The catalytic Sakurai reaction

Full text of DOI:10.1021/jo0105641

8646
J . Org. Chem. 2001, 66, 8646-8649
a stoichiometric amount or even an excess of the Lewis
Th e Ca ta lytic Sa k u r a i Rea ction
acid to obtain reasonable reaction rates and acceptable
yields of products. Although a few examples of catalytic
Sakurai reactions have been reported,4j,k herein we dis-
close a novel and catalytic Sakurai reaction using cata-
lytic amounts of InCl3 in the presence of trimethylsilyl
chloride (TMSCl).
Phil Ho Lee,*,† Kooyeon Lee,† Sun-young Sung,† and
Sukbok Chang‡
Department of Chemistry, Kangwon National University,
Chunchon 200-701, Republic of Korea, and
Department of Chemistry, Ewha Womans University,
Seoul 120-750, Republic of Korea
Resu lts a n d Discu ssion
phlee@kangwon.ac.kr
Received J une 4, 2001
During the course of our studies of indium-mediated
organic transformation,5 we observed an interesting
result of Lewis acidity of InCl3. When InCl3 was added
in a stoichiometric amount to a solution of 2-cyclohexen-
1-one (1) in CDCl3, the 1H NMR spectrum of the resulting
solution exhibited two peaks at 6.16 and 7.13 ppm, which
correspond to the R- and â-protons, respectively (Scheme
1). Although chemical shifts of the R- and â-protons were
shifted downfield relative to those of 1, the enone moiety
of 1 was maintained. In contrast, the enone moiety of 1
was entirely consumed to produce allylic carbocation
species 3 in the presence of stoichiometric amounts of
TiCl4 indicating that the Ti complex coordinates to the
enone irreversibly. These results strongly imply that
although InCl3 activates 2-cyclohexen-1-one, the extent
of the activation is weak enough to have a reversible
coordination; thus, InCl3 may act as a catalyst in Sakurai
reactions.
In tr od u ction
Sakurai reactions, Lewis acid additions of allyltrim-
ethylsilane with conjugated enones to form δ,ꢀ-enones,1
have been extensively applied in organic synthesis, in
natural product synthesis,2 and in the preparation of
some heterocyclic compounds.3 They are now considered
to be one of the most efficient means of C-C bond
formation, and examples of both inter- and intramolecu-
lar reactions4 have been reported. Sakurai reactions are
regiospecific with regard to the newly formed C-C bond.
The range of Lewis acids employed in Sakurai reac-
tions is extensive, among which TiCl4, AlCl3, and
BF3:OEt2 are in general the most effective for the
allylations. In all cases, however, the procedures require
Representative results are summarized in Table 1. The
choice of the solvent was important in this reaction, and
of the solvents tested CH2Cl2, CHCl3, THF, DMF and
H2O, CH2Cl2 and CHCl3 were the only choices. When R,â-
enone 1 was treated with allyltrimethylsilane in the
presence of a stoichiometric amount of InCl3 in dichlo-
romethane, 1,4-addition product 4 was produced in a 62%
yield (entry 1). When this reaction was carried out with
0.5 equiv of InCl3, 4 was isolated in a 52% yield (entry
2). However, 4 was not obtained with 0.25 equiv of InCl3
(entry 3). Thus, we next examined the effects of some
additives on the reaction and found that the reaction
could indeed be catalytic with InCl3 in the presence of
TMSCl. Of the catalytic systems examined, the best
results were obtained with the combination of 0.1 equiv
of InCl3 and 5 equiv of TMSCl (entry 6). The use of less
than 5 equivalents of TMSCl gave lower yields as well
as longer reaction times (entry 5). Surprisingly, 1,4-
addition product 4 was not produced at all with a
catalytic amount of TiCl4 and AlCl3 regardless of the
presence of TMSCl (entries 13-15). Even when InF3 and
In(OTf)3, which are stronger Lewis acids than InCl3, were
used, the desired product was obtained in lower yield
(entries 8-11).
* To whom correspondence should be addressed.
† Kangwon National University.
‡ Ewha Womans University.
(1) (a) Colvin, E. Silicon in Organic Synthesis; Butterworth: London,
1981; p 97. (b) Weber, W. P. Silicon Reagents for Organic Synthesis;
Springer-Verlag: Berlin, 1983; Vol. 12, p 173. (c) Hosomi, A. Acc. Chem.
Res. 1988, 21, 200. (d) Fleming, I.; Dunogues, J .; Smithers, R. Org.
React. 1989, 37, 57. (e) Langkopf, E.; Schinzer, D. Chem. Rev. 1995,
95, 1375. (f) Hosomi, A.; Sakurai, H. J . Am. Chem. Soc. 1977, 99, 1673.
(g) Ojima, I.; Kumagai, M.; Miyazawa, Y. Tetrahedron Lett. 1977, 18,
1385. (h) Pardo, R.; Zahra, J .-P.; Santelli, M. Tetrahedron Lett. 1979,
20, 4557. (i) Fleming, I.; Paterson, I. Synthesis 1979, 446. (j) Yanami,
T.: Miyashita, M.: Yoshikoshi, A. J . Org. Chem. 1980, 45, 607. (k)
Hosomi, K.: Kobayashi, H.; Sakurai, H. Tetrahedron Lett. 1980, 21,
955. (l) Majetich, G.; Casares, A. M.; Chapman, D.; Behnke, M.
Tetrahedron Lett. 1983, 24, 1909. (m) Blumenkopf, T. A.; Heathcock,
C. H. J . Am. Chem. Soc. 1983, 105, 2354.
(2) (a) Tokoroyama, T.; Tsukamoto, M.; Asada, T.; Iio, H. Tetrahe-
dron Lett. 1987, 28, 6645. (b) Nakamura, H.; Oya, T.; Murai, A. Bull.
Chem. Soc. J pn. 1992, 65, 929. (c) Majetich, G.; Defauw, J . Tetahedron
1988, 44, 3833. (d) Yamamoto, Y.; Furuta, T. J . Org. Chem. 1990, 55,
3971. (e) Majetich, G.; Song, J .-S.; Ringold, C.; Nemeth, G. A.
Tetrahedron Lett. 1990, 31, 2239. (f) Majetich, G.; Lowery, D.; Khetani,
V.; Song, J .-S.; Hull, K.; Ringold, C. J . Org. Chem. 1991, 56, 3988. (g)
Majetich, G.; Hull, K. Tetrahedron 1987, 43, 5621. (h) Dauben, W. G.;
Friedrich, L. F.; Oberhansli, P.; Aoyagi, E. I. J . Org. Chem. 1972, 37,
9. (i) Majetich, G.; Ringold, C. Heterocycles 1987, 25, 271. (j) Majetich,
G.; Behnke, M.; Hull, K. J . Org. Chem. 1985, 50, 3615. (k) Schinzer,
D.; Feber, K.; Puppelt, M. J ustus Liebigs Ann. Chem. 1992, 139.
(3) (a) Heathcock, C. H.; Kleinman, E. F.; Binkley, E. S. J . Am.
Chem. Soc. 1982, 104, 1054. (b) Majetich, G.; Song, J .-S.; Leigh, A. J .;
Condon, S. M. J . Org. Chem. 1993, 58, 1030. (c) Kuroda, C.; Inoue, S.;
Takemura, R.; Satoh, J . Y. J . Chem. Soc., Perkin Trans. 1 1994, 521.
(4) (a) Schinzer, D. Synthesis 1988, 263. (b) Schinzer, D.; Allagiannis,
C.; Wichmann, S. Tetrahedron 1988, 44, 3851. (c) Schinzer, D.; Solyom,
S.; Becker, M. Tetrahedron Lett. 1985, 26, 1831. (d) Majetich, G.;
Desmond, R.; Casares, A. M. Tetrahedron Lett. 1983, 24, 1913. (e)
Wilson, S. R.; Price, M. F. J . Am. Chem. Soc. 1982, 104, 1124. (f)
Tokoroyama, T.; Tsukamoto, M.; Iio, H. Tetrahedron Lett. 1984, 25,
5067. (g) Schinzer, D. Angew. Chem., Int. Ed. Engl. 1984, 23, 308. (h)
Majetich, G.; Defauw, J .; Hull, K.; Shawe, T. Tetrahedron Lett. 1985,
26, 4711. (i) Majetich, G.; Hull, K.; Defauw, J .; Shawe, T. Tetrahedron
Lett. 1985, 26, 2755. (j) Schinzer, D.; Ringe, K. Synlett 1994, 463. (k)
Kuhnert, N.; Peverley, J .; Robertson, J . Tetrahedron Lett. 1998, 39,
3215.
To demonstrate the efficiency and scope of the present
method, we applied this catalytic system to a variety of
R,â-enones. The results are summarized in Table 2.
Under the optimized conditions, methyl vinyl ketone was
reacted to allyltrimethylsilane to afford 6-hepten-2-one
in a 62% yield (entry 1). It should be noted that other
acyclic R,â-enones (entries 2-6) containing a â-substitu-
(5) (a) Lee, P. H.; Bang, K.; Lee, C.-H.; Chang, S. Tetrahedron Lett.
2000, 41, 7521. (b) Lee, P. H.; Ahn, H.; Lee, K.; Sung, S.-Y.; Kim, S.
Tetrahedron Lett. 2001, 42, 37.
10.1021/jo0105641 CCC: $20.00 © 2001 American Chemical Society
Published on Web 11/10/2001

Notes
J . Org. Chem., Vol. 66, No. 25, 2001 8647
Sch em e 1
Ta ble 1. Ca ta lytic Activity of Sever a l Lew is Acid s in th e
Sa k u r a i Rea ction
when mesityl oxide, isophorone, pulegone, or 3-methyl-
2-cyclohexen-1-one was treated with allyltrimethylsilane
and a catalytic or stoichiometric amount of InCl3 under
the same reaction conditions, the desired products were
not obtained. These results are consistent in that InCl3
is the weaker acid and less oxophilic than TiCl4. R,â-
Unsaturated esters such as methyl acrylate and methyl
methacrylate did not provide the added product, which
is similar with TiCl4.1f
Lewis acid
(equiv)
additive
(equiv)
isolated
entry
yield, %a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
InCl3 (1.0)
InCl3 (0.5)
InCl3 (0.25)
InCl3 (0.2)
InCl3 (0.1)
In Cl3 (0.1)
InCl3 (0.1)
InF3 (0.1)
In(OTf)3 (0.1)
InCl3 (0.1)
In(OTf)3 (0.1)
TiCl4 (1.0)
TiCl4 (0.1)
TiCl4 (0.1)
AlCl3 (0.1)
62
52
0
72
56 (23)
73
64b
0
52
25
32
82c
0
Further synthetic utility of this catalytic procedure is
shown in Scheme 2. (2-Methylallyl)trimethylsilane and
2-chloromethyl-3-trimethylsilyl-1-propene were reacted
to R,â-enone 1 to produce 3-(2-methylallyl)cyclohexanone
and 3-(2-chloromethylallyl)cyclohexanone, respectively,
in good yields.
TMSCl (1.0)
TMSCl (1.0)
TMSCl (5.0)
TMSCl (5.0)
TMSCl (5.0)
TMSCl (5.0)
TMSOTf (5.0)
TMSOTf (5.0)
When a mixture of 4-(2-oxopropyl)-2-cyclohexen-1-one
(5)6 and allyltrimethylsilane in dichloromethane was
treated with InCl3 (0.1 equiv) and TMSCl (5 equiv), the
allyl group was added chemoselectively to the CdC
double bond to afford 6 in a 73% yield (Scheme 3).
However, allyltrimethylsilane in the presence of a cata-
lytic or stoichiometric amount of TiCl4 and AlCl3 did not
react with either the ketone or the enone moiety.
TMSCl (5.0)
TMSCl (5.0)
0
0
a
Number in parentheses indicates recovered yield of 2-cyclo-
hexen-1-one. CHCl3 was used. c From ref 1f.
b
We briefly studied catalytic intramolecular Sakurai
reactions, and the results are shown in Table 3. Treat-
ment of 77 with InCl3 (0.1 equiv) and TMSCl (5 equiv) in
dichloromethane for 2 h diastereoselectively afforded 8
(R:â ) 1:34) in an excellent yield.8 Ordinarily, these
reactions proceed only when 1.3 equiv of EtAlCl2 is used,
which was the most effective in the intramolecular
Sakurai reaction to afford the desired product 8 (R:â )
4:1).4a
Ta ble 2. In d iu m Tr ich lor id e-Ca ta lyzed Sa k u r a i
Rea ction w ith Allyltr im eth ylsila n e
Although the role of the TMSCl in the Sakurai reaction
is not clear at the present moment, we believe that the
TMSCl traps the enolate intermediate to drive the
equilibrium to completion.9 This and other plausible
mechanistic pathways are under investigation, especially
with regard to the design of enantioselective catalytic
systems.
In conclusion, we have shown that catalytic amounts
of InCl3 promote inter- and intramolecular Sakurai
reactions in the presence of TMSCl. The present method
complements existing synthetic methods due to its mild
reaction conditions and some of the advantageous prop-
erties of indium metal over other metals such as ease of
(6) Compound 5 was prepared from 1,3-cyclohexadione in five steps
(PhH, EtOH, p-TsOH/LDA, allyl iodide/DiBAL-H/H3O+/Wacker oxida-
tion).
(7) Compound 7 was prepared from 1,3-cyclohexadione in seven
steps (PhH, EtOH, p-TsOH/LDA, allyl iodide/Sia2BH, H2O2, NaOH/
Swern oxidation/Ph3PdCHCH2TMS/DIBAL-H/H3O+).
(8) Stork, G.; Reynolds, M. E. J . Am. Chem. Soc. 1988, 110, 6911.
(9) Support for the formation of such TMSCl/R,â-enone complexes
is lacking; 1H NMR measurement for a mixture of 2-cyclohexen-1-one
and TMSCl failed to detect the Lewis acid/Lewis base complex. 29Si
NMR measurement for a mixture of TMSCl and InCl3 failed to detect
the TMS+InCl4 or TMSCl f InCl3 complex: (a) Corey, E. J .; Boaz, N.
W. Tetrahedron Lett. 1985, 26, 6015. (b) Corey, E. J .; Boaz, N. W.
Tetrahedron Lett. 1985, 26, 6019.
a
Allylbenzyldimethylsilane was used.
ent underwent the catalytic Sakurai reaction with almost
the same efficiency. Also, the reaction worked equally
well with cyclic R,â-enones (entries 7-10). Unlike TiCl4,

8648 J . Org. Chem., Vol. 66, No. 25, 2001
Notes
Sch em e 2
Sch em e 3
Ta ble 3. In d iu m Tr ich lor id e-Ca ta lyzed In tr a m olecu la r
Sa k u r a i Rea ction
42.85, 33.03, 30.95, 22.77 ppm; IR (film) 3020, 2950, 1700, 1430,
1410 cm-1; HRMS (EI) calcd for C7H12O M+ 112.0888, found
112.0886.
5-Meth yl-7-octen -3-on e: 1H NMR (400 MHz, CDCl3) δ 5.77
(ddt, J ) 17.53, 10.34, 7.10 Hz, 1H), 5.01 (d, J ) 10.34 Hz, 1H),
5.00 (d, J ) 17.53 Hz, 1H), 2.49-2.41 (m, 3H), 2.24 (dd, J )
15.72, 7.88 Hz, 1H), 2.17-1.71 (m, 3H), 1.06 (t, J ) 5.87 Hz,
3H), 0.94 (d, J ) 6.47 Hz, 3H); 13C NMR (100 MHz, CDCl3)
211.47, 136.72, 116.39, 48.94, 41.20, 36.56, 28.97, 19.81, 7.79
ppm; IR (film) 3060, 3000, 1720, 1440, 1430 cm-1; HRMS (EI)
calcd for C9H16O M+ 140.1201, found 140.1203.
Lewis acid
solvent
temp, °C
isolated yield, %a
b
b
1.3 equiv EtAlCl2
1.3 equiv EtAlCl2
0.1 equiv EtAlCl2
PhCH3
PhCH3
PhCH3
CH2Cl2
-78
0
-78
25
92 (4:1)
84 (1:1)
10
4-Allyl-2-n on a n on e: 1H NMR (400 MHz, CDCl3) δ 5.73 (ddt,
J ) 16.97, 9.95, 6.60 Hz, 1H), 5.01 (d, J ) 9.95 Hz, 1H), 5.00 (d,
J ) 16.97 Hz, 1H), 2.35 (ddd, J ) 35.03, 16.46, 6.33 Hz, 2H),
2.12 (s, 3H), 2.04-1.952 (m, 2H), 1.32-1.21 (m, 9H), 0.88 (t, J
) 6.65 Hz, 3H); 13C NMR (100 MHz, CDCl3) 209.09, 136.61,
116.54, 48.05, 38.30, 33.85, 33.47, 32.00, 30.57, 26.41, 22.62,
c
0.1 equiv InCl3
89 (1:34)
a
b
Ratio in parentheses indicates the ratio of R to â. From ref
4c. c A 5 equiv quantity of TMSCl was used.
14.06 ppm; IR (film) 3020, 2960, 2800, 1700, 1430, 1410 cm-1
HRMS (EI) calcd for
183.1745.
;
C
12H22O [M + H]+ 183.1749, found
handling, high reactivity and selectivity, low toxicity, and
operational simplicity.
4-P h en yl-6-h ep ten -2-on e: 1H NMR (400 MHz, CDCl3) δ
7.29-7.13 (m, 5H), 5.64 (ddt, J ) 17.10, 10.08, 7.04 Hz, 1H),
4.99 (d, J ) 17.10 Hz, 1H), 4.96 (d, J ) 10.08 Hz, 1H), 3.25
(quint, J ) 7.13 Hz, 1H), 2.76 (dd, J ) 16.24, 6.34 Hz, 1H), 2.70
(dd, J ) 16.23 Hz, 7.54, 1H), 2.33 (dd, J ) 8.84, 7.10 Hz, 2H),
2.02 (s, 3H);13C NMR (100 MHz, CDCl3) 207.75, 144.05, 136.16,
128.48, 127.45, 126.45, 116.78, 49.50, 40.87, 40.69, 30.68 ppm;
IR (film) 3010, 2950, 1700, 1440, 1420, 1400 cm-1; HRMS (EI)
calcd for C13H17O [M + H]+ 189.1279, found 189.1282.
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
indium trichloride (22.0 mg, 0.1 mmol) in CH2Cl2 (3 mL) was
added sequentially trans-chalcone (208.0 mg, 1.0 mmol), chlo-
rotrimethylsilane (543.0 mg, 5.0 mmol), and allyltrimethylsilane
(126.0 mg, 1.1 mmol) at room temperature under nitrogen
atmosphere. After 30 min, the reaction mixture was quenched
with saturated aqueous NaHCO3. The aqueous layer was
extracted with ether (3 × 25 mL), and the combined organics
were washed with water (20 mL) and brine (20 mL), dried with
MgSO4, filtered, and concentrated under reduced pressure. The
residue was purified by silica gel column chromatography
(hexane/EtOAc ) 20/1) leading to 1,3-diphenyl-1-oxo-5-hexene
(223.0 mg, 89%): 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J ) 7.28
Hz, 2H), 7.52 (t, J ) 7.29 Hz, 1H), 7.41 (t, J ) 7.85 Hz, 2H),
7.29-7.22 (m, 4H), 7.17 (t, J ) 6.96 Hz, 1H), 5.69 (ddt, J ) 17.15,
10.11, 7.05 Hz, 1H), 5.00 (d, J ) 17.10 Hz, 1H), 4.96 (d, J )
10.08 Hz, 1H), 3.48 (quint, J ) 7.08 Hz, 1H), 3.29 (d, J ) 6.04
Hz, 2H), 2.48-2.44 (m, 2H); 13C NMR (100 MHz, CDCl3) 198.90,
144.34, 137.20, 136.26, 132.92, 128.51, 128.42, 128.00, 127.56,
126.36, 116.78, 44.53, 40.72, 40.68 ppm; IR (film) 3010, 2950,
1670, 1430, 1400 cm-1; HRMS (EI) calcd for C18H19O [M + H]+
251.1436, found 251.1440.
4-(2-Th ien yl-)-6-h ep ten -2-on e: 1H NMR (400 MHz, CDCl3)
δ 7.13 (d, J ) 5.10 Hz, 1H), 6.91 (dd, J ) 5.06, 3.50 Hz, 1H),
6.81 (d, J ) 3.37 Hz, 1H), 5.71 (ddt, J ) 16.47, 13.29, 6.86 Hz,
1H), 5.04 (d, J ) 16.47 Hz, 1H), 5.03 (d, J ) 13.29 Hz, 1H), 3.62
(quint, J ) 6.99 Hz, 1H), 2.78 (d, J ) 1.95 Hz, 1H), 2.76 (d, J )
2.78 Hz, 1H), 2.43-2.39 (m, 2H), 2.08 (s, 3H); 13C NMR (100
MHz, CDCl3) 207.17, 147.95, 135.64, 126.59, 123.91, 123.11,
117.28, 50.19, 41.56, 35.89, 30.69 ppm; IR (film) 3040, 2970,
1710, 1420, 1410 cm-1; HRMS (EI) calcd for C11H14OS [M + H]+
195.0480, found 195.0474.
3-Allylcyclop en ta n on e: 1H NMR (400 MHz, CDCl3) δ 5.75
(ddt, J ) 17.03, 10.19, 6.83 Hz, 1H), 5.04 (d, J ) 17.03 Hz, 1H),
5.03 (d, J ) 10.19 Hz, 1H), 2.40-2.11 (m, 7H), 2.38 (dd, J )
17.71, 9.0 Hz, 1H), 1.64-1.53 (m, 1H); 13C NMR (100 MHz,
CDCl3) 219.70, 136.28, 116.48, 44.71, 39.56, 38.36, 36.68, 29.00
ppm; IR (film) 3020, 2960, 2900, 1680, 1430, 1410 cm-1; HRMS
(EI) calcd for C8H12O M+ 124.0888, found 124.0891.
1
6-Hep ten -2-on e: H NMR (400 MHz, CDCl3) δ 5.77 (ddt, J
3-Allylcycloh exa n on e: 1H NMR (400 MHz, CDCl3) δ 5.74
(ddt, J ) 17.83, 10.87, 7.22 Hz, 1H), 5.04 (d, J ) 17.83 Hz, 1H),
5.04 (d, J ) 10.87 Hz, 1H), 2.44-2.25 (m, 3H), 2.12-1.83 (m,
6H), 1.67-1.60 (m, 1H), 1.41-1.34 (m, 1H); 13C NMR (100 MHz,
CDCl3) 211.61, 135.60, 116.70, 47.64, 41.30, 40.71, 38.67, 30.78,
) 17.01, 10.26, 6.78 Hz, 1H), 5.02 (d, J ) 17.01 Hz, 1H),
4.98 (d, J ) 10.26 Hz, 1H), 2.44 (t, J ) 7.43 Hz, 2H), 2.14 (s,
3H), 2.06 (q, J ) 7.22 Hz, 2H), 1.68 (quint, J ) 7.49 Hz,
2H); 13C NMR (100 MHz, CDCl3) 209.01, 137.95, 115.25,

Notes
J . Org. Chem., Vol. 66, No. 25, 2001 8649
25.05 ppm; IR (film) 3020, 2960, 2900, 1680, 1430, 1410
cm-1; HRMS (EI) calcd for C9H15O [M + H]+ 139.1123, found
139.1118.
1690, 1410, 1250 cm-1; HRMS (EI) calcd for C10H16ClO [M +
H]+ 187.0890, found 187.0895.
3-Allyl-4-(2-oxop r op yl)cycloh exa n on e: 1H NMR (400
MHz, CDCl3) δ 5.69 (ddt, J ) 16.90, 10.04, 7.04 Hz, 1H), 5.08
(d, J ) 10.4 Hz, 1H), 5.04 (d, J ) 16.90 Hz, 1H), 2.75 (dd, J )
17.00, 4.02 Hz, 1H), 2.32-1.78 (m, 9H), 1.85 (s, 3H), 1.43-1.40
(m, 1H), 1.22-1.44 (m, 1H); 13C NMR (100 MHz, CDCl3) (major
isomer) 211.15, 207.62, 134.59, 117.79, 46.81, 45.60, 41.77, 40.32,
38.05, 35.11, 31.08, 30.68 ppm, (minor isomer) 210.90, 207.45,
135.75, 117.23, 44.51, 43.80, 40.22, 39.22, 34.26, 33.37, 30.51,
28.22 ppm; IR (film) 3000, 2940, 1690, 1400 cm-1; HRMS (CI)
calcd for C12H19O2 [M + H]+ 195.1385, found 195.1380.
9-Vin ylbicyclo[4.3.0]n on a n -3-on e: 1H NMR (400 MHz,
CDCl3) δ 5.65 (ddt, J ) 17.52, 10.13, 7.59 Hz, 1H), 5.02 (d, J )
17.52, 1H), 4.97 (d, J ) 10.13 Hz, 1H), 2.46 (dd, J ) 15.19, 6.48
Hz, 1H), 2.35-1.89 (m, 9H), 1.71-1.61 (m, 1H), 1.46-1.36 (m,
2H); 13C NMR (100 MHz, CDCl3) (major isomer) 213.65, 141.03,
114.68, 50.66, 43.77, 41.46, 38.47, 36.97, 32.02, 31.11, 27.64 ppm,
(minor isomer) 214.14, 138.65, 115.27, 48.21, 43.13, 39.19, 37.57,
37.39, 28.92, 28.30, 27.53 ppm; IR (film) 3000, 2940, 2920, 1690,
1400 cm-1; HRMS (EI) calcd for C11H16O [M + H]+ 164.1201,
found 164.1205.
3-Allyl-4,4-d im eth ylcycloh exa n on e: 1H NMR (400 MHz,
CDCl3) δ 5.67 (ddt, J ) 16.86, 10.87, 8.40 Hz, 1H), 5.02 (d, J )
10.87 Hz, 1H), 5.01 (d, J ) 16.86 Hz, 1H), 2.45-2.24 (m, 4H),
2.04 (dd, J ) 16.00, 11.97 Hz, 1H), 1.78-1.56 (m, 4H), 1.06 (s,
3H), 1.02 (s, 3H); 13C NMR (100 MHz, CDCl3) 211.98, 136.78,
116.62, 46.40, 42.60, 40.36, 38.32, 35.42, 32.78, 28.75, 19.56 ppm;
IR (film) 3040, 2940, 2910, 1700, 1410 cm-1; HRMS (EI) calcd
for C11H19O [M + H]+ 167.1436, found 167.1436.
3-Allylcycloh ep ta n on e: 1H NMR (400 MHz, CDCl3) δ 5.75
(ddt, J ) 17.33, 10.40, 7.11 Hz, 1H), 5.04 (d, J ) 10.40 Hz, 1H),
5.03 (d, J ) 17.33 Hz, 1H), 2.52-2.46 (m, 3H), 2.38 (dd, J )
10.90, 6.00 Hz, 1H), 2.08-1.57 (m, 7H), 1.44-1.24 (m, 2H); 13
C
NMR (100 MHz, CDCl3) 214.81, 136.58, 117.31, 49.93, 44.35,
42.18, 36.97, 36.23, 29.03, 23.73 ppm; IR (film) 3080, 3020, 2960,
1720, 1450, 1470 cm-1; HRMS (EI) calcd for C10H17O [M + H]+
153.1279, found 153.1277.
3-(2-Met h yla llyl)cycloh exa n on e: 1H NMR (400 MHz,
CDCl3) δ 4.77 (s, 1H), 4.68 (s, 1H), 2.41-2.26 (m, 3H), 2.10-
1.88 (m, 6H), 1.74-1.60 (m, 1H), 1.69 (s, 3H), 1.33-1.29 (m, 1H);
13C NMR (100 MHz, CDCl3) 211.90, 142.83, 112.38, 47.93, 45.25,
41.47, 36.76, 31.19, 25.18, 22.13 ppm; IR (film) 3000, 2940, 1690,
1440, 1400, 1250, 1240 cm-1; HRMS (CI) calcd for C10H17O M+
152.1201, found 152.1200.
Ack n ow led gm en t. This work was supported by
Korea Science and Engineering Foundation (KOSEF-
2000-1-123-002-5). Gas chromatograms were provided
by the GC facility supported by Research Center for
Advanced Mineral Aggregate Composite Products.
3-(2-Ch lor om eth yla llyl)cycloh exa n on e: 1H NMR (400
MHz, CDCl3) δ 5.21 (s, 1H), 4.97 (s, 1H), 4.01 (s, 2H), 2.43-2.27
(m, 4H), 2.18-1.91 (m, 5H), 1.70-1.64 (m, 1H), 1.37-1.34 (m,
1H); 13C NMR (100 MHz, CDCl3) 211.66, 142.60, 117.15, 48.29,
48.16, 41.76, 40.66, 37.08, 31.60, 25.42 ppm; IR (film) 3000, 2960,
J O0105641