Highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles

Article abstract of DOI:10.1021/jo026121u

This paper describes highly efficient allyl cross-coupling reactions of allylindiums with organic electrophiles such as aryl and vinyl triflates, vinyl halides, dibromoolefin, and alkynyl iodide. The reactions were carried out using 4 mol % Pd(PPh₃)₄ in the presence of 3 equiv of LiCl in DMF at 100 °C under a nitrogen atmosphere. Allylindium, generated from the reaction of 1 equiv of indium with 1.5 equiv of allyl halide, gave the best result as a coupling partner. The present method is mild and simple to apply, and it produces a diverse range of allylic compounds in good to excellent yields.

Full text of DOI:10.1021/jo026121u

SCHEME 1
High ly Efficien t Allyl Cr oss-Cou p lin g
Rea ction s of Allylin d iu m s w ith Or ga n ic
Electr op h iles
Kooyeon Lee, J insung Lee, and Phil Ho Lee*
Department of Chemistry, Kangwon National University,
Chunchon 200-701, Kangwondo, Republic of Korea
phlee@kangwon.ac.kr
Received J une 29, 2002
Abstr a ct: This paper describes highly efficient allyl cross-
coupling reactions of allylindiums with organic electrophiles
such as aryl and vinyl triflates, vinyl halides, dibromoolefin,
and alkynyl iodide. The reactions were carried out using 4
mol % Pd(PPh3)4 in the presence of 3 equiv of LiCl in DMF
at 100 °C under a nitrogen atmosphere. Allylindium, gener-
ated from the reaction of 1 equiv of indium with 1.5 equiv
of allyl halide, gave the best result as a coupling partner.
The present method is mild and simple to apply, and it
produces a diverse range of allylic compounds in good to
excellent yields.
reaction of allylmetals containing Mg, Zn, or Al with aryl
and alkenyl halides has not given the desired cross-
coupling products in high yields. Inhibition of Pd catalysis
by the allylmetal reagents may be suspected, since the
charge-affinity-inverted reaction of aryl and alkenylmet-
als with ally electrophiles is highly satisfactory.1e There-
fore, overcoming these difficulties is a prerequisite for
developing new allylmetals as coupling partners. In
connection with our current research interest in the
synthetic utility of organoindium,4 we had previously
reported on Pd-catalyzed cross-coupling reactions of
allylindiums with aryl halides.5,6 Here we examine the
feasibility and efficiency of Pd-catalyzed allyl cross-
coupling reactions of in situ generated allylindiums with
a variety of organic electrophiles such as aryl and vinyl
triflates, vinyl halides, dibromoolefin, and alkynyl iodide
(Scheme 1).
Of the catalytic systems screened, the best results were
obtained with 4 mol % Pd(PPh3)4 in the presence of 3
equiv of LiCl in DMF at 100 °C under a nitrogen
atmosphere. Allylindium, in situ generated from the
reaction of 1 equiv of indium with 1.5 equiv of allyl halide,
gave the best result as a coupling partner. To demon-
strate the efficiency and scope of the present method, we
applied this catalytic system to a variety of allyl halides
and organic electrophiles such as aryl and vinyl triflates,
vinyl halide, dibromoolefin, and alkynyl iodide. The
presence of various alkyl substituents at the R and γ
position did not diminish the efficiency and selectivity
for the allyl halides as coupling partners. The results are
summarized in Table 1. Under the optimized conditions,
Coupling reactions of organometallic compounds with
organic electrophiles catalyzed by transition metals have
received much attention in the area of synthetic methods
for C-C bond formation.1 Especially, allyl cross-coupling
reactions have been focused on in recent years because
the double bond can be further functionalized.2 One of
the most frequently used methods for allyl cross-coupling
reactions is the use of allylstannane for coupling part-
ners, which has attracted much attention as a result of
its availability as well as its air- and moisture-stability,
and its compatibility with a variety of functional groups.
Using allylstannanes for nucleophilic coupling partners,
however, is faced with several limitations: (1) difficulties
associated with the preparation of regiochemically de-
fined allylstannanes, (2) its tendency to undergo allylic
isomerization, (3) tin removal from the product, and (4)
tin toxicity.2b,3 On the other hand, the Pd-catalyzed
(1) (a) Heck, R. F. Palladium Reagents in Organic Synthesis;
Academic Press: New York, 1985. (b) Trost, B. M.; Verhoeven, T. R.
In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F.
G., Abel, E. W., Eds.; Pergamon: Oxford, UK, 1982; Vol. 8, pp 799-
938. (c) Farina, V. In Comprehensive Organometallic Chemistry II;
Wilkinson, G., Stone, F. G., Abel, E. W., Eds.; Pergamon: Oxford, UK,
1995; Vol. 12, pp 161-240. (d) Tsuji, J . Palladium Reagents and
Catalyst; Wiley: Chichester, UK, 1995; Chapter 4. (e) Diederich, F.;
Stang, P. J ., Eds. Metal-Catalyzed Cross-couplings Reactions; Wiley-
VCH: Weinheim, Germany, 1998. (f) Malleron, J .; Fiaud, J .; Legros,
J . Handbook of Palladium-Catalyzed Organic Reactions; Academic
Press: San Diego, CA, 1997.
(2) (a) Labadie, J . W.; Tueting, D.; Stille, J . K. J . Org. Chem. 1983,
48, 4634. (b) Stille, J . K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
(c) Echavarren, A. M.; Stille, J . K. J . Am. Chem. Soc. 1987, 109, 5478.
(d) Verhac, J .-B.; Pereyre, M.; Quintard, J .-P. Tetrahedron 1990, 46,
6399. (e) Yamamoto, Y.; Hatsuya, S.; Yamada, J .-i. J . Org. Chem. 1990,
55, 3118. (f) Farina, V.; Krishnan, B. J . Am. Chem. Soc. 1991, 113,
9585.
(4) (a) Lee, P. H.; Bang, K.; Lee, K.; Lee, C.-H.; Chang, S. Tetrahe-
dron Lett. 2000, 41, 7521. (b) Lee, P. H.; Ahn, H.; Lee, K.; Sung, S.-Y.;
Kim, S. Tetrahedron Lett. 2001, 42, 37. (c) Lee, P. H.; Lee, K.; Kim, S.
Org. Lett. 2001, 3, 3205. (d) Lee, P. H.; Bang, K.; Ahn, H.; Lee, K.
Bull. Korean Chem. Soc. 2001, 22, 1385. (e) Lee, P. H.; Seomoon, S.;
Lee, K. Bull. Korean Chem. Soc. 2001, 22, 1380. (f) Lee, P. H.; Lee, K.;
Sung, S.-Y.; Chang, S. J . Org. Chem. 2001, 66, 8646. (g) Lee, P. H.;
Lee, K.; Chang, S. Synth. Commun. 2001, 31, 3189. (h) Lee, P. H.;
Bang, K.; Lee, K.; Sung, S.-Y.; Chang, S. Synth. Commun. 2001, 31,
3781. (i) Lee, P. H.; Sung, S.-Y.; Lee, K.; Chang, S. Synlett 2002, 146.
(5) Lee, P. H.; Sung, S.-Y.; Lee, K. Org. Lett. 2001, 3, 3201.
(6) For some previously reported examples of indium-mediated cross-
coupling reactions, see: (a) Nomura, R.; Miyazaki, S.-I.; Matsuda, H.
J . Am. Chem. Soc. 1992, 114, 2738. (b) Perez, I.; Sestelo, J . P.;
Sarandeses, L. A. Org. Lett. 1999, 1, 1267. (c) Gelman, D.; Schumann,
H.; Blum, J . Tetrahedron Lett. 2000, 41, 7555. (d) Perez, I.; Sestelo, J .
P.; Sarandeses, L. A. J . Am. Chem. Soc. 2001, 123, 4155. (e) Hirashita,
T.; Yamamura, H.; Kawai, M.; Araki, S. Chem. Commun. 2001, 387.
(f) Takami, K.; Yorimitsu, H.; Shnokubo, H.; Matsubara, S.; Oshima,
K. Org. Lett. 2001, 3, 1997. (g) Lee, P. H.; Sung, S.-Y.; Lee, K. Org.
Lett. 2001, 3, 3201.
(3) (a) Farina, V.; Krishnamurthy, V.; Scott, W. J . The Stille
Reaction; Wiley: New York, 1998. (b) Pereyre, M.; Quintard, J .; Rahm,
A. Tin in Organic Synthesis; Butterworth: London 1987. (c) Stille, J .
K. Pure Appl. Chem. 1985, 57, 1771. (d) Mitchell, T. N. Synthesis 1992,
803. (e) Farina, V.; Krishnamurthy, V.; Scott. W. J . Org. React. 1997,
50, 1.
10.1021/jo026121u CCC: $22.00 © 2002 American Chemical Society
Published on Web 10/12/2002
J . Org. Chem. 2002, 67, 8265-8268
8265

TABLE 1. P d -Ca ta lyzed Allyl Cr oss-Cou p lin g Rea ction s of Allylin d iu m s w ith Or ga n ic Electr op h iles
a
b
2 mol % Pd2dba3CHCl3/16 mol % PPh3 was used as catalyst. Isomeric ratio of 25 and 26. c Isomeric ratio of crotyl bromide: cis:trans
) 1:5. Isomeric ratio of 27: cis:trans ) 1:1. e 27(R):28(γ) ratio. f Cis:trans ratio. Isomeric ratio of â-bromostyrene: cis:trans ) 1:4.
equiv of In and 3 equiv of allyl iodide were used. Pd(0) catalyst was not used. Yield of 1-allyl-3-iodo-2-cyclohexenol.
2
d
g
h
i
8266 J . Org. Chem., Vol. 67, No. 23, 2002

6 was treated with allyl iodide and indium to produce
16 in 92% yield (entry 1). Whereas addition of prenylin-
dium to carbonyl groups usually yielded the product
resulting from γ-attack,7 we found that the reaction of 6
with prenylindium regioselectively produced 17 resulting
from R-attack due to the steric effect in 87% yield (entry
2). The reaction of 7 with 3-bromocyclohexene in the
presence of indium afforded 2-(2′-cyclohexenyl)naphtha-
lene in 87% yield (entry 6). Vinyl triflates worked equally
well with allylindiums (entries 7-9), producing allylic
compounds in good to excellent yield. R-Bromostyrene
was treated with allylindium to give 2-phenyl-1,4-pen-
tadiene and trans-1-phenyl-1,4-pentadiene in 65% and
32% yields, respectively. Although mechanism of forma-
tion of trans-1-phenyl-1,4-pentadiene is not clear at the
present time, we believe that 1,4-diene 26 was produced
via oxidative addition of Pd(0) to R-bromostyrene, dehy-
dropalladation due to steric effect to produce pheny-
lacetylene, hydropalladation to phenylacetylene, followed
by the allyl cross-coupling reaction (entry 10).8 The
reaction of R-bromostyrene with crotyl bromide (cis:trans
) 1:5) in the presence of indium produced a 1.9:1 mixture
of R (cis:trans ) 1:1, 27) and γ products (28), but the
product resulting from R attack predominated (entry 11).
Treatment of 10 with geranylindium produced the de-
sired product 30 in 97% yield (entry 13). The reaction of
â-bromostyrene (cis:trans ) 1:4) with allylindium gave
cross-coupling product 1-phenyl-1,4-pentadiene (cis:trans
) 1:4, 31) in 96% yield (entry 14). In the case of
â,â-dibromostyrene (12),9 double cross-coupling product
32 was obtained in 92% yield with 2 equiv of allylindium
(entry 15). It should be noted that 2-iodo or 3-iodo-2-
cyclohexen-1-one having a labile ketone group toward
allylindium provided the desired products 33 and 34 in
good yields (entries 16 and 17), respectively. The reaction
of 14 with allylindium in the absence of Pd(0) produced
1-allyl-3-iodo-2-cyclohexenol in 77% yield. These results
mean that 3-allyl-2-cyclohexen-1-one was produced not
via 1,4-addition of allylindium followed by an elimination
reaction, but through a Pd-catalyzed cross-coupling reac-
tion. Treatment of iodophenylacetylene10 with prenylin-
dium regioselectively produced 5-methyl-1-phenyl-4-
hexen-1-yne in 82% yield (entry 19).
Exp er im en ta l Section
Typ ica l Exp er im en ta l P r oced u r e. To a suspension of
Pd(PPh3)4 (23.0 mg, 4 mol %) and lithium chloride (63.5 mg, 1.5
mmol) in DMF (1 mL) was added trifluoromethanesulfonic acid
naphthalen-1-yl ester (138.1 mg, 0.5 mmol) at room temperature
under a nitrogen atmosphere. After 15 min, allyl indium, which
is generated from allyl iodide (126.0 mg, 0.75 mmol) and indium
(57.0 mg, 0.5 mmol) in DMF (1 mL), was added and the mixture
was stirred at 100 °C for 1 h. The reaction mixture was quenched
with NaHCO3 (saturated aqueous). The aqueous layer was
extracted with ether (3 × 20 mL), and the combined organics
were washed with water and brine, dried with MgSO4, filtered,
and concentrated under reduced pressure. The residue was
purified by silica gel column chromatography using n-hexane
1
to give 1-allylnaphthalene (77.3 mg, 92%). H NMR (400 MHz,
CDCl3) δ 8.01 (d, J ) 8.08 Hz, 1H), 7.83 (t, J ) 7.76 Hz, 1H),
7.72 (d, J ) 6.89 Hz, 1H), 7.50-7.42 (m, 2H), 7.39 (d, J ) 7.25
Hz, 1H), 7.32 (d, J ) 6.89 Hz, 1H), 6.16-6.65 (m, 1H), 5.11-
5.06 (m, 2H), 3.82 (d, J ) 6.30 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 135.13, 133.27, 132.01, 130.15, 126.84, 125.13, 124.44,
123.96, 123.77, 123.68, 122.19, 114.33, 35.43; IR (film) 3003,
2916, 1684, 1606, 1414, 1358 cm-1; HRMS (EI) calcd for C13H12
M+ 168.0939, found 168.0934.
1-P r en yln a p h th a len e (17): 1H NMR (400 MHz, CDCl3) δ
8.03 (d, J ) 8.04 Hz, 1H), 7.85 (d, J ) 9.05 Hz, 1H), 7.71 (d, J
) 8.11 Hz, 1H), 7.49 (m, 2H), 7.40 (dd, J ) 7.91, 7.25 Hz, 1H),
7.33 (d, J ) 6.83 Hz, 1H), 5.40 (t, J ) 6.92 Hz, 1H), 3.77 (d, J )
6.92 Hz, 2H), 1.80 (s, 3H), 1.76 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 137.78, 133.85, 132.69, 132.04, 128.30, 126.56, 125.71,
125.64, 125.58, 125.44, 124.00, 122.88, 31.78, 25.74, 17.95; IR
(film) 3053, 2986, 2305, 1422, 1269 cm-1; HRMS (EI) calcd for
C
15H16 M+ 196.1252, found 196.1251.
1-(2′-Cycloh exen yl)n a p h th a len e (18): 1H NMR (400 MHz,
CDCl3) δ 8.14 (d, J ) 8.27 Hz, 1H), 7.87 (d, J ) 8.07 Hz, 1H),
7.72 (d, J ) 7.76 Hz, 1H), 7.53-7.38 (m, 4H), 6.04-5.99 (m, 1H),
5.83 (dd, J ) 9.98, 1.80 Hz, 1H), 4.24-4.22 (m, 3H), 2.21-2.11
(m, 3H), 1.76-1.66 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
137.78, 133.85, 132.69, 132.04, 128.30, 126.56, 125.71, 125.64,
125.58, 125.44, 124.00, 122.88, 31.78, 25.74, 17.95; IR (film)
3053, 2978, 2870, 2305, 1422 cm-1; HRMS (EI) calcd for C16H16
M+ 208.1252, found 208.1256.
2-Allyln a p h th a len e (19): 1H NMR (400 MHz, CDCl3) δ
7.86-7.77 (m, 3H), 7.63 (s, 1H), 7.49-7.40 (m, 3H), 7.33 (dd, J
) 8.46, 1.42 Hz, 1H), 6.05 (ddt, J ) 16.98, 10.09, 6.77 Hz, 1H),
5.16-5.11 (m, 2H), 3.55 (d, J ) 6.66 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 137.55, 137.32, 133.65, 132.12, 128.04, 127.62,
127.48, 127.39, 126.66, 125.93, 125.27, 40.36; IR (film) 3003,
2916, 1684, 1606, 1414, 1358 cm-1; HRMS (EI) calcd for C13H12
M+ 168.0939, found 168.0934.
2-P r en yln a p h th a len e (20): 1H NMR (400 MHz, CDCl3) δ
7.84-7.78 (m, 3H), 7.64 (s, 1H), 7.49-7.35 (m, 2H), 7.36 (d, J )
8.33 Hz, 1H), 5.45 (t, J ) 10.24 Hz, 1H), 3.54 (d, J ) 7.31 Hz,
2H), 1.82 (s, 3H), 1.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
139.76, 134.13, 133.26, 128.29, 128.01, 127.86, 127.80, 126.51,
126.26, 125.47, 123.46, 34.97, 26.22, 18.33; IR (film) 3691, 3054,
2986, 2305, 1422, 1270 cm-1; HRMS (EI) calcd for C15H16 M+
196.1252, found 196.1258.
2-(2′-Cycloh exen yl)n a p h th a len e (21): 1H NMR (400 MHz,
CDCl3) δ 7.81-7.77 (m, 3H), 7.64 (s, 1H), 7.46-7.36 (m, 3H),
5.97-5.94 (m, 1H), 5.81 (dd, J ) 10.04, 1.42 Hz, 1H), 3.56 (s,
1H), 2.12-2.05 (m, 3H), 1.81-1.70 (m, 1H), 1.67-1.61 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 144.05, 133.54, 132.15, 130.05,
128.64, 127.84, 127.58, 127.55, 126.71, 125.81, 125.79, 125.14,
41.90, 32.41, 25.09, 21.12; IR (film) 3053, 2978, 2870, 2305, 1422
cm-1; HRMS (EI) calcd for C16H16 M+ 208.1252, found 208.1256.
1-Allyl-4-(ter t-bu tyl)-1-cycloh exen e (22): 1H NMR (400
MHz, CDCl3) δ 5.80 (ddt, J ) 16.1, 9.96, 6.89 Hz, 1H), 5.43 (d,
J ) 3.61 Hz, 1H), 5.02 (d, J ) 15.33 Hz, 1H), 4.99 (d, J ) 8.31
Hz, 1H), 2.68 (d, J ) 6.66 Hz, 2H), 2.05-1.74 (m, 5H), 1.26-
1.12 (m, 2H), 0.86 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 136.99,
136.14, 122.08, 115.41, 44.15, 42.01, 32.20, 29.83, 27.25, 26.87,
24.26; IR (film) 3054, 2862, 2305, 1637, 1423, 1267 cm-1; HRMS
(EI) calcd for C13H22 M+ 178.1721, found 178.1717.
In conclusion, we have shown here several noteworthy
features (availability, ease of preparation and handling,
high reactivity as well as selectivity, and operational
simplicity) of allylindium reagents for the cross-coupling
reaction. The present method is mild and simple to apply,
and it produces a diverse range of allylic compounds in
good to excellent yields. This protocol can be readily
applied to cross-coupling reactions with aryl and vinyl
triflates, vinyl halides, dibromoolefin, and alkynyl iodide.
(7) (a) Araki, S.; Ito, H.; Butsugan, Y. J . Org. Chem. 1988, 53, 1833.
(b) Araki, S.; Katsumura, N.; Ito, H.; Butsugan, Y. Tetrahedron Lett.
1989, 30, 1581. (c) Isaac, M. B.; Chan, T.-H. Tetrahedron Lett. 1995,
36, 8957. (d) Loh, T.-P.; Li, X.-R. Angew. Chem., Int. Ed. Engl. 1997,
36, 980.
(8) Although we tried to detect phenylacetylene to confirm the
proposed mechanism, we failed to detect phenylacetylene. Efforts to
further understand the mechanism are currently in progress.
(9) (a) Corey, E. J .; Fuchs, P. L. Tetrahedron Lett. 1972, 13, 3769.
(b) Ramirez, F.; Desai, N. B.; McKelvie, N. J . Am. Chem. Soc. 1962,
84, 1745. (c) Shen, W.; Wang, L. J . Org. Chem. 1999, 64, 8873.
(10) (a) Rao, M. L. N.; Periasamy, M. Synth. Commun. 1995, 25,
2295. (b) J effery, T. Chem. Commun. 1988, 909.
J . Org. Chem, Vol. 67, No. 23, 2002 8267

4-Allyl-8-m eth oxy-1,2-d ih yd r on a p h th a len e (23): 1H NMR
(400 MHz, CDCl3) δ 7.15 (d, J ) 7.86 Hz, 1H), 6.92 (d, J ) 7.86
Hz, 1H), 6.79 (d, J ) 8.20 Hz, 1H), 5.95 (ddt, J ) 16.70, 10.17,
6.35 Hz, 1H), 5.90-5.88 (m, 1H), 5.11 (dd, J ) 17.16, 1.58 Hz,
1H), 5.06 (dd, J ) 10.07, 1.58 Hz, 1H), 3.83 (s, 3H), 3.18 (dd, J
) 6.36, 1.28 Hz, 2H), 2.76 (t, J ) 8.07 Hz, 2H), 2.27-2.21 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 156.02, 136.79, 135.91,
134.47, 126.17, 124.40, 115.96, 115.89, 109.46, 55.48, 37.37,
22.53, 19.89; IR (film) 3054, 2986, 1573, 1422, 1263 cm-1; HRMS
(EI) calcd for C14H16O M+ 200.1201, found 200.1202.
4-(2′-Cycloh e xe n yl)-8-m e t h oxy-1,2-d ih yd r on a p h t h a -
len e (24): 1H NMR (400 MHz, CDCl3) δ 7.18 (t, J ) 8.03 Hz,
1H), 7.00 (d, J ) 9.82 Hz, 1H), 6.78 (d, J ) 8.19 Hz, 1H), 5.89-
5.82 (m, 2H), 5.68-5.64 (m, 1H), 3.83 (s, 3H), 3.43 (s, 1H), 2.83-
2.62 (m, 2H), 2.25-2.19 (m, 2H), 2.04-1.86 (m, 3H), 1.70-1.53
(m, 3H); 13C NMR (100 MHz, CDCl3) δ 156.59, 139.78, 136.19,
130.48, 128.45, 126.61, 126.22, 125.44, 115.94, 109.66, 55.96,
37.05, 31.78, 29.10, 25.74, 22.94, 20.64, 20.40; IR (film) 3054,
2986, 2305, 1422, 1265 cm-1; HRMS (EI) calcd for C17H20O M+
240.1514, found 240.1510.
141.54, 136.80, 131.42, 128.18, 127.29, 126.23, 124.25, 121.89,
112.12, 39.71, 33.78, 26.59, 25.70, 23.43, 17.69; IR (film) 3054,
2986, 2305, 1674, 1422, 1269 cm-1; HRMS (EI) calcd for C18H24
M+ 240.1878, found 240.1877 (cis isomer), 240.1877 (trans
isomer).
1-P h en yl-1,4-p en ta d ien e (31): 1H NMR (400 MHz, CDCl3)
cis isomer δ 7.36-7.19 (m, 5H), 6.52 (d, J ) 11.57 Hz, 1H), 5.96-
5.86 (m, 1H), 5.71 (dt, J ) 11.54, 7.57 Hz, 1H), 5.11 (d, J ) 17.13
Hz, 1H), 5.07 (d, J ) 10.12 Hz, 1H), 3.06 (t, J ) 9.02 Hz, 2H),
trans isomer δ 7.36-7.19 (m, 5H), 6.41 (d, J ) 15.90 Hz, 1H),
6.23 (dt, J ) 15.77, 6.66 Hz, 1H), 5.96-5.86 (m, 1H), 5.11 (d, J
) 17.13 Hz, 1H), 5.07 (d, J ) 10.12 Hz, 1H), 2.96 (t, J ) 7.04
Hz, 2H); 13C NMR (100 MHz, CDCl3) cis isomer δ 137.29, 136.66,
130.05, 129.47, 128.63, 128.17, 126.71, 115.28, 32.70, trans
isomer δ 137.62, 136.47, 130.85, 128.49, 128.18, 127.02, 126.04,
115.67, 37.00; IR (film) 3053, 2986, 2305, 1422, 1269 cm-1
;
HRMS (EI) calcd for C11H12 M+ 144.0939, found 144.0933 (cis
isomer), 144.0935 (trans isomer).
2-Allyl-1-p h en yl-1,4-p en ta d ien e (32): 1H NMR (400 MHz,
CDCl3) δ 7.33-7.18 (m, 5H), 6.41 (s, 1H), 5.93-5.83 (m, 2H),
5.12 (d, J ) 8.32 Hz, 2H), 5.07 (d, J ) 15.97 Hz, 2H), 2.99 (d, J
) 5.94 Hz, 2H), 2.92 (d, J ) 6.76 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 134.97, 132.73, 131.16, 128.47, 127.71, 126.23, 121.03,
2-P h en yl-1,4-p en ta d ien e (25): 1H NMR (400 MHz, CDCl3)
δ 7.44 (d, J ) 7.15 Hz, 2H), 7.36-7.42 (m, 3H), 5.94-5.86 (m,
1H), 5.39 (s, 1H), 5.12 (d, J ) 13.69 Hz, 1H), 5.10 (s, 1H), 5.07
(d, J ) 8.60 Hz, 1H), 3.25 (d, J ) 6.49 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 146.33, 140.94, 136.20, 128.25, 127.44, 125.99,
116.46, 113.15, 39.51; IR (film) 3053, 2986, 2305, 1422, 1265
cm-1; HRMS (EI) calcd for C11H12 M+ 144.0939, found 144.0935.
tr a n s-1-P h en yl-1,4-p en ta d ien e (26): 1H NMR (400 MHz,
CDCl3) δ 7.36-7.19 (m, 5H), 6.41 (d, J ) 15.90 Hz, 1H), 6.23
(dt, J ) 15.77, 6.66 Hz, 1H), 5.96-5.86 (m, 1H), 5.11 (d, J )
17.13 Hz, 1H), 5.07 (d, J ) 10.12 Hz, 1H), 2.96 (t, J ) 7.04 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 137.62, 136.47, 130.85,
128.49, 128.18, 127.02, 126.04, 115.67, 37.00; IR (film) 3053,
2986, 2395, 1421, 1270 cm-1; HRMS (EI) calcd for C11H12 M+
144.0939, found 144.0935.
115.97, 40.91, 34.93; IR (film) 3054, 2987, 1530, 1423, 1267 cm-1
HRMS (EI) calcd for C14H16 M+ 184.1252, found 184.1250.
;
2-(2′-Cycloh exen yl)-2-cycloh exen -1-on e (33): 1H NMR
(400 MHz, CDCl3) δ 6.71 (t, J ) 4.22 Hz, 1H), 5.87-5.82 (m,
1H), 5.45-5.41 (m, 1H), 3.44 (s, 1H), 2.44 (t, J ) 6.54 Hz, 2H),
2.38 (q, J ) 10.32 Hz, 2H), 2.01-1.96 (m, 4H), 1.88-1.81 (m,
1H), 1.59-1.50 (m, 2H), 1.33-1.26 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 198.81, 145.56, 143.04, 129.17, 128.85, 38.80, 33.36,
28.90, 26.12, 25.12, 23.09, 20.07; IR (film) 3053, 2986, 2305, 1733,
1422, 1269 cm-1; HRMS (EI) calcd for C12H16O M+ 176.1201,
found 176. 1199.
3-Allyl-2-cycloh exen -1-on e (34): 1H NMR (400 MHz, CDCl3)
δ 5.77 (s, 1H), 5.80 (ddt, J ) 17.01, 10.25, 6.87 Hz, 1H), 5.16 (d,
J ) 10.25 Hz, 1H), 5.14 (d, J ) 17.01 Hz, 1H), 2.95 (d, J ) 6.87
Hz, 2H), 2.39 (t, J ) 7.59 Hz, 2H), 2.30 (t, J ) 6.00 Hz, 2H),
2.00 (quint, J ) 6.25 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
199.91, 164.21, 133.26, 126.28, 118.31, 42.22, 37.32, 29.48, 22.63;
IR (film) 3055, 2985, 2305, 1733, 1422, 1265 cm-1; HRMS (EI)
calcd for C9H12O M+ 136.0888, found 136.0885.
2-P h en yl-1,4-h exa d ien e (27): 1H NMR (400 MHz, CDCl3)
cis/trans mixture δ 7.44-7.24 (m, 5H), 5.60-5.46 (m, 4H), 5.36
(s, 1H), 5.34 (s, 1H), 5.10 (s, 1H), 5.08 (s, 1H), 3.21 (d, J ) 6.99
Hz, 2H), 3.17 (s, 2H), 1.67 (s, 3H), 1.65 (s, 3H); 13C NMR (100
MHz, CDCl3) cis isomer δ 147.16, 141.30, 128.13, 127.39, 126.98,
126.00, 125.45, 112.43, 32.77, 12.81, trans isomer δ 146.80,
114.17, 128.22, 127.92, 127.35, 126.66, 125.99, 112.62, 41.85,
19.25; IR (film) 3053, 2986, 2305, 1422, 1269 cm-1; HRMS (EI)
calcd for C12H14 M+ 158.1096, found 158.1091 (cis isomer),
158.1091 (trans isomer).
3-(2′-Cycloh exen yl)-2-cycloh exen -1-on e (35): 1H NMR
(400 MHz, CDCl3) δ 5.88 (s, 1H), 5.87-5.85 (m, 1H), 5.52 (dd, J
) 10.07, 2.28 Hz, 1H), 2.90-2.94 (m, 1H), 2.41-2.34 (m, 4H),
2.26-2.19 (m, 2H), 2.03-1.96 (m, 4H), 1.91-1.84 (m, 1H), 1.74-
1.67 (m, 2H), 1.57-1.50 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
200.24, 169.57, 132.34, 129.77, 122.35, 43.28, 37.60, 37.54, 34.67,
3-Met h yl-2-p h en yl-1,4-p en t a d ien e (28): 1H NMR (400
MHz, CDCl3) δ 7.44-7.24 (m, 5H), 5.91 (ddd, J ) 17.06, 10.39,
6.67 Hz, 1H), 5.26 (s, 1H), 5.08 (s, 1H), 5.07 (d, J ) 15.06 Hz,
1H), 5.01 (d, J ) 10.59 Hz, 1H), 3.40 (quint, J ) 6.85 Hz, 1H),
1.21 (d, J ) 6.98 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 152.65,
142.38, 142.20, 128.62, 128.15, 127.20, 113.67, 112.14, 38.31,
17.95; IR (film) 3053, 2986, 2305, 1422, 1269 cm-1; HRMS (EI)
calcd for C12H14 M+ 158.1096, found 158.1094.
31.60, 28.35, 20.64; IR (film) 3055, 2986, 1733, 1422, 1269 cm-1
HRMS (EI) calcd for C12H16O M+ 176.1201, found 176.1199.
;
5-Meth yl-1-p h en yl-1-h ex-4-en -1-yn e (36): 1H NMR (400
MHz, CDCl3) δ 7.53 (d, J ) 7.87 Hz, 2H), 7.40-7.31 (m, 3H),
5.40 (t, J ) 6.82 Hz, 1H), 3.76 (d, J ) 6.82 Hz, 1H), 1.80 (s, 3H),
1.76 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 134.70, 132.52,
129.21, 128.45, 121.80, 117.90, 81.55, 73.90, 42.50, 39.65; IR
(film) 3540, 2986, 1422, 1269 cm-1; HRMS (EI) calcd for C13H14
M+ 170.1096, found 170.1091.
r-(2′-Cycloh exen yl)styr en e (29): 1H NMR (400 MHz, CDCl3)
δ 7.40-7.23 (m, 5H), 5.86-5.82 (m, 1H), 5.73-5.70 (m, 1H), 5.29
(s, 1H), 5.05 (s, 1H), 2.04-1.99 (m, 2H), 1.83-1.48 (m, 4H); 13
C
NMR (100 MHz, CDCl3) δ 152.44, 141.99, 128.24, 128.18, 128.01,
127.16, 126.56, 113.06, 39.87, 28.39, 25.24, 20.29; IR (film) 3053,
2986, 1531, 1351, 1267 cm-1; HRMS (EI) calcd for C14H16 M+
184.1252, found 184.1251.
Ack n ow led gm en t. This work was supported by the
Korea Research Foundation (KRF-99-005-D00048). We
thank Whasook Choi for the preliminary experiments.
The gas chromatograms were provided by the GC
facility, supported by the Research Center for Advanced
Mineral Aggregate Composite Products.
5,9-Dim eth yl-2-p h en yl-1,4,8-d eca tr ien e (30): 1H NMR (400
MHz, CDCl3) cis isomer δ 7.45-7.24 (m, 5H), 5.32 (s, 1H), 5.26-
5.22 (m, 1H), 5.13-5.11 (m, 1H), 5.07 (t, J ) 1.39 Hz, 1H), 2.09-
2.10 (m, 4H), 1.72 (s, 3H), 1.69 (s, 3H), 1.66 (s, 3H), trans isomer
δ 7.45-7.24 (m, 5H), 5.32 (s, 1H), 5.26-5.22 (m, 1H), 5.09-5.05
(m, 1H), 5.07 (t, J ) 1.39 Hz, 1H), 3.18 (d, J ) 6.86 Hz, 2H),
1.72 (s, 3H), 1.69 (s, 3H), 5.40 (t, J ) 6.92 Hz, 1H), 3.77 (d, J )
6.92 Hz, 2H), 2.09-2.01 (m, 4H), 1.65 (s, 3H), 1.61 (s, 3H), 1.59
(s, 3H); 13C NMR (100 MHz, CDCl3) cis isomer δ 147.46, 141.47,
136.88, 131.67, 128.20, 127.50, 126.01, 124.20, 122.47, 112.28,
33.59, 32.02, 26.50, 25.73, 17.66, 16.03, trans isomer δ 147.19,
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra. This material is available free of charge via the
Internet at http://pubs.acs.org.
J O026121U
8268 J . Org. Chem., Vol. 67, No. 23, 2002