
12
8
22
5
5
4
0
9
0
42
51
60
67
51
trace
22
26
3
2
3
DMSO NaH (1.1)
85
85
85
85
85
DMF
NaH (1.1)
NaH (1.1)
KOH (2.0)
4c DMF
5
6
7
DMF
toluene NaH (1.1)
CH3CN NaH (1.1)
reflux 12
reflux
reflux 12
8
9
10
11
12
THF
THF
THF
THF
THF
NaH (1.1)
LiOH (2.0)
7
0
0
NaOH (2.0) reflux 12
LDA (1.1) reflux 12
n-BuLi (1.1) reflux 12
20
trace
trace
trace
trace
a
b
PhI (1.2 equiv) was used. Numbers in parentheses are the
equivalents of the base used in the reaction. c Pd(PPh3)4 (5 mol
%) was used instead of Pd2(dba)3‚CHCl3 and dppe as the catalyst.
the formation of cyclopropane derivatives (entries 12-
14, Table 5). The reaction of 1a with E-(1-phenyl ethenyl)
iodide afforded the three-membered cyclic product 2e in
a highly selective manner in 45% yield, probably due to
the steric effect at the 2′-position (entry 15, Table 5).
With the decreased steric hindrance at the 2-position
of the allene moiety, the regioselectivity control for the
formation of five-membered cyclic products would be a
new challenge. The similar reaction of dimethyl 2-(2′,3′-
butadienyl)malonate 1a with PhI under Conditions C
afforded a mixture of 2a and 3a in 8 and 42% yields,
respectively (entry 1, Table 6). When the reaction using
NaH as the base was carried out in other solvents, the
selectivity was still not good enough (entries 2-4, Table
6). Thus, the effects of different bases for this reaction
in THF were studied (entries 8-12, Table 6). In most
cases, excellent selectivities with low yields were achieved
(entries 8-10, Table 6). Better yields were achieved with
KOH as the base and DMF as the solvent (entry 5, Table
6). With these results in hand, we were able to develop
a set of optimized reaction conditions for the cyclopen-
tene-formation reaction, i.e., Conditions D (Conditions D
) 5 mol % Pd(PPh3)4, NaOH (2.0 equiv), DMF, 85 °C)
(entry 5, Table 7). The amount of NaOH used is impor-
tant for both the regioselectivity and yield of 3a (compare
entries 3-5, Table 7). Some typical results are sum-
marized in Table 8. It is obvious that the reactions of 1c
with p-methylphenyl iodide and p-methoxylphenyl iodide
under Conditions D afforded the five-membered rings 3
exclusively (compare entries 3 and 5 in Table 8 with
entries 6 and 7 in Table 5).
a
b
RI (1.2 equiv) was used. NaH (1.1 equiv) was used instead
of NaOH as the base.
Here, the electronic effect of the substituent in aryl
iodide again has a major effect on the regioselectivity.
Using p-methoxycarbonylphenyl iodide, the reaction af-
forded 2g and 3g in 55% combined yield with a ratio of
34:66 (2g/3g). Similar reaction under Cazes’ conditions7,8
afforded 2g and 3g in very low yields with 37% of 1a
recovered (Scheme 6).
On the basis of these results, it is obvious that the
steric hindrance of the allene moiety is one of the major
factors controlling the regioselectivity of this coupling-
cyclization reaction. A similar phenomenon was observed
with aryl iodide. The corresponding reaction of 1b with
o-methylphenyl iodide under Conditions A afforded the
cyclopentene derivative 3i-o-Me in 80% yield as the sole
product (compare Scheme 7 with the results in Table 3).
When a mixture of an equimolar ratio of 1b, PhI, and
o-methylphenyl iodide was submitted to Conditions A,
(8) Cazes’ conditions: compound 1a and 1.06 equiv of NaH in THF
were stirred at rt for 1∼2 h first, and then the above solution was
added to another flask that was charged with 2 mol % Pd2(dba)3‚CHCl3
and 4 mol % dppe in THF. The solution was then treated with PhI
and stirred under reflux. See: Ahmar, M.; Cazes, B.; Gore, J .
Tetrahedron 1987, 43, 3453.

Control of Regioselectivity
Sch em e 6
J . Org. Chem., Vol. 67, No. 9, 2002 2841
Sch em e 9
a
b
Determined by 300 MHz 1H NMR spectra. Compound 1a
(37%) was recovered.
Sch em e 10
Sch em e 7
with those in Scheme 4), implying that three-membered
cyclic products may be formed via intermediate syn-4a
(Scheme 9), which may be formed exclusively in a
thermodynamically controlled manner due to the absence
of a base.
Thus, it is reasonable that under relatively weaker
basic conditions, the reaction favors the formation of
three-membered cyclic products via intermediate syn-4.
Con clu sion
Sch em e 8
(1) The regioselectivity of this reaction can be tuned:
with Conditions A and B, the reaction tends to afford
three-membered cyclic products 2, while with Conditions
C and D, the reaction favors the formation of five-
membered cyclic products 3. (2) The regioselectivity
depends largely on the structures of both organic halides
and 2-(2′,3′-allenyl)malonates. The reaction with 1-alk-
enyl halides favors the formation of three-membered
cyclic products 2. (3) The electronic effects of the sub-
stituent in aryl halides have an influence on the regi-
oselectivity. (4) With increased steric effects at the 2′-
position of the allene moiety and organic halides, the
reaction tends to form five-membered cyclic products.
the reaction afforded 2i in 64% yield, 3i in 8% yield, and
3i-o-Me in 19% yield, respectively (Scheme 7), implying
a strong steric effect on the regioselectivity of this
reaction.
Mech a n istic Con sid er a tion . For the regioselectivity
of this coupling-cyclization reaction, two types of π-allyl
palladium intermediates, i.e., anti- and syn-4, may be
considered (Scheme 8). It is commonly believed that
anti-4 will lead to the favorable formation of five-
membered cyclic products 3, while syn-4 will form three-
membered cyclic products 2.7c Thus, compared with
alkenyl halide, due to the larger steric hindrance, aryl
halides tend to favor the formation of five-membered
cyclic products 3. With the introduction of non-hydrogen
R1, the reaction also tends to form five-membered ring 3
via anti-4.
The carbopalladation reaction may occur before or after
deprotonation of the malonate moiety. When 1b and PhI
were treated with 20 mol % Pd(PPh3)4 in DMSO for 6 h
first followed by the addition of NaH, the reaction
afforded 2i in 29% yield exclusively (compare this result
Exp er im en ta l Section
Sta r tin g Ma ter ia ls: Syn th esis of 2,3-Allen oic Acid
Ester s 6b-e.9,10 These compounds were synthesized according
to the Wittig-type reactions shown in Scheme 10.
1. 2-Ben zylbu ta -2,3-d ien oic Acid Eth yl Ester (6b). To
a solution of 4b (87.6 g, 0.2 mol) in dichloromethane (300 mL)
was added a solution of Et3N (36.2 mL, 0.26 mol) in 30 mL of
dichloromethane dropwise within 45 min. After the solution
was stirred for 5 min at rt, acetyl chloride 5b (18.5 mL, 0.26
mol) in 20 mL of CH2Cl2 was added dropwise, and the solution
was stirred overnight at rt. Then, the solvent was removed in
vacuo. The residue was treated with 150 mL of ether and then
filtered. The organic phase was combined and dried over
anhydrous sodium sulfate. After evaporation, the residue was
purified by flash chromatography on silica gel (eluent, 40:1
petroleum ether/ethyl acetate) to afford 19.4 g (56%) of

2842 J . Org. Chem., Vol. 67, No. 9, 2002
Ma et al.
2.10 (m, 2 H), 1.55 (brs, 1 H), 1.10-1.40 (m, 8 H), 0.87 (t, J )
6.66 Hz, 3 H); MS m/z (%) 137 (M+ - CH3, 1.74), 84 (100).
4. 2-Meth ylh ep ta -2,3-d ien -1-ol (7e). Starting from 6e (2.6
g, 16.8 mmol) afforded 1.34 g (63%) of 7e:13 liquid; IR (neat)
3317, 2959, 1967, 1458, 1377 cm-1; 1H NMR (300 MHz, CDCl3)
δ 5.19-5.31 (m, 1 H), 3.98 (s, 2 H), 1.98 (dt, J ) 7.08, 7.08 Hz,
2 H), 1.70 (d, J ) 2.92 Hz, 3 H), 1.31-1.54 (m, 2 H), 0.92 (t, J
) 7.34 Hz, 3 H); MS m/z (%) 126 (M+, 6.86), 84 (100).
Syn t h esis of 2-(2′,3′-Dien yl)m a lon a t es 1. Compounds
1a -e were prepared from the alkylation reaction of malonates
with the corresponding bromide and NaH in THF as re-
ported.14 2,3-Dienyl bromides were prepared from 2,3-dien-1-
ols15 and PBr3 as reported.16
Sch em e 11
1. Meth yl 2-(2′,3′-Bu ta d ien yl)m a lon a te (1a ).17 Starting
from 4-bromo-1,2-butadiene16 (5.3 g, 40 mmol) afforded 5.15 g
(70%) of 1a : liquid; IR (neat) 2956, 1957, 1737, 1437, 1271
cm-1; 1H NMR (300 MHz, CDCl3) δ 5.02-5.13 (m, 1 H), 4.61-
4.72 (m, 2 H), 3.68 (s, 6 H), 3.45 (t, J ) 7.34 Hz, 1 H), 2.48-
2.59 (m, 2 H); MS m/z (%) 184 (M+, 6.64), 93 (100).
2. Meth yl 2-(2′-Ben zyl-2′,3′-bu ta d ien yl)m a lon a te (1b).
Starting from 3-bromomethyl-4-phenyl-1,2-butadiene (4.2 g,
19 mmol) afforded 4.27 g (82%) of 1b: liquid; IR (neat) 3029,
2955, 1960, 1737, 1602, 1493 cm-1; 1H NMR (300 MHz, CDCl3)
δ 7.15-7.36 (m, 5 H), 4.66 (br s, 2 H), 3.63 (s, 6 H), 3.50 (t, J
) 7.59 Hz, 1 H), 3.26 (s, 2 H), 2.38-2.49 (m, 2 H); MS m/z (%)
274 (M+, 0.49), 142 (100); HRMS m/z (EI) calcd for C16H18O4
274.12051, found 274.11866.
3. Meth yl 2-(2′-P r op yl-2′,3′-bu ta d ien yl)m a lon a te (1c).
Starting from 3-bromomethyl-1,2-hexadiene (3.15 g, 18 mmol)
afforded 3.7 g (91%) of 1c: liquid; IR (neat) 2957, 1958, 1755,
1739, 1436 cm-1; 1H NMR (300 MHz, CDCl3) δ 4.65-4.76 (m,
2 H), 3.70 (s, 6 H), 3.57 (t, J ) 7.56 Hz, 1 H), 2.47-2.56 (m, 2
H), 1.88-2.02 (m, 2 H), 1.33-1.50 (m, 2 H), 0.87 (t, J ) 7.31
Hz, 3 H); MS m/z (%) 226 (M+, 13.42), 79 (100); HRMS m/z
(EI) calcd for C12H18O4 226.12051, found 226.12083.
2-benzylbuta-2,3-dienoic acid ethyl ester (6b): IR (neat) 2585,
1967, 1712, 1602, 1496, 1258 cm-1; 1H NMR (300 MHz, CDCl3)
δ 7.13-7.34 (m, 5 H), 5.08-5.14 (m, 2 H), 4.20 (q, J ) 7.12
Hz, 2 H), 3.53-3.62 (m, 2 H), 1.26 (t, J ) 7.02 Hz, 3 H).
2. 2-Met h ylh ep t a -2,3-d ien oic Acid E t h yl E st er (6e).
Starting from 4e (19 g, 52.5 mmol) and 5e (6.4 g, 53.1 mmol)
afforded 7.6 g (86%) of 6e: IR (neat) 2962, 1961, 1712, 1459,
1368, 1272 cm-1; 1H NMR (300 MHz, CDCl3) δ 5.38-5.54 (m,
1 H), 4.08-4.26 (m, 2 H), 2.02-2.18 (m, 2 H), 1.83-1.91 (m, 3
H), 1.41-1.58 (m, 2 H), 1.27 (t, J ) 7.33 Hz, 3 H), 0.98 (t, J )
7.33 Hz, 3 H); MS m/z (%) 168 (M+, 12.23), 139 (100).
3. Compounds 6c and 6d are known compounds prepared
as reported.9,10
Syn th esis 2,3-Allen -1-ols 7b-e. Syntheses of 2,3-allenols
7 were performed by the reduction reaction of 2,3-allenoates
6 with DIBAL-H (Scheme 11).
4. Meth yl 2-(Deca -2′,3′-d ien yl)m a lon a te (1d ). Starting
from 1-bromo-2,3-decadiene (1.09 g, 5.0 mmol) afforded 0.80
g (60%) of 1d : liquid; IR (neat) 2955, 2929, 1960, 1756, 1739,
1. Syn th esis of 2-Ben zylbu ta -2,3-d ien -1-ol (7b): Typ ica l
P r oced u r e. A dry three-necked flask equipped with a mag-
netic stirring bar, and a dropping funnel was charged with
6b (10.1 g, 50 mmol) in dry toluene (130 mL). The solution
was rapidly stirred, and DIBAL-H (1.0 M solution in toluene,
105 mL, 2.1 equiv) was added dropwise at -78 °C under
nitrogen. When the addition was complete, the mixture was
stirred at -78 °C for 4 h. After the starting material 6b
disappeared completely as monitored by TLC, 50 mL of
methanol was added to quench the reaction at 0 °C. Then, 150
mL of brine was added, and the mixture was stirred for 5 min,
filtered, and separated; the aqueous layer was extracted with
ether (3 × 50 mL). The combined ether layer was dried over
anhydrous sodium sulfate. Evaporation and purification with
flash chromatography on silica gel (eluent, 10:1 petroleum
ether/ethyl acetate) afforded 5.3 g (67%) of 7b:11 liquid; IR
(neat) 3347, 2912, 1951, 1599, 1491 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.05-7.50 (m, 5 H), 4.65-5.05 (m, 2 H), 4.03 (t, J )
2.59 Hz, 2 H), 3.39 (t, J ) 2.59 Hz, 2 H), 1.50-1.89 (br s, 1 H);
MS m/z (%) 160 (M+, 59.43), 115 (100).
2. 2-P r op ylbu ta -2,3-d ien -1-ol (7c). Starting from 6c (7.7
g, 50 mmol) afforded 2.94 g (53%) of 7c:12 liquid; IR (neat) 3387,
2962, 1958, 1723, 1459, 1179 cm-1; 1H NMR (300 MHz, CDCl3)
δ 4.71-4.98 (m, 2 H), 4.03 (t, J ) 2.97 Hz, 2 H), 1.82-2.09
(m, 2 H), 1.57 (s, 1 H), 1.32-1.55 (m, 2 H), 0.98 (t, J ) 7.34
Hz, 3 H); MS m/z (%) 112 (M+, 3.68), 95 (100).
3. Deca -2,3-d ien -1-ol (7d ). Starting from 6d (15.7 g, 80
mmol) afforded 1.64 g (13%) of 7d . The yield was improved to
42% using the corresponding methyl ester: liquid; IR (neat)
3346, 2926, 1963, 1466, 1378, 1180, 1015 cm-1; 1H NMR (300
MHz, CDCl3) δ 5.20-5.39 (m, 2 H), 4.00-4.20 (m, 2 H), 1.92-
1
1436 cm-1; H NMR (300 MHz, CDCl3) δ 4.98-5.18 (m, 2 H),
3.67 (s, 6 H), 3.44 (t, J ) 7.52 Hz, 1 H), 2.43-2.55 (m, 2 H),
1.78-1.92 (m, 2 H), 1.13-1.38 (m, 8 H), 0.81 (t, J ) 6.75 Hz,
3 H); MS m/z (%) 268 (M+, 1.03), 138 (100); HRMS m/z (EI)
calcd for C15H24O4 268.16746, found 268.16992.
5. Meth yl 2-(2′-Meth ylh ep ta -2′,3′-d ien yl)m a lon a te (1e).
Starting from 1-bromo-2-methyl-2,3-heptadiene (0.47 g, 2.46
mmol) afforded 0.31 g (53%) of 1e: liquid; IR (neat) 2957, 1960,
1
1756, 1738, 1436 cm-1; H NMR (300 MHz, CDCl3) δ 5.00-
5.11 (m, 1 H), 3.72 (s, 6 H), 3.56 (dt, J ) 7.40 and 1.34 Hz, 1
H), 2.56 (dd, J ) 7.40, 3.05 Hz, 2 H), 1.88 (dt, J ) 7.19, 7.19
Hz, 2 H), 1.69 (d, J ) 2.57 Hz, 3 H), 1.26-1.42 (m, 2 H), 0.90
(t, J ) 7.33 Hz, 3 H); MS m/z (%) 240 (M+, 24.4), 93 (100);
HRMS m/z (EI) calcd for C13H20O4 240.13616, found 240.13347.
P d (0)-Ca ta lyzed Cou p lin g-Cycliza tion Rea ction of
2-(2′,3′-Bu tadien yl)m alon ates with Or gan ic Halides. Con -
d ition s A: P r ep a r a tion of 1,1-Bis(m eth oxyca r bon yl)-2-
(1′-p h en yleth en yl)cyclop r op a n e (2a ). Typ ica l P r oced u r e.
To a mixture of potassium carbonate (352 mg, 2.55 mmol),
TBAB (20 mg, 0.064 mmol, 10 mol %), and Pd(PPh3)4 (37 mg,
0.032 mmol, 5 mol %) in CH3CN (3 mL) were added dimethyl
2-(2′,3′-butadienyl)malonate 1a (117 mg, 0.64 mmol) and
iodobenzene (156 mg, 0.76 mmol, 1.2 equiv) subsequently
under nitrogen. The resulting mixture was refluxed for 15 h
as monitored by TLC. After filtration, washing with ether, and
evaporation, the residue was purified by flash chromatography
(13) Claesson, A.; Ta¨mnefors, I.; Olsson, L.-I. Tetrahedron Lett. 1975,
1509.
(9) (a) Buono, G. Tetrahedron Lett. 1972, 3257. (b) Ma, S.; Li, L.;
Qi, W.; Xie, H.; Wang, G.; Shi, Z.; Zhang, J . Pure Appl. Chem. 2000,
72 (9), 1739. (c) Ma, S.; Xie, H.; Wang, G.; Zhang, J .; Shi, Z. Synthesis
2001, 713.
(10) J ones, V. K.; Deutschman, A. J . J . Org. Chem. 1965, 30, 3978.
(11) Lumbroso-Bader, N.; Michel, E.; Troyanowsky, C. Bull. Soc.
Chim. Fr. 1967, 189.
(14) Ma, S.; Negishi, E.-i. J . Am. Chem. Soc. 1995, 117, 6345.
(15) Adegoke, E. A.; Emokpae, T. A.; Ephraim-Bassey, H. J . Het-
erocycl. Chem. 1986, 23, 1195.
(16) (a) Pattenden, G.; Robertson, G. M. Tetrahedron 1985, 41, 4001.
(b) Ma, S.; Negishi, E.-i. J . Org. Chem. 1994, 59, 4730. (c) Brandsma,
L. Preparative Acetylenic Chemistry, 2nd ed.; Elsevier Science: New
York, 1988; p 247.
(12) Gelin, R.; Gelin, S.; Albrand, M. Bull. Soc. Chim. Fr. 1971, 4146.
(17) Ahmar, M.; Cazes, B.; Gore, J . Tetrahedron Lett. 1985, 26, 3795.

Control of Regioselectivity
J . Org. Chem., Vol. 67, No. 9, 2002 2843
on silica gel (eluent, 20:1 petroleum ether/ethyl acetate) to
afford 132 mg (80%) of 2a .
3.78 (s, 3 H), 3.46 (s, 3 H), 2.98 (t, J ) 8.52 Hz, 1 H), 2.32 (s,
3 H), 2.05 (dd, J ) 8.52, 5.02 Hz, 1 H), 1.63 (dd, J ) 8.52, 5.02
Hz, 1 H); MS m/z (%) 274 (M+, 6.36), 155 (100); HRMS m/z
(EI) calcd for C16H18O4 274.1205, found 274.1205.
Con d ition s B: P r ep a r a tion of 1,1-Bis(m eth oxyca r bo-
n yl)-2-(1′-p h en yleth en yl)cyclop r op a n e (2a ). Typ ica l P r o-
ced u r e. To a mixture of potassium carbonate (201 mg, 1.5
mmol, 4.0 equiv) and Pd(PPh3)4 (21 mg, 5 mol %) in THF (3
mL) were added subsequently dimethyl 2-(2′,3′-butadienyl)-
malonate 1a (67 mg, 0.36 mmol) and iodobenzene (96 mg, 0.47
mmol, 1.3 equiv) under nitrogen. Then, the resulting mixture
was refluxed for 15.5 h as monitored by TLC. After filtration,
washing with ether, and evaporation, the residue was purified
by flash chromatography on silica gel (eluent, 20:1 petroleum
ether/ethyl acetate) to afford 81 mg (85%) of 2a .
Con d ition s C: P r ep a r a tion of 1-P h en yl-2-ben zyl-4,4-
bis(m eth oxyca r bon yl)cyclop en ten e (3i). Typ ica l P r oce-
d u r e. To a mixture of NaH (60% dispersion in mineral oil, 7
mg, 1.1 equiv) and Pd(PPh3)4 (8.7 mg, 5 mol %) in dry DMSO
(1.5 mL) were added subsequently dimethyl 2-(2′-benzyl-2′,3′-
butadienyl)malonate 1b (41 mg, 0.15 mmol) dropwise and
iodobenzene (37 mg, 1.2 equiv) under nitrogen. The resulting
mixture was heated at 85 °C for 12 h as monitored by TLC.
Then, the reaction was quenched with an aqueous solution of
saturated NaCl (2 mL) and the mixture extracted with ether
(20 mL). The organic layer was washed with brine (3 × 8 mL)
and dried over anhydrous sodium sulfate. After evaporation,
the residue was purified by flash chromatography on silica gel
(eluent, 10:1 petroleum ether/ethyl acetate) to afford 46 mg
(88%) of 3i.
Con dition s D: P r epar ation of 1-P h en yl-4,4-bis(m eth ox-
yca r bon yl)cyclop en t en e (3a ). Typ ica l P r oced u r e. To a
mixture of anhydrous sodium hydroxide (20 mg, 0.5 mmol, 2.0
equiv) and Pd(PPh3)4 (14.5 mg, 5 mol %) in anhydrous DMF
(2.0 mL) were added subsequently dimethyl 2-(2′,3′-butadi-
enyl)malonate 1a (46 mg, 0.25 mmol) dropwise and iodoben-
zene (61 mg, 1.2 equiv) under nitrogen. The resulting mixture
was heated at 85 °C for 10.5 h as monitored by TLC. Then, 30
mL of ether was added, and the solution was washed with
brine (3 × 8 mL), dried over anhydrous sodium sulfate, and
filtered. The solvent was removed in vacuo, and the residue
was purified via flash chromatography on silica gel (eluent,
20:1 petroleum ether/ethyl acetate) to afford 43 mg (66%) of
3a .
1. 1,1-Bis(m et h oxyca r b on yl)-2-(1′-p h en ylet h en yl)cy-
clop r op a n e (2a ). Starting from 1a (117 mg, 0.64 mmol) and
PhI (157 mg, 0.77 mmol) afforded 132 mg (80%) of 2a using
Conditions A; starting from 1a (67 mg, 0.36 mmol) and PhI
(96 mg, 0.47 mmol) afforded 81 mg (85%) of 2a using Condi-
tions B: liquid; IR (neat) 1624, 1728 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.47 (d, J ) 8.17 Hz, 2 H), 7.20-7.40 (m, 3 H), 5.51
(s, 1 H), 5.05 (s, 1 H), 3.78 (s, 3 H), 3.44 (s, 3 H), 2.99 (t, J )
8.05 Hz, 1 H), 2.04 (dd, J ) 8.05 and 5.15 Hz, 1 H), 1.60 (dd,
J ) 8.05 and 5.15 Hz, 1 H); MS m/z (%) 260 (M+, 2.91), 200
(100); HRMS m/z (EI) calcd for C15H16O4 260.1049, found
260.1053.
4. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-(4′′-m eth oxyp h en yl)-
eth en yl)cyclop r op a n e (2d ). Starting from 1a (118 mg, 0.641
mmol) and 4-iodoanisole (180 mg, 0.769 mmol) afforded 128
mg (69%) of 2d using Conditions A; starting from 1a (105 mg,
0.571 mmol) and 4-iodoanisole (174 mg, 0.742 mmol) afforded
98 mg (59%) of 2d using Conditions B: liquid; IR (neat) 1606,
1724 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.46 (d, J ) 7.06 Hz,
2 H), 6.86 (d, J ) 7.06 Hz, 2 H), 5.43 (s, 1 H), 4.97 (s, 1 H),
3.82 (s, 3 H), 3.80 (s, 3 H), 3.47 (s, 3 H), 2.97 (t, J ) 8.00 Hz,
1 H), 2.06 (dd, J ) 8.00, 5.04 Hz, 1 H), 1.59 (dd, J ) 8.00, 5.04
Hz, 1 H); MS m/z (%) 290 (M+, 9.31), 230 (100); HRMS m/z
(EI) calcd for C16H18O5 290.1154, found 290.1145.
5. (E)-1,1-Bis(m et h oxyca r b on yl)-2-(1′-m et h ylen e-3′-
p h en yl-2′-p r op en yl)cyclop r op a n e (2e). Starting from 1a
(94 mg, 0.511 mmol) and (E)-1-iodo-2-phenylethylene18 (141
mg, 0.613 mmol) afforded 67 mg (46%) of 2e using Conditions
A; starting from 1a (101 mg, 0.549 mmol) and (E)-1-iodo-2-
phenylethylene (164 mg, 0.714 mmol) afforded 71 mg (45%)
of 2e using Conditions B: liquid; IR (neat) 1603, 1730 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.10-7.38 (m, 5 H), 6.71 (s, 2
H), 5.21 (s, 1 H), 5.02 (s, 1 H), 3.75 (s, 3 H), 3.49 (s, 3 H), 2.81
(t, J ) 8.40 Hz, 1 H), 1.95 (dd, J ) 8.40, 4.97 Hz, 1 H), 1.48
(dd, J ) 8.40, 4.97 Hz, 1 H); MS m/z (%) 286 (M+, 9.77), 167
(100); HRMS m/z (EI) calcd for C17H18O4 286.1205, found
286.1198.
6. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-n a p h th yleth en yl)cy-
clop r op a n e (2f). Starting from 1a (97 mg, 0.527 mmol) and
1-iodonaphthalene19 (162 mg, 0.632 mmol) afforded 166 mg
(purity 93%, yield 95%) of 2f using Conditions A; starting from
1a (80 mg, 0.435 mmol) and 1-iodonaphthalene (133 mg, 0.566
mmol) afforded 122 mg (91%) of 2f using Conditions B: liquid;
1
IR (neat) 1580, 1625, 1723 cm-1; H NMR (300 MHz, CDCl3)
δ 7.10-8.15 (m, 7 H), 5.44 (s, 1 H), 5.32 (s, 1 H), 3.69 (s, 3 H),
3.61 (s, 3 H), 3.07 (t, J ) 8.53 Hz, 1 H), 1.95 (dd, J ) 8.53,
5.06 Hz, 1 H), 1.64 (dd, J ) 8.53, 5.06 Hz, 1 H); MS m/z (%)
310 (M+, 5.39), 191 (100); HRMS m/z (EI) calcd for C19H18O4
310.1205, found 310.1244.
7. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-(4′′-m eth oxyca r bon -
ylp h en yl)eth en yl)cyclop r op a n e (2g). Starting from 1a (120
mg, 0.652 mmol) and 4-iodobenzoic acid methyl ester20 (199
mg, 0.76 mmol) afforded 120 mg (58%) of 2g using Conditions
A; starting from 1a (82 mg, 0.446 mmol) and 4-iodobenzoic
acid methyl ester (152 mg, 0.58 mmol) afforded 103 mg (73%)
of 2g using Conditions B: liquid; IR (neat) 1608, 1727 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.98 (d, J ) 8.44 Hz, 2 H), 7.52
(d, J ) 8.44 Hz, 2 H), 5.62 (s, 1 H), 5.17 (s, 1 H), 3.90 (s, 3 H),
3.79 (s, 3 H), 3.43 (s, 3 H), 2.98 (t, J ) 8.52 Hz, 1 H), 2.03 (dd,
J ) 8.52, 5.15 Hz, 1 H), 1.63 (dd, J ) 8.52, 5.15 Hz, 1 H); MS
m/z (%) 318 (M+, 1.08), 258 (100); HRMS m/z (EI) calcd for
C
17H18O6 318.1103, found 318.1098.
2. 1,1-Bis(m et h oxyca r b on yl)-2-(1′-(4′′-b r om op h en yl)-
eth en yl)cyclop r op a n e (2b). Starting from 1a (100 mg, 0.543
mmol) and 4-bromophenyl iodide (183 mg, 0.65 mmol) afforded
184 mg (purity 87%, yield 87%) of 2b using Conditions A;
starting from 1a (79 mg, 0.429 mmol) and 4-bromophenyl
iodide (158 mg, 0.556 mmol) afforded 111 mg (76%) of 2b using
Conditions B: liquid; IR (neat) 1585, 1622, 1716 cm-1; 1H NMR
(300 MHz, CDCl3) δ 7.44 (d, J ) 8.62 Hz, 2 H), 7.33 (d, J )
8.62 Hz, 2 H), 5.50 (s, 1 H), 5.07 (s, 1 H), 3.78 (s, 3 H), 3.47 (s,
3 H), 2.92 (t, J ) 8.54 Hz, 1 H), 2.02 (dd, J ) 8.54 and 5.34
Hz, 1 H), 1.59 (dd, J ) 8.54 and 5.34 Hz, 1 H); MS m/z (%)
340 (M(81Br)+, 4.50), 338 (M(79Br)+, 4.65), 278(100); HRMS m/z
(EI) calcd for C15H15BrO4 338.0154, found 338.0148.
8. (E)-1,1-Bis(m et h oxyca r b on yl)-2-(1′-m et h ylen e-2′-
h ep ten yl)cyclop r op a n e (2h ). Starting from 1a (94 mg, 0.511
mmol) and (E)-1-iodo-1-hexene21 (129 mg, 0.613 mmol) afforded
91 mg (67%) of 2h using Conditions A; starting from 1a (95
mg, 0.516 mmol) and (E)-1-iodo-1-hexene (141 mg, 0.67 mmol)
afforded 2h (84 mg, yield 61%) using Conditions B: liquid; IR
1
(neat) 1607, 1647, 1730 cm-1; H NMR (300 MHz, CDCl3) δ
6.00 (d, J ) 16.36 Hz, 1 H), 5.80 (dt, J ) 16.36, 6.82 Hz, 1 H),
4.95 (s, 1 H), 4.79 (s, 1 H), 3.71 (s, 3 H), 3.53 (s, 3 H), 2.69 (t,
J ) 8.18 Hz, 1 H), 2.01 (q, J ) 6.74 Hz, 2 H), 1.88 (dd, J )
8.18, 4.88 Hz, 1 H), 1.41 (dd, J ) 8.18, 4.88 Hz, 1 H), 1.10-
1.35 (m, 4 H), 0.87 (t, J ) 7.02 Hz, 3 H); MS m/z (%) 91 (100),
3. 1,1-Bis(m et h oxyca r b on yl)-2-(1′-(4′′-m et h ylp h en yl)-
eth en yl)cyclop r op a n e (2c). Starting from 1a (140 mg, 0.76
mmol) and 4-iodotoluene (199 mg, 0.91 mmol) afforded 170
mg (82%) of 2c using Conditions A; starting from 1a (92 mg,
0.50 mmol) and 4-iodotoluene(131 mg, 0.65 mmol) afforded 78
mg (57%) of 2c using Conditions B: liquid; IR (neat) 1606,
1732 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.36 (d, J ) 7.95 Hz,
2 H), 7.12 (d, J ) 7.95 Hz, 2 H), 5.47 (s, 1 H), 5.00 (s, 1 H),
(18) (a) J ohnson, M. D.; Meeks, B. S. Chem. Commun. 1970, 1027.
(b) Dodd, D.; J ohnson, M. D.; Meeks, B. S.; Titchmarsh, D. M.; Duong,
K. N. V.; Gaudemer, A. J . Chem. Soc., Perkin Trans. 2 1976, 1261.
(19) (a) Barker, I. R. L.; Waters, W. A. J . Chem. Soc. 1952, 150. (b)
Singh, R.; J ust, G. Synth. Commun. 1988, 18, 1327.
(20) Whitmore, F. C.; Woodward, G. E. Organic Syntheses; Wiley:
New York, 1932; Collect. Vol. I, p 325.
(21) Zweifel, G.; Steele, R. B. J . Am. Chem. Soc. 1967, 89, 2753.

2844 J . Org. Chem., Vol. 67, No. 9, 2002
Ma et al.
265 (M+ - 1, 0.52); HRMS m/z (EI) calcd for C15H22O4
mg, 0.15 mmol) and (Z)-1-iodo-1-hexene22 (38 mg, 0.18 mmol)
afforded 23 mg (45%) of 2n using Conditions A: viscous liquid;
266.1518, found 266.1516.
IR (neat) 2954, 1736, 1435, 1264 cm-1 1H NMR (300 MHz,
;
9. 1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-p h en yleth e-
n yl)cyclop r op a n e (2i). Starting from 1b (41 mg, 0.15 mmol)
and PhI (37 mg, 0.18 mmol) afforded 41 mg (80%) of 2i using
Conditions A: liquid; IR (neat) 3030, 2954, 1735, 1601, 1493,
1432, 1370 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.41-7.55 (m,
2 H), 7.10-7.38 (m, 6 H), 6.87-6.98 (m, 2 H), 5.52 (s, 1 H),
4.98 (s, 1 H), 3.90 (s, 3 H), 3.50 (s, 3 H), 3.26 (AB, A part of
AB, J ) 13.72 Hz, ∆ν ) 290.15 Hz, 1 H), 2.30 (AB, B part of
AB, J ) 13.72 Hz, ∆ν ) 290.15 Hz, 1 H), 2.00 (AB, A part of
AB, J ) 5.46 Hz, ∆ν ) 29.57 Hz, 1 H), 1.91 (AB, B part of AB,
J ) 5.46 Hz, ∆ν ) 29.57 Hz, 1 H); 13C NMR (75 MHz, CDCl3)
δ 168.8, 168.1, 143.8, 138.5, 138.4, 129.7, 128.5, 128.2, 127.8,
127.0, 126.8, 118.2, 53.1, 52.7, 42.4, 41.4, 40.7, 23.9; MS m/z
(%) 350 (M+, 1.29), 231 (100); HRMS m/z (EI) calcd for
CDCl3) δ 6.98-7.23 (m, 5 H), 5.68 (d, J ) 11.78 Hz, 1 H), 5.51
(dt, J ) 11.78, 6.98 Hz, 1 H), 4.89 (s, 1 H), 4.79 (s, 1 H), 3.75
(s, 3 H), 3.58 (s, 3 H), 3.07 (AB, A part of AB, J ) 13.98 Hz,
∆ν ) 187.67 Hz, 1 H), 2.45 (AB, B part of AB, J ) 13.98 Hz,
∆ν ) 187.67 Hz, 1 H), 1.86-1.97 (m, 3 H), 1.76 (d, J ) 5.44
Hz, 1 H), 1.12-1.29 (m, 4 H), 0.74-0.86 (m, 3 H); MS m/z (%)
356 (M+, 1.47), 91 (100); HRMS m/z (EI) calcd for C22H28O4
356.19876, found 356.19738.
15. 1,1-Bis(m eth oxycar bon yl)-2-ben zyl-2-(1′-(2′′-th ien yl)-
eth en yl)cyclop r op a n e (2o). Starting from 1b (68 mg, 0.25
mmol) and 2-iodothiophene23 (63 mg, 0.3 mmol) afforded 86
mg (97%) of 2o using Conditions A: viscous liquid; IR (neat)
3028, 2952, 1735, 1602, 1495, 1435 cm-1; 1H NMR (300 MHz,
CDCl3) δ 6.75-7.32 (m, 8 H), 5.37 (s, 1 H), 4.56 (s, 1 H), 3.84
(s, 3 H), 3.42 (s, 3 H), 3.32 (AB, A part of AB, J ) 13.49 Hz,
∆ν ) 345.48 Hz, 1 H), 2.17 (AB, B part of AB, J ) 13.49 Hz,
∆ν ) 345.48 Hz, 1 H), 1.87 (AB, J ) 5.23 Hz, ∆ν ) 20.31 Hz,
2 H); MS m/z (%) 356 (M+, 10.66), 354 (100); HRMS m/z (EI)
calcd for C20H20O4S 356.10823, found 356.10914.
16. 1,1-Bis(m eth oxycar bon yl)-2-pr opyl-2-(1′-ph en yleth e-
n yl)cyclop r op a n e (2p ). Starting from 1c (56.5 mg, 0.25
mmol) and PhI (61 mg, 0.3 mmol) afforded 58 mg (77%) of 2p
using Conditions A: viscous liquid; IR (neat) 2941, 1740, 1433
cm-1; 1H NMR (300 MHz, CDCl3) δ 7.55 (d, J ) 8.69 Hz, 2 H),
7.15-7.32 (m, 3 H), 5.62 (s, 1 H), 5.14 (s, 1 H), 3.78 (s, 3 H),
3.43 (s, 3 H), 1.82-2.00 (m, 2 H), 1.44-1.47 (m, 2 H), 1.12-
1.35 (m, 2 H), 0.66-0.81 (m, 3 H); MS m/z (%) 302 (M+, 30.80),
242 (100); HRMS m/z (EI) calcd for C18H22O4 302.15181, found
302.15451.
C
22H22O4 350.15181, found 350.14733.
10. 1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-(4′′-m eth -
oxyp h en yl)eth en yl)cyclop r op a n e (2j). Starting from 1b (41
mg, 0.15 mmol) and 4-iodoanisole (42 mg, 0.18 mmol) afforded
36 mg (63%) of 2j using Conditions A: viscous liquid; IR (neat)
3029, 2952, 1725, 1607, 1513, 1435 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.36 (d, J ) 8.75 Hz, 2 H), 7.05-7.16 (m, 3 H), 6.73-
6.88 (m, 4 H), 5.34 (s, 1 H), 4.70 (s, 1 H), 3.82 (s, 3 H), 3.74 (s,
3 H), 3.43 (s, 3 H), 3.17 (AB, A part of AB, J ) 13.68 Hz, ∆ν
) 294.18 Hz, 1 H), 2.19 (AB, B part of AB, J ) 13.68 Hz, ∆ν
) 294.18 Hz, 1 H), 1.92 (AB, A part of AB, J ) 5.45 Hz, ∆ν )
31.40 Hz, 1 H), 1.82 (AB, B part of AB, J ) 5.45 Hz, ∆ν )
31.40 Hz, 1 H); 13C NMR (75 MHz, CDCl3) δ 168.9, 168.1,
159.4, 143.1, 138.5, 131.0, 129.6, 128.2, 126.7, 116.3, 113.9,
55.5, 53.1, 52.7, 42.6, 41.3, 40.6, 23.8; MS m/z (%) 380 (M+,
21.34), 229 (100); HRMS m/z (EI) calcd for C23H24O5 380.16238,
found 380.16477.
17. 1,1-Bis(m eth oxyca r bon yl)-2-p r op yl-2-(1′-(4′′-m eth -
oxyp h en yl)eth en yl)cyclop r op a n e (2q). Starting from 1c
(56.5 mg, 0.25 mmol) and 4-iodoanisole (70 mg, 0.3 mmol)
afforded 37 mg (45%) of 2q using Conditions A: IR (neat) 2956,
11. 1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-(4′′-m eth -
oxyca r bon yl)p h en yl-eth en yl)cyclop r op a n e (2k ). Starting
from 1b (41 mg, 0.15 mmol) and 4-iodobenzoic acid methyl
ester (47 mg, 0.18 mmol) afforded 50 mg (82%) of 2k , and 10
mg (16%) of 3k using Conditions A. 2k : viscous liquid; IR
(neat) 2952, 1724, 1608, 1435, 1281 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.93 (d, J ) 8.42 Hz, 2 H), 7.46 (d, J ) 8.42 Hz, 2 H),
7.03-7.17 (m, 3 H), 6.77-6.90 (m, 2 H), 5.56 (s, 1 H), 4.94 (s,
1 H), 3.85 (s, 3 H), 3.84 (s, 3 H), 3.44 (s, 3 H), 3.17 (AB, A part
of AB, J ) 13.80 Hz, ∆ν ) 279.00 Hz, 1 H), 2.24 (AB, B part
of AB, J ) 13.80 Hz, ∆ν ) 279.00 Hz, 1 H), 1.91 (AB, J ) 5.38
Hz, ∆ν ) 13.85 Hz, 2 H); MS m/z (%) 408 (M+, 6.69), 348 (100);
HRMS m/z (EI) calcd for C24H24O6 408.15729, found 408.15967.
1737, 1608, 1514, 1435 cm-1 1H NMR (300 MHz, CDCl3) δ
;
7.49 (d, J ) 6.77 Hz, 2 H), 6.80 (d, J ) 6.77 Hz, 2 H), 5.51 (s,
1 H), 5.04 (s, 1 H), 3.77 (s, 3 H), 3.75 (s, 3 H), 3.42 (s, 3 H),
1.80-2.00 (m, 2 H), 1.48-1.55 (m, 2 H), 1.08-1.28 (m, 2 H),
0.71 (t, J ) 7.33 Hz, 3 H); 13C NMR (75 MHz, CDCl3) δ 168.9,
168.2, 159.3, 143.3, 130.8, 128.0, 115.0, 113.8, 55.4, 52.9, 52.6,
41.7, 41.0, 36.8, 24.1, 20.6, 14.0; MS m/z (%) 332 (M+, 78.78),
272 (100); HRMS m/z (EI) calcd for C19H24O5 332.16238, found
332.16497.
18. 1,1-Bis(m eth oxyca r bon yl)-2-p r op yl-2-(1′-(4′′-m eth -
oxyca r bon ylp h en yl) eth en yl)cyclop r op a n e (2r ). Starting
from 1c (56.5 mg, 0.25 mmol) and 4-iodobenzoic acid methyl
ester (79 mg, 0.3 mmol) afforded 64 mg (71%) of 2r using
Conditions A: viscous liquid; IR (neat) 2955, 1725, 1608, 1435,
1279 cm-1; 1H NMR (300 MHz, CDCl3) δ 8.00 (d, J ) 8.49 Hz,
2 H), 7.68 (d, J ) 8.49 Hz, 2 H), 5.78 (s, 1 H), 5.31 (s, 1 H),
3.88 (s, 3 H), 3.84 (s, 3 H), 3.48 (s, 3 H), 1.80-2.12 (m, 2 H),
1.48-1.72 (m, 2 H), 1.12-1.38S (m, 2 H), 0.76 (t, J ) 7.30 Hz,
3 H); 13C NMR (75 MHz, CDCl3) δ 168.6, 168.1, 167.1, 143.3,
142.9, 129.8, 129.3, 126.7, 118.9, 53.0, 52.7, 52.3, 41.2, 41.1,
36.7, 24.1, 20.6, 14.0; MS m/z (%) 360 (M+, 21.45), 300 (100);
HRMS m/z (EI) calcd for C20H24O6 360.15729, found 360.15819.
12. (E)-1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-m eth -
ylen e-3′-p h en yl-2′-p r op en yl)cyclop r op a n e (2l). Starting
from 1b (68 mg, 0.25 mmol) and (E)-1-iodo-2-phenylethylene
(69 mg, 0.3 mmol) afforded 79 mg (84%) of 2l using Conditions
A: viscous liquid; IR (neat) 3027, 2951, 1734, 1603, 1495, 1435
cm-1; 1H NMR (300 MHz, CDCl3) δ 7.40 (d, J ) 7.22 Hz, 2 H),
7.23-7.31 (m, 2 H), 7.07-7.22 (m, 5 H), 6.96-7.07 (m, 2 H),
6.60 (d, J ) 16.64 Hz, 1 H), 5.11 (s, 1 H), 4.63 (s, 1 H), 3.87 (s,
3 H), 3.45 (s, 3 H), 3.31 (AB, A part of AB, J ) 13.61 Hz, ∆ν
) 342.50 Hz, 1 H), 2.17 (AB, B part of AB, J ) 13.61 Hz, ∆ν
) 342.50 Hz, 1 H), 1.81 (AB, J ) 3.60 Hz, ∆ν ) 12.00 Hz, 2
H); MS m/z (%) 376 (M+, 7.07), 165 (100); HRMS m/z (EI) calcd
for C24H24O4 376.16746, found 376.16917.
19. (E)-1,1-Bis(m eth oxyca r bon yl)-2-p r op yl-2-(1′-m eth -
ylen e-3′-p h en yl-2-p r op en yl)cyclop r op a n e (2s). Starting
from 1c (56.5 mg, 0.25 mmol) and (E)-1-iodo-2-phenylethylene
(69 mg, 0.3 mmol) afforded 62 mg (71%) of 2s using Conditions
13. (E)-1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-m eth -
ylen e-2′-h ep ten yl)cyclop r op a n e (2m ). Starting from 1b (71
mg, 0.26 mmol) and (E)-1-iodo-1-hexene (66 mg, 0.31 mmol)
afforded 60 mg (67%) of 2m using Conditions A: viscous liquid;
A: viscous liquid; IR (neat) 2956, 1736, 1608, 1435, 1222 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.11-7.44 (m, 5 H), 7.02 (d, J )
16.57 Hz, 1 H), 6.61 (d, J ) 16.57 Hz, 1 H), 5.31 (s, 1 H), 5.12
(s, 1 H), 3.81 (s, 3 H), 3.43 (s, 3 H), 1.98-2.10 (m, 1 H), 1.83
(AB, A part of AB, J ) 4.62 Hz, ∆ν ) 109.83 Hz, 1 H), 1.47
(AB, B part of AB, J ) 4.62 Hz, ∆ν ) 109.83 Hz, 1 H), 1.10-
1.41 (m, 2 H), 0.78 (t, J ) 7.34 Hz, 3 H), 0.58-0.72 (m, 1 H);
IR (neat) 2954, 1736, 1434, 1240 cm-1 1H NMR (400 MHz,
;
CDCl3) δ 7.08-7.20 (m, 3 H), 6.91-7.01 (m, 2 H), 6.12 (dt, J
) 15.98, 7.00 Hz, 1 H), 5.86 (d, J ) 15.98 Hz, 1 H), 4.87 (s, 1
H), 4.44 (s, 1 H), 3.80 (s, 3 H), 3.54 (s, 3 H), 3.24 (d, J ) 13.50
Hz, 1 H), 1.98-2.30 (m, 3 H), 1.73 (AB, J ) 5.15 Hz, ∆ν )
18.35 Hz, 2 H), 1.15-1.41 (m, 4 H), 0.77-0.92 (m, 3 H); MS
m/z (%) 356 (M+, 9.84), 91 (100); HRMS m/z (EI) calcd for
(22) Brown, H. C.; Bule, C. D.; Nelson, D. J .; Bhat, N. G. J . Org.
Chem. 1989, 54, 6064.
(23) Lew, H. Y.; Noller, C. R. Organic Syntheses; Wiley: New York,
1963; Collect. Vol. IV, p 545.
C
22H28O4 356.19876, found 356.19623.
14. (Z)-1,1-Bis(m eth oxyca r bon yl)-2-ben zyl-2-(1′-m eth -
ylen e-2′-h ep ten yl)cyclop r op a n e (2n ). Starting from 1b (41

Control of Regioselectivity
J . Org. Chem., Vol. 67, No. 9, 2002 2845
MS m/z (%) 328 (M+, 10.75), 268 (100); HRMS m/z (EI) calcd
for C20H24O4 328.16746, found 328.17123.
25. 1,1-Bis(m eth oxycar bon yl)-2-(1′-(4′′-m eth oxyph en yl)-
oct-1′-en yl)cyclop r op a n e (2y). Starting from 1d (40.2 mg,
0.15 mmol) and 4-iodoanisole (42 mg, 0.18 mmol) afforded 32
mg (57%) of 2y and 5 mg (9%) of 3y using Conditions A. 2y:
viscous liquid; IR (neat) 2953, 1730, 1608, 1512, 1437, 1283
cm-1; 1H NMR (300 MHz, CDCl3) E-isom er δ 7.08 (d, J ) 8.81
Hz, 2 H), 6.74 (d, J ) 8.81 Hz, 2 H), 5.71 (dt, J ) 7.24, 1.98
Hz, 1 H), 3.72 (s, 3 H), 3.71 (s, 3 H), 3.34 (s, 3 H), 2.92 (t, J )
8.94 Hz, 1 H), 2.07-2.30 (m, 2 H), 1.72 (AB, A part of AB, dd,
J ) 8.94, 4.72 Hz, ∆ν ) 27.67 Hz, 1 H), 1.63 (AB, B part of
AB, dd, J ) 8.94, 4.72 Hz, ∆ν ) 27.67 Hz, 1 H), 1.04-1.35 (m,
8 H), 0.82 (t, J ) 6.54 Hz, 3 H); Z-isom er δ 7.04 (d, J ) 8.52
Hz, 2 H), 6.79 (d, J ) 8.52 Hz, 2 H), 5.39 (dt, J ) 7.37, 1.07
Hz, 1 H), 3.73 (s, 3 H), 3.64 (s, 3 H), 3.52 (s, 3 H), 2.79 (dt, J
) 8.92, 1.07 Hz, 1 H), 1.80-1.98 (m, 3 H), 1.45 (AB, B part of
AB, dd, J ) 8.92, 5.04 Hz, 1 H), 1.04-1.35 (m, 8 H), 0.77 (t, J
) 6.78 Hz, 3 H); MS m/z (%) 374 (M+, 19.55), 44 (100); HRMS
m/z (EI) calcd for C22H30O5 374.20932, found 374.21264.
26. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-(4′′-m eth oxyca r bo-
n ylp h en yl)oct-1′-en yl)cyclop r op a n e (2z). Starting from 1d
(40.2 mg, 0.15 mmol) and 4-iodobenzoic acid methyl ester (48
mg, 0.18 mmol) afforded 43 mg (71%) of 2z and 5 mg (8%) of
3z using Conditions A. 2z: viscous liquid; IR (neat) 2953, 1726,
20. (E)-1,1-Bis(m eth oxyca r bon yl)-2-p r op yl-2-(1′-m eth -
ylen e-2′-h ep ten yl)cyclop r op a n e(2t). Starting from 1c (56.5
mg, 0.25 mmol) and (E)-1-iodo-1-hexene (63 mg, 0.3 mmol)
afforded 54 mg (70%) of 2t using Conditions A: viscous liquid;
IR (neat) 2957, 1738, 1435, 1222 cm-1 1H NMR (300 MHz,
;
CDCl3) δ 6.13 (dt, J ) 15.92, 7.08 Hz, 1 H), 5.92 (d, J ) 15.92
Hz, 1 H), 5.11 (s, 1 H), 4.96 (s, 1 H), 3.79 (s, 3 H), 3.57 (s, 3 H),
1.92-2.14 (m, 4 H), 1.81 (AB, A part of AB, J ) 4.89 Hz, ∆ν )
109.51 Hz, 1 H), 1.45 (AB, B part of AB, J ) 4.89 Hz, ∆ν )
109.51 Hz, 1 H), 1.11-1.41 (m, 5 H), 0.89 (t, J ) 7.06 Hz, 3
H), 0.82 (t, J ) 7.34 Hz, 3 H), 0.58-0.72 (m, 1 H); MS m/z (%)
308 (M+, 7.96), 41 (100); HRMS m/z (EI) calcd for C18H28O4
308.19876, found 308.19912.
21. (Z)-1,1-Bis(m eth oxyca r bon yl)-2-p r op yl-2-(1′-m eth -
ylen e-2′-h ep ten yl)cyclop r op a n e (2u ). Starting from 1c
(56.5 mg, 0.25 mmol) and (Z)-1-iodo-1-hexene (63 mg, 0.3
mmol) afforded 44 mg (57%) of 2u using Conditions A: viscous
1
liquid; IR (neat) 2957, 1738, 1435, 1223, 1120 cm-1; H NMR
(300 MHz, CDCl3) δ 5.67 (d, J ) 11.78 Hz, 1 H), 5.51 (dt, J )
11.78, 7.05 Hz, 1 H), 5.06 (s, 1 H), 5.05 (s, 1 H), 3.70 (s, 3 H),
3.56 (s, 3 H), 2.03-2.26 (m, 2 H), 1.86 (AB, A part of AB, dd,
J ) 5.19, 1.58 Hz, ∆ν ) 132.63 Hz, 1 H), 1.42 (AB, B part of
AB, J ) 5.19 Hz, ∆ν ) 132.63 Hz, 1 H), 1.71-1.82 (m, 1 H),
1.10-1.37 (m, 6 H), 0.71-0.95 (m, 7 H); MS m/z (%) 308 (M+,
6.28), 248 (100); HRMS m/z (EI) calcd for C18H28O4 308.19876,
found 308.19952.
22. 1,1-Bis(m et h oxyca r b on yl)-2-p r op yl-2-(1′-(2′′-t h ie-
n yl)eth en yl)cyclop r op a n e (2v). Starting from 1c (56.5 mg,
0.25 mmol) and 2-iodothiophene (63 mg, 0.3 mmol) afforded
61 mg (79%) of 2v using Conditions A: viscous liquid; IR (neat)
2956, 1737, 1620, 1435, 1223 cm-1; 1H NMR (300 MHz, CDCl3)
δ 7.35 (d, J ) 2.94 Hz, 1 H), 7.13 (dd, J ) 2.94, 0.86 Hz, 1 H),
6.93-7.00 (m, 1 H), 5.63 (s, 1 H), 5.08 (s, 1 H), 3.80 (s, 3 H),
3.46 (s, 3 H), 2.02-2.17 (m, 1 H), 1.92 (AB, A part of AB, dd,
J ) 5.10, 1.7 Hz, ∆ν ) 119.95 Hz, 1 H), 1.52 (AB, B part of
AB, J ) 5.10 Hz, ∆ν ) 119.95 Hz, 1 H), 1.13-1.41 (m, 2 H),
0.81 (t, J ) 7.35 Hz, 3 H), 0.63-0.77 (m, 1 H); MS m/z (%) 308
(M+, 8.49), 219 (100); HRMS m/z (EI) calcd for C16H20O4S
308.10823, found 308.10760.
23. 1,1-Bis(m eth oxycar bon yl)-2-((1′-ph en yl)oct-1′-en yl)-
cyclop r op a n e (2w ). Starting from 1d (40.2 mg, 0.15 mmol)
and PhI (37 mg, 0.18 mmol) afforded 37 mg (72%) of 2w and
3 mg (6%) of 3w using Conditions A. 2w : viscous liquid; IR
(neat) 2926, 1730, 1437, 1281, 1130 cm-1; 1H NMR (300 MHz,
CDCl3) E-isom er δ 6.99-7.28 (m, 5 H), 5.79 (dt, J ) 7.28,
1.84 Hz, 1 H), 3.72 (s, 3 H), 3.31 (s, 3 H), 2.95 (t, J ) 8.88 Hz,
1 H), 2.10-2.31 (m, 2 H), 1.72 (AB, A part of AB, dd, J ) 8.88,
4.74 Hz, ∆ν ) 23.48 Hz, 1 H), 1.64 (AB, B part of AB, dd, J )
8.88, 4.74 Hz, ∆ν ) 23.48 Hz, 1 H), 1.00-1.39 (m, 8 H), 0.83
(t, J ) 6.42 Hz, 3 H); Z-isom er δ 6.99-7.28 (m, 5 H), 5.45 (t,
J ) 7.46, Hz, 1 H), 3.65 (s, 3 H), 3.53 (s, 3 H), 2.82 (t, J ) 8.72
Hz, 1 H), 1.83-1.97 (m, 3 H), 1.40-1.51 (m, 1 H), 1.00-1.39
(m, 8 H), 0.78 (t, J ) 6.86 Hz, 3 H); MS m/z (%) 344 (M+, 6.34),
141 (100); HRMS m/z (EI) calcd for C21H28O4 344.19876, found
344.20307.
1607, 1437, 1278 cm-1 1H NMR (300 MHz, CDCl3) E-
;
isom er : δ 7.93 (d, J ) 8.20 Hz, 2 H), 7.18 (d, J ) 8.20 Hz, 2
H), 5.90 (dt, J ) 7.25 and 1.99 Hz, 1 H), 3.83 (s, 3 H), 3.72 (s,
3 H), 3.00 (s, 3 H), 2.95 (t, J ) 9.14 Hz, 1 H), 2.11-2.35 (m, 2
H), 1.61-1.73 (m, 2 H), 0.94-1.37 (m, 8 H), 0.82 (t, J ) 6.84
Hz, 3 H); Z-isom er : δ 7.88 (d, J ) 8.52 Hz, 2 H), 7.24 (d, J )
8.52 Hz, 2 H), 5.51 (t, J ) 7.62 Hz, 1 H), 3.85 (s, 3 H), 3.65 (s,
3 H), 3.52 (s, 3 H), 2.81 (t, J ) 8.56 Hz, 1 H), 1.80-1.97 (m, 3
H), 1.38-1.53 (m, 1 H), 0.94-1.37 (m, 8 H), 0.77 (t, J ) 6.93
Hz, 3 H); MS m/z (%) 402 (M+, 3.79), 342 (100); HRMS m/z
(EI) calcd for C23H30O6 402.20424, found 402.20062. 1-(4′-
Met h oxyca r b on ylp h en yl)-4,4-b is(m et h oxyca r b on yl)-5-
(n -h exyl)cyclop en ten e (3z): viscous liquid; IR (neat) 2953,
1735, 1607, 1435, 1280 cm-1 1H NMR (300 MHz, CDCl3) δ
;
7.92 (d, J ) 7.85 Hz, 2 H), 7.43 (d, J ) 7.85 Hz, 2 H), 5.93 (s,
1 H), 3.88-4.01 (m, 1 H), 3.84 (s, 3 H), 3.70 (s, 3 H), 3.66 (s, 3
H), 3.37 (AB, A part of AB, J ) 18.42 Hz, ∆ν ) 143.78 Hz 1
H), 2.89 (AB, B part of AB, J ) 18.42 Hz, ∆ν ) 148.78 Hz 1
H), 1.23-1.46 (m, 2 H), 0.88-1.20 (m, 8 H), 0.73 (t, J ) 6.75
Hz, 3 H); MS m/z (%) 402 (M+, 31.66), 254 (100); HRMS m/z
(EI) calcd for C23H30O6 402.20424, found 402.20502.
27. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-((E)-2′′-p h en yleth e-
n yl)oct-1′-en yl)cyclop r op a n e (2r). Starting from 1d (40.2
mg, 0.15 mmol) and (E)-1-iodo-2-phenylethylene (41.4 mg, 0.18
mmol) afforded 49 mg (88%) of 2R using Conditions A: viscous
1
liquid; IR (neat) 2927, 1730, 1590, 1436, 1285 cm-1; H NMR
(300 MHz, CDCl3) E-isom er δ 6.46-7.48 (m, 7 H), 5.74 (t, J
) 7.47 Hz, 1 H), 3.74 (s, 3 H), 3.45 (s, 3 H), 2.61 (t, J ) 8.45
Hz, 1 H), 2.04-2.27 (m, 2 H), 1.61-1.75 (m, 2 H), 0.94-1.40
(m, 8 H), 0.56-0.93 (m, 3 H); Z-isom er δ 6.46-7.48 (m, 7 H),
5.44 (t, J ) 7.51 Hz, 1 H), 3.73 (s, 3 H), 3.43 (s, 3 H), 2.81 (t,
J ) 8.28 Hz, 1 H), 2.04-2.27 (m, 2 H), 1.77-2.00 (m, 1 H),
1.41-1.59 (m, 1 H), 0.94-1.40 (m, 8 H), 0.56-0.93 (m, 3 H);
MS m/z (%) 370 (M+, 9.22), 310 (100); HRMS m/z (EI) calcd
for C23H30O4 370.21441, found 370.21503.
24. 1,1-Bis(m eth oxyca r bon yl)-2-(1′-(4′′-m eth ylp h en yl)-
oct-1′-en yl)cyclop r op a n e (2x). Starting from 1d (40.2 mg,
0.15 mmol) and 4-iodotoluene (43 mg, 0.19 mmol) afforded 47
mg (88%) of 2x and 2 mg (4%) of 3x using Conditions A. 2x:
28. 1,1-Bis(m eth oxyca r bon yl)-2-m eth yl-2-((1′-p h en yl)-
p en t-1′-en yl)cyclop r op a n e (2â). Starting from 1e (36 mg,
0.15 mmol) and PhI (37 mg, 0.18 mmol) afforded 20 mg (42%)
of 2â and 10 mg (21%) of 3â using Conditions A. Z-2â: viscous
1
viscous liquid; IR (neat) 2924, 1731, 1513, 1437, 1281 cm-1
;
liquid; IR (neat) 2957, 1737, 1600, 1436, 1235 cm-1; H NMR
1H NMR (300 MHz, CDCl3) E-isom er δ 6.94-7.26 (m, 4 H),
5.75 (dt, J ) 7.27, 1.95 Hz, 1 H), 3.71 (s, 3 H), 3.33 (s, 3 H),
2.93 (t, J ) 8.70 Hz, 1 H), 2.24 (s, 3 H), 2.05-2.21 (m, 2 H),
1.71 (AB, A part of AB, dd, J ) 8.70, 4.73 Hz, ∆ν ) 26.24 Hz,
1 H), 1.63 (AB, B part of AB, dd, J ) 8.70, 4.73 Hz, ∆ν ) 26.24
Hz, 1 H), 1.05-1.45 (m, 8 H), 0.80 (t, J ) 6.70 Hz, 3 H);
Z-isom er δ 6.94-7.26 (m, 4 H), 5.39 (dt, J ) 7.44, 1.16 Hz, 1
H), 3.65 (s, 3 H), 3.51 (s, 3 H), 2.79 (dt, J ) 8.99, 1.05 Hz, 1
H), 2.25 (s, 3 H), 1.84-1.96 (m, 3 H), 1.43 (AB, B part of AB,
dd, J ) 8.99, 5.04 Hz, 1 H), 1.05-1.45 (m, 8 H), 0.76 (t, J )
6.86 Hz, 3 H); MS m/z (%) 358 (M+, 11.97), 298 (100); HRMS
m/z (EI) calcd for C22H30O4 358.21441, found 358.21098.
(300 MHz, CDCl3) δ 7.04-7.29 (m, 5 H), 5.61 (t, J ) 7.44 Hz,
1 H), 3.70 (s, 3 H), 3.58 (s, 3 H), 1.77-1.92 (m, 3 H), 1.37 (AB,
B part of AB, J ) 5.31 Hz, 1 H), 1.30 (s, 3 H), 1.13-1.26 (m,
2 H), 0.76 (t, J ) 7.35 Hz, 3 H); MS m/z (%) 316 (M+, 9.90),
256 (100); HRMS m/z (EI) calcd for C19H24O4 316.16746, found
316.16741. 1-P h en yl-2-m eth yl-4,4-bis(m eth oxyca r bon yl)-
5-p r op yl-cyclop en ten e (3â): viscous liquid; IR (neat) 2956,
1736, 1434, 1253, 1159 cm-1 1H NMR (300 MHz, CDCl3) δ
;
7.16-7.40 (m, 5 H), 3.88-3.97 (m, 1 H), 3.76 (s, 3 H), 3.74 (s,
3 H), 3.50 (AB, A part of AB, J ) 16.02 Hz, ∆ν ) 227.76 Hz 1
H), 2.74 (AB, B part of AB, J ) 16.02 Hz, ∆ν ) 227.76 Hz 1
H), 1.73 (s, 3 H), 1.18-1.41 (m, 2 H), 0.92-1.13 (m, 2 H), 0.68

2846 J . Org. Chem., Vol. 67, No. 9, 2002
Ma et al.
(t, J ) 7.18 Hz, 3 H); MS m/z (%) 316 (M+, 21.72), 256 (100);
HRMS m/z (EI) calcd for C19H24O4 316.16746, found 316.16896.
29. 1-P h en yl-2-ben zyl-4,4-bis(m eth oxyca r bon yl)cyclo-
p en ten e (3i). Starting from 1b (41 mg, 0.15 mmol) and PhI
(37 mg, 0.18 mmol) afforded 46 mg (88%) of 3i using Conditions
mg, 0.3 mmol) afforded 49 mg (54%) of 3r and 7 mg (8%) of 2r
using Conditions C. 3r : viscous liquid; IR (neat) 2956, 1731,
1
1608, 1432, 1276 cm-1; H NMR (300 MHz, CDCl3) δ 8.01 (d,
J ) 8.28 Hz, 2 H), 7.31 (d, J ) 8.28 Hz, 2 H), 3.92 (s, 3 H),
3.77 (s, 6 H), 3.41 (s, 2 H), 3.18 (s, 2 H), 2.21 (t, J ) 7.62 Hz,
2 H), 1.40-1.55 (m, 2 H), 0.89 (t, J ) 7.34 Hz, 3 H); 13C NMR
(75 MHz, CDCl3) δ 172.4, 166.9, 141.8, 138.5, 131.7, 129.5,
128.3, 127.7, 127.6, 57.3, 52.9, 52.0, 44.6, 44.3, 30.9, 21.1, 14.0;
MS m/z (%) 360 (M+, 20.32), 300 (100); HRMS m/z (EI) calcd
for C20H24O6 360.15729, found 360.15892.
1
C: viscous liquid; IR (neat) 1736, 1494, 1434, 1263 cm-1; H
NMR (300 MHz, CDCl3) δ 7.02-7.31 (m, 10 H), 3.65 (s, 6 H),
3.51 (s, 2 H), 3.40 (s, 2 H), 2.97 (s, 2 H); 13C NMR (75 MHz,
CDCl3) δ 172.7, 139.2, 136.8, 134.9, 134.0, 128.8, 128.7, 128.6,
127.8, 127.4, 126.4, 57.6, 53.1, 45.1, 44.5, 35.1; MS m/z (%)
350 (M+, 38.30), 290 (100); HRMS m/z (EI) calcd for C22H22O4
350.15181, found 350.14790.
30. 1-(4′-Meth ylp h en yl)-2-ben zyl-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3ø). Starting from 1b (41 mg, 0.15
mmol) and 4-iodotoluene (40 mg, 0.18 mmol) afforded 43 mg
(79%) of 3ø using Conditions C: viscous liquid; IR (neat) 3026,
2952, 1736, 1514, 1495, 1434, 1262 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.08-7.32 (m, 9 H), 3.72 (s, 6 H), 3.57 (s, 2 H), 3.44
(s, 2 H), 3.03 (s, 2 H), 2.34(s, 3 H); MS m/z (%) 364 (M+, 61.81),
304 (100); HRMS m/z (EI) calcd for C23H24O4 364.16746, found
364.16657.
31. 1-(4′-Meth oxyp h en yl)-2-ben zyl-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3j). Starting from 1b (41 mg, 0.15
mmol) and 4-iodoanisole (42 mg, 0.18 mmol) afforded 56 mg
(98%) of 3j using Conditions C: viscous liquid; IR (neat) 2953,
1735, 1609, 1512, 1495, 1435 cm-1; 1H NMR (300 MHz, CDCl3)
δ 7.00-7.26 (m, 7 H), 6.80 (d, J ) 8.80 Hz, 2 H), 3.73 (s, 3 H),
3.65 (s, 6 H), 3.50 (s, 2 H), 3.40 (s, 2 H), 2.96(s, 2 H); 13C NMR
(75 MHz, CDCl3) δ 172.8, 158.9, 139.3, 134.3, 132.7, 129.2,
128.9, 128.8, 128.7, 128.6, 126.3, 114.0, 57.5, 55.5, 53.1, 45.1,
44.5, 35.1; MS m/z (%) 380 (M+, 94.31), 229 (100); HRMS m/z
(EI) calcd for C23H24O5 380.16238, found 380.16258.
37. 1-P h en yl-4,4-bis(m eth oxyca r bon yl)-5-(n -h exyl)cy-
clop en ten e (3w ). Starting from 1d (40.2 mg, 0.15 mmol) and
PhI (37 mg, 0.18 mmol) afforded 42 mg (81%) of 3w using
Conditions C: viscous liquid; IR (neat) 2953, 1736, 1434, 1252
1
cm-1; H NMR (300 MHz, CDCl3) δ 7.20-7.49 (m, 5 H), 5.86
(s, 1 H), 3.93-4.05 (m, 1 H), 3.76 (s, 3 H), 3.72 (s, 3 H), 3.40
(AB, A part of AB, J ) 17.53 Hz, ∆ν ) 140.67 Hz 1 H), 2.93
(AB, B part of AB, dd, J ) 17.53, 3.16 Hz, ∆ν ) 140.67 Hz 1
H), 1.31-1.50 (m, 2 H), 0.98-1.30 (m, 8 H), 0.80 (t, J ) 6.86
Hz, 3 H); 13C NMR (75 MHz, CDCl3) δ 173.1, 170.9, 146.3,
135.9, 128.6, 127.7, 126.5, 122.0, 64.8, 53.1, 52.7, 50.1, 39.4,
31.8, 29.8, 29.7, 27.1, 22.8, 14.3; MS m/z (%) 344 (M+, 47.52),
196 (100); HRMS m/z (EI) calcd for C21H28O4 344.19876, found
344.19945.
38. 1-(4′-Meth ylp h en yl)-4,4-bis(m eth oxyca r bon yl)-5-(n -
h exyl)cyclop en ten e (3x). Starting from 1d (40.2 mg, 0.15
mmol) and 4-iodotoluene (40 mg, 0.18 mmol) afforded 44 mg
(82%) of 3x and 3 mg (5%) of 2x using Conditions C. 3x:
viscous liquid; IR (neat) 2952, 1737, 1434, 1251 cm-1; 1H NMR
(300 MHz, CDCl3) δ 7.26 (d, J ) 8.00 Hz, 2 H), 7.06 (d, J )
8.00 Hz, 2 H), 5.74 (t, J ) 2.40 Hz, 1 H), 3.91 (t, J ) 4.97 Hz,
1 H), 3.69 (s, 3 H), 3.65 (s, 3 H), 3.32 (AB, A part of AB, J )
17.44 Hz, ∆ν ) 138.45 Hz 1 H), 2.86 (AB, B part of AB, dd, J
) 17.44, 3.20 Hz, ∆ν ) 138.45 Hz 1 H), 2.27 (s, 3 H), 1.25-
1.40 (m, 2 H), 0.86-1.16 (m, 8 H), 0.74 (t, J ) 6.89 Hz, 3 H);
MS m/z (%) 358 (M+, 57.67), 299 (100); HRMS m/z (EI) calcd
for C22H30O4 358.21441, found 358.20982.
39. 1-(4′-Meth oxyp h en yl)-4,4-bis(m eth oxyca r bon yl)-5-
(n -h exyl)cyclop en ten e (3y). Starting from 1d (40.2 mg, 0.15
mmol) and 4-iodoanisole (42 mg, 0.18 mmol) afforded 44 mg
(78%) of 3y and 11 mg (20%) of 2y using Conditions C. 3y:
viscous liquid; IR (neat) 2953, 1736, 1607, 1512, 1458, 1258
cm-1; 1H NMR (300 MHz, CDCl3) δ 7.18 (d, J ) 8.59 Hz, 2 H),
6.66 (d, J ) 8.59 Hz, 2 H), 5.56 (s, 1 H), 3.74 (t, J ) 5.46 Hz,
1 H), 3.62 (s, 3 H), 3.57 (s, 3 H), 3.53 (s, 3 H), 3.19 (AB, A part
of AB, J ) 17.22 Hz, ∆ν ) 139.01 Hz 1 H), 2.73 (AB, B part of
AB, dd, J ) 17.22, 3.01 Hz, ∆ν ) 139.01 Hz 1 H), 1.12-1.33
(m, 2 H), 0.78-1.10 (m, 8 H), 0.62 (t, J ) 6.76 Hz, 3 H); MS
m/z (%) 374 (M+, 5.25), 73 (100); HRMS m/z (EI) calcd for
32.
1-(4′-Meth oxyca r bon ylp h en yl)-2-ben zyl-4,4-bis-
(m eth oxyca r bon yl)cyclop en ten e (3k ). Starting from 1b (41
mg, 0.15 mmol) and 4-iodobenzoic acid methyl ester (47 mg,
0.18 mmol) afforded 47 mg (77%) of 3k using Conditions C:
viscous liquid; IR (neat) 2953, 1735, 1607, 1435, 1277 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.94 (d, J ) 8.29 Hz, 2 H), 7.31
(d, J ) 8.29 Hz, 2 H), 7.02-7.26 (m, 5 H), 3.84 (s, 3 H), 3.65
(s, 6 H), 3.51 (s, 2 H), 3.40 (s, 2 H), 3.00 (s, 2 H); MS m/z (%)
408 (M+, 28.21), 348 (100); HRMS m/z (EI) calcd for C24H24O6
408.15729, found 408.15473.
33. 1-P h en yl-2-p r op yl-4,4-bis(m eth oxyca r bon yl)cyclo-
p en ten e (3p ). Starting from 1c (56.5 mg, 0.25 mmol) and PhI
(61 mg, 0.3 mmol) afforded 49 mg (65%) of 3p using Conditions
1
C: viscous liquid; IR (neat) 2956, 1737, 1434, 1262 cm-1; H
NMR (300 MHz, CDCl3) δ 7.12-7.38 (m, 5 H), 3.74 (s, 6 H),
3.37 (s, 2 H), 3.14 (s, 2 H), 2.18 (t, J ) 7.44 Hz, 2 H), 1.49-
1.54 (m, 2 H), 0.86 (t, J ) 7.34 Hz, 3 H); MS m/z (%) 302 (M+,
38.29), 242 (100); HRMS m/z (EI) calcd for C18H22O4 302.15181,
found 302.15330.
C
22H30O5 374.20933, found 374.21299.
40. (E)-1-(2′-P h en yleth en yl)-2-ben zyl-4,4-bis(m eth oxy-
34. 1-(4′-Meth ylp h en yl)-2-p r op yl-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3δ). Starting from 1c (56.5 mg, 0.25
mmol) and 4-iodotoluene (65.4 mg, 0.3 mmol) afforded 43 mg
(54%) of 3δ using Conditions C: viscous liquid; IR (neat) 2958,
ca r bon yl)cyclop en ten e (3l). Starting from 1b (41 mg, 0.15
mmol) and 1-iodo-2-phenylethylene (41.4 mg, 0.18 mmol)
afforded 18 mg (32%) of 3l and 22 mg (39%) of 2l using
Conditions C. 3l: viscous liquid; IR (neat) 1735, 1494, 1432,
1254 cm-1; 1H NMR (300 MHz, CDCl3) δ 6.98-7.32 (m, 11 H),
6.46 (d, J ) 16.04 Hz, 1 H), 3.63 (s, 6 H), 3.56 (s, 2 H), 3.28 (s,
2 H), 2.95 (s, 2 H); MS m/z (%) 376 (M+, 77.96), 316 (100);
HRMS m/z (EI) calcd for C24H24O4 376.16746, found 376.16831.
41. (E)-1-Ben zyl-2-(h ex-1′-en yl)-4,4-bis(m eth oxyca r bo-
n yl)cyclop en ten e (3m ). Starting from 1b (68 mg, 0.25 mmol)
and (E)-1-iodo-1-hexene (63 mg, 0.3 mmol) afforded 21 mg
(24%) of 3m and 36 mg (40%) of 2m using Conditions C. 3m :
viscous liquid; IR (neat) 2955, 1737, 1434, 1259 cm-1; 1H NMR
(300 MHz, CDCl3) δ 7.04-7.30 (m, 5 H), 6.37 (d, J ) 15.60
Hz, 1 H), 5.65 (dt, J ) 15.60, 6.97 Hz, 1 H), 3.68 (s, 6 H), 3.50
(s, 2 H), 3.18 (s, 2 H), 2.92 (s, 2 H), 2.08-2.10 (m, 2 H), 1.20-
1.46 (m, 4 H), 0.90 (t, J ) 7.12 Hz, 3 H); MS m/z (%) 356 (M+,
21.92), 91 (100); HRMS m/z (EI) calcd for C22H28O4 356.19876,
found 356.19571.
1756, 1732, 1432, 1271 cm-1 1H NMR (300 MHz, CDCl3) δ
;
7.05 (s, 4 H), 3.66 (s, 6 H), 3.28 (s, 2 H), 3.05 (s, 2 H), 2.25 (s,
3 H), 2.10 (t, J ) 7.70 Hz, 2 H), 1.32-1.47 (m, 2 H), 0.79 (t, J
) 7.34 Hz, 3 H); MS m/z (%) 316 (M+, 47.23), 256 (100); HRMS
m/z (EI) calcd for C19H24O4 316.16746, found 316.17144.
35. 1-(4′-Meth oxyp h en yl)-2-p r op yl-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3q). Starting from 1c (56.5 mg, 0.25
mmol) and 4-iodoanisole (70.2 mg, 0.3 mmol) afforded 39 mg
(47%) of 3q and 6 mg (7%) of 2q using Conditions C. 3q:
viscous liquid; IR (neat) 2956, 1736, 1620, 1512, 1250 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.19 (d, J ) 8.44 Hz, 2 H), 6.88
(d, J ) 8.44 Hz, 2 H), 3.82 (s, 3 H), 3.76 (s, 6 H), 3.36 (s, 2 H),
3.14 (s, 2 H), 2.19 (t, J ) 7.54 Hz, 2 H), 1.36-1.62 (m, 2 H),
0.89 (t, J ) 7.30 Hz, 3 H); 13C NMR (75 MHz, CDCl3) δ 172.7,
158.3, 134.9, 131.8, 129.5, 128.8, 113.5, 57.3, 55.2, 52.8, 44.9,
44.1, 30.8, 21.2, 14.0; MS m/z (%) 332 (M+, 4.12), 317 (100);
HRMS m/z (EI) calcd for C19H24O5 332.16238, found 332.15920.
42. (E)-1-(Hex-1′-en yl)-2-p r op yl-4,4-bis(m eth oxyca r bo-
n yl)cyclop en ten e (3t). Starting from 1c (56.5 mg, 0.25 mmol)
and (E)-1-iodo-1-hexene (63 mg, 0.3 mmol) afforded 14 mg
(18%) of 3t and 25 mg (32%) of 2t using Conditions C. 3t:
36.
1-(4′-Meth oxyca r bon ylp h en yl)-2-p r op yl-4,4-bis-
(m eth oxyca r bon yl)cyclop en ten e (3r ). Starting from 1c
(56.5 mg, 0.25 mmol) and 4-iodobenzoic acid methyl ester (79
viscous liquid; IR (neat) 2957, 1738, 1434, 1258, 1164 cm-1
;

Control of Regioselectivity
J . Org. Chem., Vol. 67, No. 9, 2002 2847
1H NMR (300 MHz, CDCl3) δ 6.16 (d, J ) 15.63 Hz, 1 H), 5.47
(dt, J ) 15.63, 6.94 Hz, 1 H), 3.66 (s, 6 H), 3.06 (s, 2 H), 2.97
(s, 2 H), 1.96-2.11 (m, 4 H), 1.09-1.43 (m, 6 H), 0.73-0.87
(m, 6 H); MS m/z (%) 308 (M+, 28.22), 248 (100); HRMS m/z
(EI) calcd for C18H28O4 308.19876, found 308.19851.
43. (E)-1,1-Bis(m et h oxyca r b on yl)-2-(1′-m et h ylen e-3′-
p h en yl-2-p r op en yl)cyclop r op a n e (2e). Starting from 1a (46
mg, 0.25 mmol) and (E)-1-iodo-2-phenylethylene (69 mg, 0.3
mmol) afforded 32 mg (45%) of 2e using Conditions C.
44. 1-Ben zyl-2-(2′-m eth ylp h en yl)-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3i-o-Me). Starting from 1b (41 mg, 0.15
mmol) and o-iodotoluene (40 mg, 0.18 mmol) afforded 44 mg
(80%) of 3i-o-Me using Conditions A. viscous liquid; IR (neat)
2952, 1736, 1492, 1435, 1262 cm-1; 1H NMR (300 MHz, CDCl3)
δ 6.89-7.13 (m, 9 H), 3.66 (s, 6 H), 3.20 (s, 2 H), 3.17 (s, 2 H),
2.95 (s, 2 H), 2.19 (s, 3 H); MS m/z (%) 364 (M+, 42.17), 304
(100); HRMS m/z (EI) calcd for C23H24O4 364.16746, found
364.17161.
using Conditions D: viscous liquid; IR (neat) 2956, 1735, 1607,
1
1576, 1436, 1259 cm-1; H NMR (300 MHz, CDCl3) δ 7.35 (d,
J ) 8.81 Hz, 2 H), 6.85 (d, J ) 8.81 Hz, 2 H), 5.87-5.91 (m, 1
H), 3.81 (s, 3 H), 3.68 (s, 6 H), 3.37-3.41 (m, 2 H), 3.18-3.11
(m, 2 H); MS m/z (%) 290 (M+, 31.98), 230 (100); HRMS m/z
(EI) calcd for C16H18O5 290.11543, found 290.11997.
48. 1-(4′-Meth oxyca r bon ylp h en yl)-4,4-bis(m eth oxyca r -
bon yl)cyclop en ten e (3g). Starting from 1a (46 mg, 0.25
mmol) and 4-iodobenzoic acid methyl ester (79 mg, 0.3 mmol)
afforded 44 mg (55%) of 3g and 2g (molar ratio of 3g/2g )
66:34 as determined by 300 MHz 1H NMR spectra) using
Conditions D. 3g: white solid; mp 99-101 °C (n-hexane); IR
(KBr) 2953, 1734, 1630, 1608, 1436, 1277 cm-1; 1H NMR (300
MHz, CDCl3) δ 7.99 (d, J ) 8.55 Hz, 2 H), 7.47 (d, J ) 8.55
Hz, 2 H), 6.17-6.21 (m, 1 H), 3.92 (s, 3 H), 3.78 (s, 6 H), 3.42-
3.48 (m, 2 H), 3.21-3.28 (m, 2 H); MS m/z (%) 318 (M+, 9.39),
258 (100); HRMS m/z (EI) calcd for C17H18O6 318.11034, found
318.11030.
45. 1-P h en yl-4,4-b is(m et h oxyca r b on yl)cyclop en t en e
(3a ).17 Starting from 1a (46 mg, 0.25 mmol) and PhI (61 mg,
0.3 mmol) afforded 43 mg (66%) of 3a using Conditions D: IR
Ack n ow led gm en t. Financial support from the Ma-
jor State Basic Research Development Program (Grant
G2000077500), Chinese Academy of Sciences, and Shang-
hai Municipal Committee of Science and Technology is
greatly appreciated. Shengming Ma is the recipient of
a 1999 Qiu Shi Award for Young Scientific Workers
issued by Hong Kong Qiu Shi Foundation of Science and
Technology (1999-2003) and the Special Starting Grant
for Outstanding Young Chemists issued by National
Natural Science Foundation of China (29525202).
1
(neat) 1600, 1734 cm-1; H NMR δ 7.15-7.55 (m, 5 H), 6.03
(s, 1 H), 3.77 (s, 6 H), 3.43 (s, 2 H), 3.22 (s, 2 H); MS (m/e) 260
(M+, 19.96), 200 (100).
46. 1-(4′-Meth ylp h en yl)-4,4-bis(m eth oxyca r bon yl)cy-
clop en ten e (3c). Starting from 1a (46 mg, 0.25 mmol) and
4-iodotoluene (65 mg, 0.3 mmol) afforded 43 mg (63%) of 3c
using Conditions D: white solid; mp 53-54 °C (n-hexane/ethyl
acetate); IR (KBr) 1733, 1608, 1514, 1435, 1263 cm-1; 1H NMR
(300 MHz, CDCl3) δ 7.32 (d, J ) 8.05 Hz, 2 H), 7.14 (d, J )
8.05 Hz, 2 H), 5.93-5.98 (m, 1 H), 3.78 (s, 6 H), 3.27-3.44 (m,
2 H), 3.17-3.25 (m, 2 H), 2.35 (s, 3 H); MS m/z (%) 274 (M+,
19.11), 214 (100); HRMS m/z (EI) calcd for C16H18O4 274.12051,
found 274.11918.
Su p p or tin g In for m a tion Ava ila ble: Tables 1 and 2,
NMR spectra for all the new products, and 1H-1H NOESY
spectra of E-2x, Z-2x, and Z-2â. This material is available free
of charge via the Internet at http://pubs.acs.org.
47. 1-(4′-Meth oxyp h en yl)-4,4-bis(m eth oxyca r bon yl)cy-
clop en ten e (3d ). Starting from 1a (46 mg, 0.25 mmol) and
4-iodoanisole (71 mg, 0.3 mmol) afforded 41 mg (57%) of 3d
J O0108616