Novel stereospecific synthesis of 3-chloroacrylate esters via palladium- catalyzed carbonylation of terminal acetylenes

Article abstract of DOI:10.1021/jo982345u

A simple and effective method for the highly regio- and stereospecific synthesis of (Z)-3-chloroacrylate esters is described. Using terminal acetylenes and primary, secondary, and tertiary aliphatic alcohols as substrates, the carbonylation reactions were

Full text of DOI:10.1021/jo982345u

5984
J . Org. Chem. 1999, 64, 5984-5987
Novel Ster eosp ecific Syn th esis of 3-Ch lor oa cr yla te Ester s via
P a lla d iu m -Ca ta lyzed Ca r bon yla tion of Ter m in a l Acetylen es
J inheng Li, Huanfeng J iang,* Aiqun Feng, and Lanqi J ia
Guangzhou Institute of Chemistry, Chinese Academy of Sciences, P.O. Box 1122, Guangzhou 510650,
China
Received November 30, 1998
A simple and effective method for the highly regio- and stereospecific synthesis of (Z)-3-chloroacrylate
esters is described. Using terminal acetylenes and primary, secondary, and tertiary aliphatic alcohols
as substrates, the carbonylation reactions were carried out under carbon monoxide (1 atm) at room
temperature in the presence of a catalytic amount of PdCl2 and 3 equiv of cupric chloride. Isolated
yields of (Z)-3-chloroacrylate esters ranging from 30% to 72% were obtained. Our results show
that the polarity of the alcohol-benzene solvent plays an important role in the stereochemistry of
the products.
In tr od u ction
Thus, new and effective stereospecific synthesis routes
to (Z)-3-chloroacrylate esters are still of considerable
interest to synthetic organic chemists. In this paper, we
report that (Z)-3-chloroacrylate esters can be efficiently
produced with high regio- and stereospecificity using
terminal acetylenes, aliphatic alcohols, and carbon mon-
oxide in the presence of a catalytic amount of PdCl2 and
an excess of cupric chloride (eq 1).
3-Chloroacrylate esters are valuable intermediates in
organic synthesis1 and are known to exhibit some biologi-
cal properties.2 There are many ways to synthesize
3-chloroacrylate esters,3 as a mixture of Z- and E-isomers,
with the E-isomers predominating. The stereospecific
synthesis of (Z)-3-chloroacrylate esters can be effected by
the esterification of the corresponding acids.3b,4 It has also
been reported that (Z)-3-chloroacrylate esters can be
synthesized stereospecifically by the reaction of lithium
chloride in acetic acid with actylenecarboxylates.5 Cur-
rently, the transition-metal-catalyzed carbonylation of
terminal acetylenes may be one of the most useful
strategies for the synthesis of (Z)-3-chloroacrylate esters.
Heck has reported that 3-chloroacrylate esters (the
E-isomers predominating) were observed as byproducts
in the dicarbonylation of terminal acetylenes using PdCl2
and mercuric dichloride.6 A related synthesis of unsatur-
ated â-chlorolactones (E-isomers) occurred when prop-
argylic alcohols were mercurated and then carbonylated
with a palladium catalyst.7 Unfortunately, the mercura-
tion was successful only with relatively low molecular
weight or symmetrically substituted propargylic alcohols.
Resu lt a n d Discu ssion
(1) (a) Modena, G. Acc. Chem. Res. 1971, 4, 73. (b) Patai, S.;
Pappoport, Z. The Chemistry of Alkenes; Patai, S., Ed.; Interscience:
London, 1964; Chapter 8. (c) Smith, A. B.; Kilenyl, S. N. Tetrahedron
Lett. 1985, 26, 4419. (d) Bey, P.; Vevert, J . P. J . Org. Chem. 1980, 45,
3249. (e) Ege, G.; Franz, H. J . Heterocycl. Chem. 1982, 19, 1267. (f)
Larock, R. C.; Narayanan, K.; Hershberger, S. S. J . Org. Chem. 1983,
48, 4377. (g) Zhang, C.; Lu, X. Synthesis 1996, 586. (h) Crousse, B.;
Alami, M.; Linstrumelle, G. Tetrahedron Lett. 1995, 36, 4245. (i) Miura,
M.; Okuro, K.; Hattori, A.; Nomura, M. J . Chem. Soc., Perkin Trans.
1 1989, 73.
(2) (a) Vanghn, T. H. Union Carbide Corp., Belg. 1963, 631, 355;
Chem. Abstr. 1964, 60, 11900h. (b) Herrett, R. A.; Kurtz, A. N. Science
1963, 141, 1192. (c) Kurtz, A. N.; Herret, R. A. Union Carbide Corp.,
Belg. 1963, 631, 083; Chem. Abstr. 1964, 60, 15071b.
(3) (a) Winterfeldt, E. Angew. Chem., Int. Ed. Engl. 1967, 6, 423
and references cited therein. (b) Kultz, A. N.; Billups, W. E.; Greenlee,
R. B.; Hamil, H. F.; Pace, W. T. J . Org. Chem. 1965, 30, 3141. (c)
Wingfort Corp. Br. Pat. 1944, 564, 261; Chem. Abstr., 1946, 40, 3768.8
(4) Andersson, K. Chem. Scr. 1972, 2, 117.
(5) (a) Ma, S.; Lu, X. J . Chem. Soc., Chem. Commun. 1990, 1643.
(b) Ma, S.; Lu, X. Tetrahedron Lett. 1990, 31, 7653. (c) Ma, S.; Lu, X.;
Li, Z. J . Org. Chem. 1992, 57, 709. (c) Lu, X.; Zhu, G.; Ma, S. Chin. J .
Chem. 1993, 11, 267.
Preliminary results showed that the polarity of the
solvent (alcohol-benzene) could affect the yield and Z/E
ratio of 3a . Thus, we tried adding different amounts of
methanol to vary the polarity of the solvent. A mixture
of phenylacetylene (1a , 102 mg, 1 mmol) and methanol
(2a , 0.04 mL, 1 mmol) reacted under CO (1 atm) in
benzene (10 mL) at room temperature for 2 h in the
presence of PdCl2 (10 mg, 0.056 mmol) and CuCl2 (269
mg, 2 mmol) (entry 1 in Table 1). The conversion of 1a
was only 50%, and methyl 3-chloro-3-phenylacrylate (3a )
was obtained in 20% GC yield (Z/E ) 84:16). The
assignment of the stereochemistry of the product 3a is
based upon the chemical shift of the olefinic proton (δ )
6.53 in the H NMR spectra).3b,8 All of the results from
1
(8) (a) Itoˆ, S.; Fugise, Y.; Sato, M. Tetrahedron Lett. 1969, 25, 691.
(b) Ma, S.; Lu, X. J . Org. Chem. 1991, 56, 5120. (c) Minami, T.; Niki,
I. J . Org. Chem. 1974, 39, 3236. (d) Tanaka, K.; Tamura, A. Chem.
Lett. 1980, 595.
(6) Heck, R. F. J . Am. Chem. Soc. 1972, 94, 2712.
(7) Larock, R. F.; Riefling, B.; Fellows, C. A. J . Org. Chem. 1978,
43, 131.
10.1021/jo982345u CCC: $18.00 © 1999 American Chemical Society
Published on Web 07/14/1999

Stereospecific Synthesis of 3-Chloroacrylate Derivatives
J . Org. Chem., Vol. 64, No. 16, 1999 5985
Ta ble 1. Rea ction of P h en yla cetylen e (1a ) w ith MeOH
(2a ) u n d er Ca r bon Dioxid e in th e P r esen ce of P d Cl2 a n d
Sch em e 1
a
Cu Cl2
good yields of (Z)-3-chloroacrylate esters.9 To our sur-
prise, some sterically hindered aliphatic alcohols, such
as s-BuOH (2d ), t-BuOH (2e), and t-pentanol (2f), showed
high activity in the reaction, indicating that this may be
a simple and efficient method for the preparation of some
sterically hindered esters. When terminal acetylenes
reacted with the same alcohol, the activity of 1a is higher
than that of 1b. It is of interest to note that an internal
acetylene (4-octyne) did not afford 3-chloroacrylate esters
under the same condition.10
entry
MeOH (mL)
CuCl2 (mmol)
yield of 3a , % (Z/E)b
1
0.04
0.5
0.6
0.7
0.6
0.6
0.3
10
2
2
2
2
3
4
3
3
20 (84/16)
47 (98/2)
48 (98/2)
25 (only Z)
58 (only Z) (31%)d
57 (only Z)
53 (only Z) (30%)d
trace
2
3c
4
5
6
7e
8f
a
Reaction conditions: 1a (1 mmol) and PdCl2 (0.056 mmol) in
When the experiments were carried out in a sealed
system, the reaction was not clean and a mixture was
formed. An open system may allow the majority of HCl
gas generated in the reaction to be released into the air,
thus delaying the acidification of the reaction mixture.
In comparing the carbonylation products with the
reaction conditions, we can come to some valuable
conclusions. In polar solvents such as methanol, adding
base (NaOAc)11 or acid (HCl)12 to the palladium-catalyzed
carbonylation of acetylenes in the presence of cupric
chloride afforded acetylenecarboxylates or unsaturated
diesters, respectively. No 3-chloroacrylate esters were
detected (Scheme 1). We found that the carbonylation
reaction of 1a in MeOH without added acid or base
afforded a mixtrue of unsaturated diesters and trace
methyl (Z)-3-chloro-3-phenylacrylate (entry 8 in Table 1).
Tsuji gave results similar to ours.11
When alcohol-benzene, a less polar solvent, was used
in the reaction, 3-chloroacrylate esters were predominate
in the products. In the presence of base (NaOAc),
however, the reaction in the same solvent afforded (Z)-
unsaturated diesters with high stereoselectivity.13 All the
results suggest that selectivity of the products may
strongly depend on the polarity of solvent and the effect
of added acid or base.
C6H6 (10 mL) under CO (1 atm) at room temperature for 2 h.
b
Determined by GC analysis using an internal standard. c The
d
conversion of 1a was 58%. Isolated yields. e Reacted in 5 mL of
C6H6. f Only methanol as solvent.
Ta ble 2. P a lla d iu m -Ca ta lyzed Ca r bon yla tion of
Ter m in a l Acetylen esa
entry
R1
Ph
Ph
Ph
Ph
Ph
C5H11
C5H11
C5H11
C5H11
C5H11
C5H11
R2
products
isolated yield (%)b
1
2
3
4
5
6
7
8
9
Bu
3b
3c
3d
3e
3f
3g
3h
3i
63 (77)
66 (82)
72 (90)
70 (86)
50 (58)
43 (60)
67 (81)
65 (81)
49 (60)
43 (49)
45 (55)
i-Pr
s-Bu
t-Bu
t-pentyl
Me
Bu
i-Pr
s-Bu
t-Bu
t-pentyl
3j
3k
3l
10
11
a
Reaction conditions: 1 (1 mmol), 2 (0.6 mL), PdCl2 (0.056
mmol), and CuCl2 (3 mmol) in C6H6 (10 mL) under CO (1 atm) at
b
room temperature for 2 h. Isolated yields; GC yields are given
in parentheses.
It is interesting to hypothesize how the reaction
proceeds mechanistically. The question regarding the
first step of the reaction is whether chloropalladation of
acetylenes or acylpalladation of acetylenes occurred first.
Heck6 observed that the chloro esters were formed as
byproducts in the 1-phenyl-1-propyne and 3,3-dimethyl-
1-butyne dicaroxylation reactions. He hypothesized that
Table 1 indicate that the addition of 0.6 mL of methanol
appears to be most effective (48% GC, Z/E ) 98/2) (entry
3). To examine this result more closely, we decreased the
amount of methanol and benzene at the same ratio,
which still resulted in a high yield (Table 1, entry 7).
Therefore, the optimal ratio of methanol/benzene (v/v) is
0.6/10.
(9) Z- and E-isomers of such compounds may be separated by TLC
on silica gel using light petroleum-ethyl ether (10:1) as eluant, but
we did not detect any E-isomer. The chemical shifts of the olefinic
proton in the 1H NMR (CDCl3) spectra for the alkyl (Z)-3-chloro-
phenylacrylates are all about δ ) 6.50 and for alkyl (Z)-3-chloro-2-
octenoates they are δ ) 5.90-6.00. GC analysis also showed that the
products contained <1% of E-isomers.
(10) The reaction condition: 4-octyne (1 mmol), PdCl2 (0.056 mmol),
CuCl2 (3 mmol), and s-BuOH (0.6 mL) in C6H6 (10 mL) under CO (1
atm) or in the absence of CO at room temperature for 10 h. After
filtration, the benzene was removed by rotary evaporation to give crude
hexapropylbenzene. Hexapropylbenzene was then purified by prepara-
tive TLC using light petroleum-ethyl ether (10:1) as eluent on silica
gel and recrystallized. The isolated yield was 98%. See: (a) Maitlis, P.
M. Acc. Chem. Res. 1976, 9, 93. (b) Yokota, T.; Sakurai, Y.; Sakaguchi,
S.; Ishii, Y. Tetrahedron Lett. 1997, 38, 3923.
Increasing the cupric chloride concentration has been
reported by Heck6 to cause an increasing formation of
3-chloroacrylic esters, so the amount of cupric chloride
was the next variable examined. Indeed, the amount of
cupric chloride affected the yield of 3a in our experi-
ments. By increasing the amount of cupric chloride from
2 to 3 mmol, the yields of 3a were increased from 48% to
58% (GC yields, only Z-isomer) (entries 3 and 5). When
the amount of CuCl2 was increased to 4 mmol, the yield
remained at 57% (entry 6). The above results encouraged
us to use the palladium-catalyzed carbonylation for a
general synthesis of (Z)-3-chloroacrylate esters.
(11) Tsuji, J .; Takahashi, M.; Takahashi, T. Tetrahedron Lett. 1980,
21, 849.
(12) Alper, H.; Despeyroux, B.; Woell, J . B. Tetrahedron Lett. 1983,
24, 5691.
The results in Table 2 indicate that terminal acetylenes
could be employed successfully in the carbonylation
reaction, together with aliphatic alcohols, to give fair to
(13) This paper has been accepted by Synth. Commun.

5986 J . Org. Chem., Vol. 64, No. 16, 1999
Li et al.
7.66-7.68 (m, 5H, C6H5); 13C NMR δ 13.6 (CH3), 19.1 (CH2),
30.3, 30.6, 30.9 (CH2), 64.2, 64.4, 64.7 (OCH2), 116.1, 116.4
(dCH), 126.6, 126.7, 126.9, 127.1, 127.6, 127.7, 127.8, 128.0,
128.1, 128.5, 128.8, 128.9, 129.8, 130.3, 130.5, 130.8, 137.2
(C6H5), 146.0 (ClCd), 164.2 (CdO); MS m/z 240 (M+(37Cl)), 238
(M+(35Cl)), 183 (M+(37Cl) - C4H9), 181 (M+(35Cl) - C4H9), 167
(M+(37Cl) - OC4H9), 165 (M+(35Cl) - OC4H9), 139 (M+(37Cl) -
CO2C4H9), 137 (M+(35Cl) - CO2C4H9), 102 (M+ - Cl -
CO2C4H9). Anal. Calcd for C13H15ClO2: C, 65.41; H, 6.33.
Found: C, 65.25; H, 6.38.
Sch em e 2
Isop r op yl (Z)-3-Ch lor o-3-p h en yla cr yla te (3c).6 IR (film)
766, 853, 1373, 1448, 1492, 1618, 1722, 3062 cm-1; 1H NMR δ
1.25 (d, 6H, J ) 6 Hz, 2CH3), 5.14 (m, 1H, CH), 6.50 (s, 1H,
HCd), 7.36-7.43, 7.65-7.68 (m, 5H, C6H5); 13C NMR δ 21.9
(2CH3), 68.1 (O-C), 116.9 (dCH), 127.2, 128.6, 130.5, 137.5
(C6H5), 144.5 (ClCd), 163.5 (CdO); MS m/z 226 (M+(37Cl)), 224
(M+(35Cl)), 183 (M+(37Cl) - C3H7), 181 (M+(35Cl) - C3H7), 167
(M+(37Cl) - OC3H7), 165 (M+(35Cl) - OC3H7), 139 (M+(37Cl) -
CO2C3H7), 137 (M+(35Cl) - CO2C3H7), 102 (M+ - Cl -
CO2C3H7).
the chloro esters may be formed either by a reductive
elimination of Pd(0) from the monocarboalkoxylated
intermediate or by PdCl2 addition of acetylenes, followed
by carbonylation and alcoholysis. In fact, no carbonyla-
tion products of 4-octyne were detected in our experi-
ments,10 indicating that chloropalladation of acetylenes
might be faster than acylpalladation of acetylenes in the
less polar solvent. Therefore, our hypothesis is that the
cis-addition of acetylenes and PdCl2 may form the cis-
chloropalladation intermediate 4,14 followed by migratory
insertion of carbon monoxide and alcoholysis15 to afford
(Z)-3-chloroacrylate esters 3. CuCl2 then oxidizes the
palladium from intermediate 5 to regenerate the active
palladium species (Scheme 2).
sec-Bu tyl (Z)-3-Ch lor o-3-p h en yla cr yla te (3d ). IR (film)
1001, 1380, 1448, 1493, 1618, 1716, 2975 cm-1 1H NMR δ
;
0.93 (t, 3H, J ) 7.4 Hz, CH3), 1.27 (d, 3H, J ) 6.4 Hz, CH3),
1.62 (m, 2H, CH2), 4.98 (m, 1H, CH), 6.52 (s, 1H, HCd),
7.37-7.41, 7.66-7.68 (m, 5H, C6H5); 13C NMR δ 9.7 (CH3),
19.0, 19.5 (CH2), 28.8 (CH2), 72.7 (OCH), 117.0 (dCH),
127.2, 127.9, 128.6, 129.6, 129.7, 130.5, 137.4 (C6H5), 145.7
(ClCd), 163.9 (CdO); MS m/z 240 (M+(37Cl)), 238 (M+(35Cl)),
183 (M+(37Cl) - C4H9), 181 (M+(35Cl) - C4H9), 167 (M+(37Cl) -
OC4H9), 165 (M+(35Cl) - OC4H9), 140 (M+(37Cl) + 1 - CO2C4H9),
138 (M+(35Cl) + 1 - CO2C4H9), 102 (M+ - Cl - CO2C4H9). Anal.
Calcd for C13H15ClO2: C, 65.41; H, 6.33. Found: C, 65.50; H,
6.30.
In summary, we have developed a novel method for
the highly regio- and stereospecific synthesis of (Z)-3-
chloroacrylate esters under mild conditions. The method
may also provide a new, efficient route for the synthesis
of some sterically hindered alkyl esters.
ter t-Bu tyl (Z)-3-Ch lor o-3-p h en yla cr yla te (3e). IR (film)
764, 1035, 1390, 1450, 1616, 1722, 3060 cm-1; 1H NMR δ 1.52
(s, 9H, 3CH3), 6.45 (s, 1H, HCd), 7.37-7.40, 7.63-7.66 (m,
5H, C6H5); 13C NMR δ 27.7, 27.9, 28.2, 28.5, 28.6 (3CH3), 81.3
(O-C), 118.2 (dCH), 126.6, 126.7, 127.1, 127.6, 127.9, 128.1,
128.5, 129.3, 130.4, 137.5 (C6H5), 144.6 (ClCd), 163.5 (CdO);
MS m/z 238 (M+(35Cl)), 183 (M+(37Cl) - C4H9), 181 (M+(35Cl)
- C4H9), 167 (M+(37Cl) - OC4H9), 165 (M+(35Cl) - OC4H9), 139
Exp er im en ta l Section
1
Gen er a l In for m a tion . All H and 13C NMR spectra were
recorded at 400 MHz with CDCl3 as solvent. MS data were
obtained using HP 5973 GC-MS. TLC was performed using
commercially prepared 100-400 mesh silica gel plates (HF254),
and visualization was effected at 254 nm. CuCl2 was dried at
130 °C under HCl gas. All other reagents were used directly
as obtained commercially.
Gen er a l P r oced u r e for th e Ca r bon yla tion of Ter m in a l
Acetylen es. To a mixture of PdCl2 (0.056 mmol) and CuCl2
(3 mmol) in C6H6 (10 mL) were added alcohol 2 (0.6 mL) and
substrate 1 (1 mmol) under CO (1 atm). The reaction was
stirred at room temperature for 2 h. After filtration, the
benzene was removed by rotary evaporation to give crude 3.
Then the products 3 were purified by preparative TLC using
light petroleum-ethyl ether (10:1) as eluent on silica gel. All
products were obtained as colorless liquids.
(M+(37Cl) - CO2C4H9), 137 (M+(35Cl) - CO2C4H9), 102 (M+
-
Cl - CO2C4H9). Anal. Calcd for C13H15ClO2: C, 65.41; H, 6.33.
Found: C, 65.77; H, 6.47.
ter t-P en tyl (Z)-3-Ch lor o-3-p h en yla cr yla te (3f). IR (film)
766, 1068, 1452, 1490, 1616, 1722, 3062 cm-1; 1H NMR δ 0.91
(t, 3H, J ) 7.6 Hz, CH3), 1.49 (s, 3H, CH3), 1.82 (q, 2H, J )
7.6 Hz, CH2), 6.45 (s, 1H, HCd), 7.37-7.40, 7.63-7.66 (m, 5H,
C6H5); 13C NMR δ 8.2 (CH3), 25.1, 25.6, 26.0 (2CH3), 33.5 (CH2),
83.9 (O-C), 118.2 (dCH), 126.7, 126.9, 127.2, 127.9, 128.1,
128.5, 129.6, 129.9, 130.3, 137.5 (C6H5), 144.5 (ClCd), 163.5
(CdO); MS m/z 252 (M+(35Cl)), 183 (M+(37Cl) - C5H11), 181
(M+(35Cl) - C5H11), 167 (M+(37Cl) - OC5H11), 165 (M+(35Cl) -
OC5H11), 139 (M+(37Cl) - CO2C5H11), 137 (M+(35Cl) - CO2C5H11),
102 (M+ - Cl - CO2C5H11). Anal. Calcd for C14H17ClO2: C,
66.53; H, 6.78. Found: C, 66.56; H, 6.76.
Meth yl (Z)-3-Ch lor o-3-p h en yla cr yla te (3a ).6 IR (film)
768, 1439, 1620, 1730, 3062 cm-1; 1H NMR δ 3.79 (s, 3H, CH3),
6.53 (Z-isomer) (s, 1H, HCd), 7.38-7.42, 7.65-7.68 (m, 5H,
C6H5); 13C NMR δ 51.6, 52.5 (CH3), 116.0, 119.3 (dCH), 126.8,
127.0, 127.2, 127.5, 127.9, 128.1, 128.4, 128.6, 129.1, 129.5,
130.0, 130.3, 130.4, 130.7, 137.2 (C6H5), 146.5, 150.2
(ClCd), 164.6(CdO); MS m/z 198 (M+(37Cl)), 196 (M+(35Cl), 167
(M+(37Cl) - OCH3), 165 (M+(35Cl) - OCH3), 139 (M+(37Cl) -
CO2CH3), 137 (M+(35Cl) - CO2CH3), 102 (M+ - Cl - CO2CH3).
Bu tyl (Z)-3-Ch lor o-3-p h en yla cr yla te (3b). IR (film) 766,
Meth yl (Z)-3-Ch lor o-2-octen oa te (3g).6 IR (film) 650, 849,
1
1007, 1375, 1462, 1635, 1720, 2933 cm-1; H NMR δ 0.88 (t,
3H, J ) 7.2 Hz, CH3), 1.25 (m, 4H, 2CH2), 1.60 (m, 2H, CH2),
2.42 (t, 2H, J ) 7.2 Hz, CH2), 3.70 (s, 3H, CH3), 6.00 (s, 1H,
HCd); 13C NMR δ 13.8 (CH3), 22.3 (CH2), 26.8 (CH2), 30.6
(CH2), 41.2 (CH2), 51.3 (OCH3), 115.7 (dCH), 151.0 (ClCd),
164.4 (CdO); MS m/z 190 (M+(35Cl)), 161 (M+(37Cl) - OCH3),
159 (M+(35Cl) - OCH3), 155 (M+ - Cl), 95 (M+ - 1 - Cl -
CO2CH3).
Bu tyl (Z)-3-Ch lor o-2-octen oa te (3h ). IR (film) 660, 852,
1
1385, 1450, 1491, 1618, 1724, 3062 cm-1; H NMR δ 0.94 (t,
1022, 1383, 1462, 1639, 1730, 2960 cm-1 1H NMR δ 0.86-
;
3H, J ) 7.2 Hz, CH3), 1.41 (m, 2H, CH2), 1.66 (m, 2H, CH2),
4.20 (t, 2H, J ) 6.8 Hz, CH2), 6.53 (s, 1H, HCd), 7.37-7.41,
0.94 (m, 6H, 2CH3), 1.26-1.39 (m, 8H, 4CH2), 1.61 (m, 2H,
CH2), 2.41 (t, 2H, J ) 7.6 Hz, CH2), 4.13 (t, 2H, J ) 6.8 Hz,
CH2), 5.98 (s, 1H, HCd); 13C NMR δ 13.6 (CH3), 13.7 (CH3),
19.1 (CH2), 22.2 (CH2), 26.8 (CH2), 30.6 (2CH2), 41.1 (CH2),
64.1 (OCH2), 116.1 (dCH), 150.4 (ClCd), 164.0 (CdO); MS
m/z 233 (M+(35Cl) + 1), 197 (M+ - Cl), 179 (M+(37Cl) + 2 -
C4H9), 177 (M+(35Cl) + 2 - C4H9), 161 (M+(37Cl) - OC4H9), 159
(14) (a) Kaneda, K.; Uchiyama, T.; Fujiwara, Y.; Imanaka, T.;
Teranishi, S. J . Org. Chem. 1979, 44, 55. (b) Ba¨ckvall, J , E.; Mcnilsson,
Y. I. M.; Gatti, R. G. Organometallics 1995, 14, 4242.
(15) Negishi, E.; Coperet, C.; Ma, S.; Liou, S. Y.; Liu, F. Chem. Rev.
1996, 96, 365.

Stereospecific Synthesis of 3-Chloroacrylate Derivatives
J . Org. Chem., Vol. 64, No. 16, 1999 5987
(M+(35Cl) - OC4H9), 95 (M+ - 1 - Cl - CO2C4H9). Anal. Calcd
for C12H21ClO2: C, 61.93; H, 9.09. Found: C, 62.49; H, 9.40.
Isop r op yl (Z)-3-Ch lor o-2-octen oa te (3i). IR (film) 654,
850, 1001, 1377, 1462, 1639, 1726, 2933 cm-1; 1H NMR δ 0.88
(t, 3H, J ) 6.8 Hz, CH3), 1.25 (d, 6H, J ) 6 Hz, 2CH3), 1.26-
1.32 (m, 4H, 2CH2), 1.60 (m, 2H, CH2), 2.40 (t, 2H, J ) 7.6
Hz, CH2), 5.10 (m, 1H, CH), 5.96 (s, 1H, HCd); 13C NMR δ
13.9 (CH3), 21.8 (2CH3), 22.3 (CH2), 26.9 (CH2), 30.7 (CH2),
41.2 (CH2), 67.7 (OCH), 116.6 (dCH), 150.2 (ClCd), 163.6 (Cd
O); MS m/z 218 (M+(35Cl)), 183 (M+ - Cl), 179 (M+(37Cl) + 2 -
C3H7), 177 (M+(35Cl) + 2 - C3H7), 161 (M+(37Cl) - OC3H7), 159
(M+(35Cl) - OC3H7), 141 (M+ + 1 - Cl - C3H7), 95 (M+ - 1 -
Cl - CO2C3H7). Anal. Calcd for C11H19ClO2: C, 60.41; H, 8.76.
Found: C, 62.03; H, 9.09
5.91 (s, 1H, HCd); 13C NMR δ 13.8 (CH3), 22.3 (CH2), 26.9
(CH2), 27.5, 27.6, 27.7, 27.9, 28.1, 28.4, 28.5 (3CH3), 30.7 (CH2),
41.1 (CH2), 80.9 (O-C), 117.6 (dCH), 149.0 (ClCd), 163.4 (Cd
O); MS m/z 197 (M+ - Cl), 179 (M+(37Cl) + 2 - C4H9), 177
(M+(35Cl) + 2 - C4H9), 161 (M+(37Cl) - OC4H9), 159 (M+(35Cl)
- OC4H9), 95 (M+ - 1 - Cl - CO2C4H9). Anal. Calcd for C12H21
-
ClO2: C, 61.93; H, 9.09. Found: C, 62.20; H, 9.29.
ter t-P en tyl (Z)-3-Ch lor o-2-octen oa te (3l). IR (film) 659,
852, 1018, 1120, 1435, 1639, 1734, 2954 cm-1 1H NMR δ
;
0.88 (t, 6H, J ) 6.4 Hz, 2CH3), 1.28 (m, 4H, 2CH2), 1.44 (s,
6H, 2CH3), 1.59 (m, 2H, CH2), 1.79 (q, 2H, J ) 7.6 Hz, CH2),
2.38 (t, 2H, J ) 7.6 Hz, CH2), 5.91 (s, 1H, HCd); 13C NMR
δ 8.2 (CH3),13.9 (CH3), 22.3 (CH2), 25.3, 25.6, 25.9 (2CH3),
26.9 (CH2), 30.7 (CH2), 33.4 (CH2), 41.1 (CH2), 83.4 (O-C),
117.6 (dCH), 148.9 (ClCd), 163.4 (CdO); MS m/z 231
(M+(35Cl) - CH3), 211 (M+ - Cl), 179 (M+(37Cl) + 2 - C5H11),
177 (M+(35Cl) + 2 - C5H11), 161 (M+(37Cl) - OC5H11), 159
(M+(35Cl) - OC5H11), 95 (M+ - 1 - Cl - CO2C5H11). Anal. Calcd
for C13H23ClO2: C, 63.27; H, 9.39. Found: C, 63.44; H, 9.79.
sec-Bu tyl (Z)-3-Ch lor o-2-octen oa te (3j). IR (film) 652,
854, 1001, 1358, 1460, 1637, 1720, 2933 cm-1; 1H NMR δ 0.88
(t, 6H, J ) 7.2 Hz, 2CH3), 1.22 (d, 3H, J ) 6 Hz, CH3), 1.28-
1.30 (m, 4H, 2CH2), 1.55-1.62 (m, 4H, 2CH2), 2.40 (t, 2H, J )
7.6 Hz, CH2), 4.90 (m, 1H, CH), 5.97 (s, 1H, HCd); 13C NMR
δ 9.6 (CH3), 13.8 (CH3), 19.4 (CH3), 22.3 (CH2), 26.8 (CH2), 28.8
(CH2), 30.7 (CH2), 41.1 (CH2), 72.3 (OCH), 116.5 (dCH), 150.1
Ack n ow led gm en t. We thank the National Natural
Science Foundation of China for financial support
(29772036) and Dr. Fanglu¨ Huang for helpful discus-
sion.
(ClCd), 163.7 (CdO); MS m/z 233 (M+(35Cl) + 1), 197 (M+
-
Cl), 179 (M+(37Cl) + 2 - C4H9), 177 (M+(35Cl) + 2 - C4H9),
161 (M+(37Cl) - OC4H9), 159 (M+(35Cl) - OC4H9), 95 (M+ - 1
- Cl - CO2C4H9). Anal. Calcd for C12H21ClO2: C, 61.93; H,
9.09. Found: C, 61.88; H, 9.22.
Su p p or tin g In for m a tion Ava ila ble: Spectral data (1H
and 13C NMR, IR, and MS) of all the compounds. This material
is available free of charge via the Internet at http://pubs.acs.org.
ter t-Bu tyl (Z)-3-Ch lor o-2-octen oa te (3k ). IR (film) 650,
1
854, 999, 1369, 1390, 1460, 1637, 1720, 2933, 2960 cm-1; H
NMR δ 0.88 (t, 3H, J ) 7.2 Hz, CH3), 1.29 (m, 4H, 2CH2), 1.47
(s, 9H, 3CH3), 1.60 (m, 2H, CH2), 2.38 (t, 2H, J ) 6.4 Hz, CH2),
J O982345U