Nickel-catalyzed intermolecular coupling of 1,3-dienes and aldehydes via transmetalation of nickelacycles with diisobutylaluminum acetylacetonate

Article abstract of DOI:10.1021/jo0106086

Intermolecular coupling reactions of 1,3-dienes and aldehydes via transmetalation of nickelacycle intermediate with ⁱBu₂Al-acac were investigated. In the reactions, a linear adduct or a branched adduct was produced, depending upon the nature of 1,3-dienes and aldehydes, via two nickelacycles that were relatively stable among the four possible nickelacycles because of the equilibrium with π-allynickel forms.

Full text of DOI:10.1021/jo0106086

656
J . Org. Chem. 2002, 67, 656-662
Nick el-Ca ta lyzed In ter m olecu la r Cou p lin g of 1,3-Dien es a n d
Ald eh yd es via Tr a n sm eta la tion of Nick ela cycles w ith
Diisobu tyla lu m in u m Acetyla ceton a te
Yoshihiro Sato, Rieko Sawaki, Nozomi Saito, and Miwako Mori*
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, J apan
mori@pharm.hokudai.ac.jp
Received J une 14, 2001
Intermolecular coupling reactions of 1,3-dienes and aldehydes via transmetalation of nickelacycle
i
intermediate with Bu2Al-acac were investigated. In the reactions, a linear adduct or a branched
adduct was produced, depending upon the nature of 1,3-dienes and aldehydes, via two nickelacycles
that were relatively stable among the four possible nickelacycles because of the equilibrium with
π-allynickel forms.
Sch em e 1
In tr od u ction
Since the first nickel-promoted co-oligomerization of
1,3-dienes was reported by Reed in 1954,1 many efforts
have been made to achieve the nickel-promoted or
-catalyzed oligomerization of 1,3-dienes with other mul-
tiple bonds.2 The intramolecular version of this type of
reaction is especially useful for producing various cyclic
compounds in a stereoselective manner.3 In this context,
we have already succeeded in the stereoselective cycliza-
tion of 1,3-diene and a tethered aldehyde, as shown in
Scheme 1.4 The cyclization of 1,3-diene 1 having a
tethered aldehyde with a catalytic amount of Ni(0)
complex and PPh3 in the presence of R3SiH proceeded
via π-allylnickel intermediate 2 to give 3′-I, having an
internal olefin in the side chain, in a stereoselective
manner (Type 1 reaction, Scheme 1).4a On the other hand,
we also found that the cyclization of 1 using the same
catalyst system in the presence of diisobutylaluminum
acetylacetonate (iBu2Al-acac) instead of R3SiH stereo-
selectively produced 3-T having a terminal olefin in the
side chain (Type 2 reaction, Scheme 1).4h
It was thought that the reaction in the presence of
iBu2Al-acac proceeded via a transmetalation of the
nickelacycle 4, formed by oxidative cycloaddition of 1 to
i
Ni(0) complex and Bu2Al-acac.
* To whom correspondence should be addressed: Phone and Fax:
+81-11-706-4982.
(1) Reed, H. W. B. J . Chem. Soc. 1954, 1931.
The Type 1 reaction has been further extended to an
intermolecular coupling reaction of 1,3-dienes and alde-
hydes as shown in Scheme 2, in which homoallyl alcohol
derivative 7 was obtained in a stereoselective manner
from 1,3-diene 5 and aldehyde 6 via π-allylnickel inter-
mediate 8.5
(2) For reviews, see: (a) Heimback, P.; J olly, P. W.; Wilke, G. In
Advances in Organometallic Chemistry; Stone, F. G. A., West, R., Eds.;
Academic: New York, 1970; Vol. 8, p 29. (b) J olly, P. W.; Wilke, G.
The Organic Chemistry of Nickel; Academic: New York, 1975; Vol.2.
(c) J olly, P. W. In Comprehensive Organometallic Chemistry; Wilkinson,
G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon: New York, 1982;
Vol. 8, p 613. (d) Keim, W.; Behr, A.; Roper, M. In Comprehensive
Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W.,
Eds.; Pergamon: New York, 1982; Vol. 8, p 371. (e) Fischer, K.; J onas,
K.; Misbach, P.; Stabba, R.; Wilke, G. Angew. Chem., Int. Ed. Engl.
1973, 12, 943. (f) Heimback, P. Angew. Chem., Int. Ed. Engl. 1973,
12, 975. (g) Wilke, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 185.
(3) For [4 + 4] cycloadditions, see: (a) Wender, P. A.; Tebbe, M. J .
Synthesis 1991, 1089. (b) Wender, P. A.; Ihle, N. C.; Correia, C. R. D.
J . Am. Chem. Soc. 1988, 110, 5904. (c) Wender, P. A.; Ihle, N. C.
Tetrahedron Lett. 1987, 28, 2451. (d) Wender, P. A.; Snapper, M. L.
Tetrahedron Lett. 1987, 28, 2221. (e) Wender, P. A.; Ihle, N. C. J . Am.
Chem. Soc. 1986, 108, 4678. For [4 + 2] cycloadditions, see: (f) Wender,
P. A.; Smith, T. E. Tetrahedron 1998, 54, 1255. (g) Wender, P. A.;
Smith, T. E. J . Org. Chem. 1996, 61, 824. (h) Wender, P. A.; Smith, T.
E. J . Org. Chem. 1995, 60, 2962. (i) Wender, P. A.; J enkins, T. E. J .
Am. Chem. Soc. 1989, 111, 6432. For a cyclization of 1,3-diene and
allene, see: (j) Wender, P. A.; J enkins, T. E.; Suzuki, S. J . Am. Chem.
Soc. 1995, 117, 1843. For other cyclizations related to 1,3-dienes, see:
(k) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett. 1992, 539. (l) Tamao, K.;
Kobayashi, K.; Ito, Y. J . Synth. Org. Chem. J pn. 1990, 48, 381. (m)
Montgomery, J .; Oblinger, E.; Savchenko, A. V. J . Am. Chem. Soc.
1997, 119, 4911.
On the other hand, an intermolecular coupling reaction
i
of 1,3-dienes and aldehyde in the presence of Bu2Al-
acac (Type 2 reaction) has not been investigated. In this
Type 2 intermolecular coupling reaction, it was possible
to produce nickelacycle intermediates I-IV (Scheme 3).
It was expected that the reaction course could be con-
(4) (a) Sato, Y.; Takimoto, M.; Hayashi, K.; Katsuhara, T.; Takagi,
K.; Mori, M. J . Am. Chem. Soc. 1994, 116, 9771. (b) Sato, Y.; Takimoto,
M.; Mori, M. Tetrahedron Lett. 1996, 37, 887. (c) Sato, Y.; Takimoto,
M.; Mori, M. Synlett 1997, 734. (d) Sato, Y.; Saito, N.; Mori, M.
Tetrahedron Lett. 1997, 38, 3931. (e) Sato, Y.; Saito, N.; Mori, M.
Tetrahedron 1998, 54, 1153. (f) Sato, Y.; Takanashi, T.; Hoshiba, M.;
Mori, M. Tetrahedron Lett. 1998, 39, 5579. (g) Sato, Y.; Takanashi, T.;
Mori, M. Organometallics 1999, 18, 4891. (h) Sato, Y.; Takimoto, M.;
Mori, M. J . Am. Chem. Soc. 2000, 122, 1624. (i) Sato, Y.; Saito, N.;
Mori, M. J . Am. Chem. Soc. 2000, 122, 2371. (j) Sato, Y.; Takimoto,
M.; Mori, M. Chem. Pharm. Bull. 2000, 48, 1753.
(5) Takimoto, M.; Hiraga, Y.; Sato, Y.; Mori, M. Tetrahedron Lett.
1998, 39, 4543.
10.1021/jo0106086 CCC: $22.00 © 2002 American Chemical Society
Published on Web 01/11/2002

Coupling of 1,3-Dienes and Aldehydes via Transmetalation
J . Org. Chem., Vol. 67, No. 3, 2002 657
Sch em e 2
Sch em e 4
Sch em e 3
Ta ble 1. Rea ction of 5a w ith Va r iou s Ald eh yd es
trolled kinetically or thermodynamically, depending upon
the stability of nickelacycle intermediates I-IV. Herein,
we report the results of investigation of intermolecular
coupling reactions of 1,3-dienes and aldehydes via nickel-
acycle intermediates (Type 2 reaction).
Resu lts a n d Discu ssion
First, the reaction of 1,3-diene 5a and benzaldehyde
6a was investigated (Scheme 4). Treatment of 5a and 6a
(1:1 mixture) with 20 mol % of Ni(0)-PPh3 complex,
generated from NiCl2(PPh3)2 (20 mol %) and BuLi (40 mol
%),7 in the presence of iBu2Al-acac (1.5 equiv) in toluene
gave linear adduct 10a (62%), branched adduct 11a (7%),
and 1:2 adduct 12a (8%). The geometry of the olefin in
10a was exclusively controlled to be an E-configuration.
Products 11a and 12a were obtained as the sole products,
although the stereochemistry of those products could not
be determined at this stage.
a
Reaction was carried out using a Ni complex generated from
b
20 mol % NiCl2(PPh3)2 and 40 mol % BuLi. Reaction was carried
out using a Ni complex genrated from 20 mol % Ni(acac)2 and 40
mol % DIBAL-H in the presence of 40 mol % PPh3. c Reaction was
carried out using a Ni complex generated from 20 mol % Ni(cod)2
and 40 mol % PPh3.
to give 14 along with the evolution of isobutene, from
which 10 was obtained via reductive elimination and
acidic workup. The branched adduct 11 was thought to
be formed via nickelacycle intermediate I in a manner
similar to that described above.
These results indicate that nickelacycle intermediates
I and IV are relatively stable among the four possible
nickelacycles in Scheme 3. It is thought that nickelacycle
I or IV was in equilibrium with π-ally-I or IV, which
would result in an increase in the stability of I and IV.
The 1:2 adduct 12 would be produced from the reaction
of π-allylnickel intermediates 13′ and/or 15′ with alde-
hyde 6 to give 12 via 17 and/or 18 (Scheme 6).
The intermolecular coupling reaction of 1,3-diene 5a
and various aldehydes was investigated, and the results
are summarized in Table 1.
The outline of the mechanism of this intermolecular
coupling reaction is depicted in Scheme 5. It was thought
that the linear adduct 10 was produced via nickelacycle
intermediate IV, which was formed by a C-C bond-
forming reaction between C4 in 1,3-diene 5 and the
carbonyl carbon of aldehyde 6. The transmetalation of
i
nickelacycle IV with Bu2Al-acac gave 13. â-Elimination
of the isobutyl group on the nickel metal in 13 occurred
(6) For other examples of nickel-promoted or -catalyzed intermo-
lecular coupling of 1,3-diene and a carbonyl compound, see: (a) Baker,
R.; Cook, A. H.; Crimmin, M. J . J . Chem. Soc., Chem. Commun. 1975,
727. (b) Baker, R.; Crimmin, M. J . J . Chem. Soc., Perkin Trans. 1 1979,
1264. (c) Kimura, M.; Ezoe, A.; Shibata, K.; Tamaru, Y. J . Am. Chem.
Soc. 1998, 120, 4033.
(7) Henningsen, M. C.; J eropoulos, S.; Smith, E. H. J . Org. Chem.
1989, 54, 3015.

658 J . Org. Chem., Vol. 67, No. 3, 2002
Sato et al.
Sch em e 5
Sch em e 6
Sch em e 7
The reaction of 5a and benzaldehyde 6a using an Ni-
(0)-PPh3 catalyst generated by reduction of Ni(acac)2
8
with DIBAL-H in the presence of PPh3 afforded linear
adduct 10a in 61% yield, branched adduct 11a in 22%
yield, and 1:2 adduct 12a in 1% yield (run 2). The use of
Ni(0)-PPh3 generated from Ni(cod)2 and PPh3 also
increased the formation of branched adduct 11a (run 3).
The ratio of linear adduct 10 to branched adduct 11 was
varied in the reaction of 5a and 6 depending upon the
nature of aldehydes, and 10 and 11 were obtained as
single isomers in all of the reactions shown in Table 1.
It was interesting that the formation of branched adduct
11 was increased in the case of the aldehyde having an
electron-withdrawing group on the aromatic ring and in
the case of aliphatic aldehydes (runs 5 and 6-8, respec-
tively). Notably, the reaction of 5a and 1-butanal 6f gave
branched adduct 11f in 61% yield as a major product (run
8). The branched adduct was also increased in the
absence of chloride anion (runs 2 and 3), which was
derived from the starting catalyst, NiCl2(PPh3)2.
Ta ble 2. Rea ction of E-5b w ith Va r iou s Ald eh yd esa
To determine the stereochemistry of 11f, the compound
11f was converted into 21 as shown in Scheme 7. From
the coupling constant between Ha and Hb in the 1H NMR
spectrum of 21, the stereochemistry of 11f was unam-
biguously determined. Thus, it was thought that 11f was
produced via the nickelacycle 22.
a
Reaction was carried out using a Ni complex genrated from
20 mol % Ni(acac)2 and 40 mol % DIBAL-H in the presence of 40
mol % PPh3.
Next, intermolecular coupling reactions of 1,3-diene
E-5b and various aldehydes were carried out (Table 2).
The reaction of E-5b and benzaldehyde 6a gave the linear
adduct 23a in 30% yield and the branched adduct a n ti-
24a in 42% yield as a single isomer (run 1). The
(8) Krysan, D. J .; Mackenzie, P. B. J . Org. Chem. 1990, 55, 4229.
Also see, ref 3j,k.

Coupling of 1,3-Dienes and Aldehydes via Transmetalation
J . Org. Chem., Vol. 67, No. 3, 2002 659
was stirred at the same temperature for 15 min. Then, a
solution of diene 5 and aldehyde 6 (1.0 equiv to diene) in
degassed toluene (0.1 M) was added to the mixture at 0 °C,
and the mixture was stirred at room temperature for several
hours. To the mixture was added 10% HCl aqueous solution
at 0 °C, and the organic layer was extracted with Et2O. The
combined organic layer was washed with saturated NaHCO3
aqueous solution and brine and dried over Na2SO4. After
removal of the solvent, the residue was purified by column
chromatography on silica gel to give the corresponding cou-
pling products.
Sch em e 8
stereochemistry of a n ti-24a was determined by X-ray
analysis of 25 derived from a n ti-24a (Scheme 8). In the
case of aldehyde 6d , the linear adduct 23d was produced
in preference to the branched adduct 24d (Table 2, run
2). The reaction of E-5b and 1-butanal 6f gave the
coupling products 23f and 24f in 72% total yield, al-
though the ratio of 23f to 24f was almost 1:1 (run 3). The
branched adducts 24d and 24f were also obtained as
single isomers in each case.
Compared with the reaction of E-5b and 6a (Table 2,
run 1), the reaction of Z-5b (Z:E ) 6.8:1) and 6a produced
preferentially branched adducts syn -24a and a n ti-24a
in 61% total yield in a ratio of 1.4:19 along with linear
adduct 23a in 13% yield (Scheme 9).
It is apparent that the branched adducts syn -24a and
a n ti-24a were produced from nickelacycle syn -26 and
a n ti-26 in Scheme 10, respectively.
Thus, this result indicates that syn -26, which seemed
to be more unstable than a n ti-26a because all of the
substituents on the nickelacycle are in the syn-configu-
ration, was preferentially produced in this reaction,
although the reason for this is not clear.
In conclusion, we developed an intermolecular coupling
reaction of 1,3-dienes and aldehydes via transmetalation
of a nickelacycle intermediate with Bu2Al-acac (Type 2
reaction). In this reaction, a linear adduct or branched
adduct was produced depending upon the nature of 1,3-
dienes and aldehydes via nickelacycle I or IV (Scheme
3), which are relatively stable among the four possible
nickelacycles because of the equilibrium with π-ally-I or
IV.
Gen er a l P r oced u r e for th e Cou p lin g Rea ction Usin g
a
Ni Com p lex Gen er a ted fr om Ni(a ca c)2, P P h 3, a n d
DIBAL-H: Meth od B. To a suspension of Ni(acac)2 (20 mol
% to substrate) and PPh3 (40 mol % to substrate) in degassed
toluene (0.02 M) was added DIBAL-H (40 mol % to substrate)
at 0 °C, and the mixture was stirred at room temperature for
i
25 min. To the mixture was added Bu2Al-acac (1.1 equiv to
substrate) at 0 °C, and the mixture was stirred at the same
temperature for 20 min. Then, a solution of diene and aldehyde
6 (1.0 equiv. to substrate) in degassed toluene (0.1 M) was
added to the mixture at 0 °C, and the mixture was stirred at
room temperature for several hours. To the mixture was added
10% HCl aqueous solution at 0 °C, and the organic layer was
extracted with Et2O. The combined organic layer was washed
with saturated NaHCO3 aqueous solution and brine and dried
over Na2SO4. After removal of the solvent, the residue was
purified by column chromatography on silica gel to give the
corresponding coupling products.
Gen er a l P r oced u r e for th e Cou p lin g Rea ction Usin g
a Ni Com p lex Gen er a ted fr om Ni(cod )2 a n d P P h 3: Meth od
C. To a solution of Ni(cod)2 (20 mol % to substrate) and PPh3
(40 mol % to substrate) in degassed toluene (0.02 M) was added
iBu2Al-acac (1.0 M in toluene, 0.75 mL, 0.75 mmol) at 0 °C,
and the mixture was stirred at the same temperature for 15
min. Then, a solution of diene 5 and aldehyde 6 (1.0 equiv to
diene) in degassed toluene (0.1 M) was added to the mixture
at 0 °C, and the mixture was stirred at room temperature. To
the mixture was added 10% HCl aqueous solution at 0 °C, and
the organic layer was extracted with Et2O. The combined
organic layer was washed with saturated NaHCO3 aqueous
solution and brine and dried over Na2SO4. After removal of
the solvent, the residue was purified by column chromatog-
raphy on silica gel to give the corresponding coupling products.
(4E)-5-(4-Meth oxym eth oxym eth ylph en yl)-1-ph en ylpen t-
4-en -1-ol (10a ), 2-(4-Meth oxym eth oxym eth ylp h en yl)-1-
p h en ylp en t-4-en -1-ol (11a ), a n d (3E)-2-(4-Meth oxym eth -
oxym eth ylp h en yl)-1,6-d ip h en ylh ex-3-en e-1,6-d iol (12a ):
(Ta ble 1, Ru n 1). Following the general procedure (Method
A), a crude product, which was obtained from the coupling
reaction of 5a (102.8 mg, 0.50 mmol) and 6a (0.052 mL, 0.51
mmol) using a Ni complex generated from NiCl2(PPh3)2 (65.4
mg, 0.10 mmol) and BuLi (1.52 M in hexane, 0.13 mL, 0.20
i
Exp er im en ta l Section
Gen er a l. All manipulations were performed under an argon
atmosphere unless otherwise mentioned. All solvents and
reagents were purified when necessary using standard pro-
cedures. Column chromatography was performed on silica gel
60 (Merck, 70-230 mesh), and flash chromatography was
performed on silica gel 60 (Merck, 230-400 mesh) using the
indicated solvent. NMR spectra were measured on a J EOL EX
270 (1H at 270 MHz, 13C at 67.5 MHz), J EOL AL 400 (1H at
400 MHz, 13C at 100 MHz), or Bruker ARX-500 (1H at 500
MHz) magnetic resonance spectrometer. Infrared spectra were
recorded on a Perkin-Elmer FTIR 1605 spectrometer. Mass
spectra were measured on Perkin-Elmer Q-Mass 910, J EOL
DX-303, J EOL J MS-HX110, and J EOL J MS-FAB mate mass
spectrometers. Fast-atom bombardment (FAB) mass spectra
were obtained using glycerol or NBA as a matrix. Melting point
was measured on a Yanaco MP-J 3 melting point apparatus.
Gen er a l P r oced u r e for th e Cou p lin g Rea ction Usin g
a Ni Com p lex Gen er a ted fr om NiCl2(P P h )3 a n d Bu Li:
Meth od A. To a suspension of NiCl2(PPh3)2 (20 mol % to
substrate) in degassed toluene (0.02 M) was added BuLi (40
mol % to substrate) at 0 °C, and the mixture was stirred at
the same temperature for 20 min. To the mixture was added
iBu2Al-acac (1.5 equiv to substrate) at 0 °C, and the mixture
i
mmol) in the presence of Bu2Al-acac (1.0 M in toluene, 0.75
mL, 0.75 mmol) at room temperature for 17 h, was purified
by column chromatography on silica gel (hexane-AcOEt, 10/
1, 7/1, 5/1, and 2/1) to give 10a (96.4 mg, 62%), 11a (11.1 mg,
7%), and 12a (16.2 mg, 8%). 10a : 1H NMR (270 MHz, CDCl3)
δ 1.87 (brs, 1H), 1.87-2.04 (m, 2H), 2.26-2.36 (m, 2H), 3.41
(s, 3H), 4.56 (s, 2H), 4.69 (s, 2H), 4.74 (dt, J ) 6.3, 12.7 Hz,
1H), 6.22 (dt, J ) 15.8, 6.7 Hz, 1H), 6.40 (d, J ) 15.8 Hz, 1H),
7.26-7.55 (m, 9H); 13C NMR (67.5 MHz, CDCl3) δ 29.0, 38.2,
54.8, 68.5, 73.3, 95.1, 125.7, 127.1, 127.8, 128.0, 129.6, 130.0,
136.1, 137.0, 144.6; IR (neat) 3448, 1606, 1046 cm-1; LRMS
(EI) m/z 313 (M+ + H), 294, 250, 232, 141, 130, 116, 105, 91,
77, 45; HRMS (EI) calcd for C20H24O3 312.1726, found 312.1697.
11a : 1H NMR (270 MHz, CDCl3) δ 1.88 (d, J ) 3.4 Hz, 1H),
2.53 (m, 2H), 3.00 (ddd, J ) 4.6, 6.3 10.4 Hz, 1H), 3.32 (s, 3H),
4.46 (s, 2H), 4.61 (s, 1H), 4.75-4.76 (m, 1H), 4.87 (d, J ) 10.1
Hz, 1H), 4.88 (d, J ) 17.0 Hz, 1H), 5.53 (ddd, J ) 6.9, 10.1,
17.0 Hz, 1H), 7.24-7.63 (m, 9H); 13C NMR (67.5 MHz, CDCl3)
δ 34.3, 53.0, 55.3, 69.0, 78.0, 95.7, 116.1, 126.5, 127.3, 127.9,
128.9, 135.9, 136.8, 140.5, 142.6; IR (neat) 3446, 1640, 1212,
916 cm-1; LRMS (EI) m/z 294 (M+ - H2O), 219, 144, 128, 104,
91; HRMS (EI) calcd for C20H24O3 312.1726, found 312.1727.
(9) Products syn -24a and a n ti-24a were obtained as an inseparable
mixture. Treatment of the mixture with PCC gave the corresponding
ketone as a single isomer, by which the stereochemistry of syn -24a
was determined to be the syn-configuration.

660 J . Org. Chem., Vol. 67, No. 3, 2002
Sato et al.
Sch em e 9
presence of iBu2Al-acac (1.0 M in toluene, 0.75 mL, 0.75 mmol)
at room temperature for 13 h, was purified by column
chromatography on silica gel (hexane-AcOEt, 10/1, 7/1, 5/1,
and 2/1) to give 10b (132.9 mg, 78%), 11b (12.2 mg, 7%), and
12b (11.3 mg, 5%). 10b: 1H NMR (270 MHz, CDCl3) δ 1.78
(d, J ) 3.2 Hz, 1H), 1.82-2.03 (m, 2H), 2.27 (dt, J ) 13.1, 6.5
Hz, 2H), 3.41 (s, 3H), 3.81 (s, 3H), 4.56 (s, 2H), 4.69 (s, 2H),
6.21 (dt, J ) 16.0, 6.7 Hz, 1H), 6.39 (d, J ) 16.0 Hz, 1H), 6.88-
7.33 (m, 8H); 13C NMR (67.5 MHz, CDCl3) δ 29.1, 38.2, 54.9,
68.6, 73.1, 95.2, 113.6, 125.8, 127.0, 127.9, 129.7, 130.1, 136.2,
136.7, 137.0, 158.7; IR (neat) 3440, 1246, 1044 cm-1; LRMS
(EI) m/z 342 (M+), 324, 130, 121, 91; HRMS (EI) calcd for
C21H26O4 342.1832, found 342.1826. 11b: 1H NMR (270 MHz,
CDCl3) δ 1.83 (d, J ) 3.5 Hz, 1H), 2.39-2.65 (m, 2H), 2.97
(ddd, J ) 4.5, 6.5, 10.9 Hz, 1H), 3.32 (s, 3H), 3.69 (s, 3H), 4.45
(s, 2H), 4.61 (s, 2H), 4.72 (dd, J ) 3.5, 6.5 Hz, 1H), 4.80 (dd, J
) 1.7, 10.2 Hz, 1H), 4.90 (dd, J ) 1.7, 17.1 Hz, 1H), 5.54 (ddt,
J ) 10.2, 17.1, 6.9 Hz, 1H), 6.68 (d, J ) 8.5 Hz, 2H), 6.96 (d,
J ) 7.9 Hz, 2H), 6.99 (d, J ) 7.9 Hz, 2H), 7.13 (d, J ) 8.5 Hz,
2H); 13C NMR (67.5 MHz, CDCl3) δ 34.7, 53.0, 55.2, 69.1, 77.6,
95.7, 113.4, 116.1, 127.7, 127.7, 129.0, 134.7, 135.9, 136.9,
Sch em e 10
12a : 1H NMR (400 MHz, CDCl3) δ 2.40 (ddd, J ) 9.0, 9.1,
15.1 Hz, 1H), 2.46-2.50 (m, 1H), 2.73 (brs, 1H), 2.92 (brs, 1H),
3.62 (s, 3H), 3.51 (dd, J ) 8.1, 9.0 Hz, 1H), 4.49 (s, 2H), 4.61-
4.64 (m, 1H), 4.64 (s, 2H), 4.75 (d, J ) 8.1 Hz, 1H), 5.60 (ddd,
J ) 5.7, 9.1, 15.2 Hz, 1H), 5.93 (dd, J ) 9.0, 15.2 Hz, 1H),
7.01 (d, J ) 8.2 Hz, 2H), 7.10-7.35 (m, 12H); 13C NMR (100
MHz, CDCl3) δ 43.2, 55.4, 58.2, 68.8, 72.9, 77.2, 95.4, 125.5,
126.4, 127.2, 127.2, 127.8 (2C), 127.9, 128.2, 129.9, 133.4,
135.7, 140.2, 141.7, 143.6; IR (neat) 3418, 1044 cm-1; LRMS
(FAB) m/z 441 (M+ + Na), 401, 339, 277, 249, 233; HRMS
(FAB) calcd for C27H30O4Na (M+ + Na) 441.2042, found
441.2047.
Ta ble 1, Ru n 2. Following the general procedure (Method
B), a crude product, which was obtained from the coupling
reaction of 5a (102.1 mg, 0.50 mmol) and 6a (0.052 mL, 0.51
mmol) using a Ni complex generated from Ni(acac)2 (25.9 mg,
0.10 mmol), PPh3 (52.5 mg, 0.20 mmol), and DIBAL-H (1.01
140.6, 158.0; IR (neat) 3450, 1612, 1512, 1248, 1044 cm-1
;
LRMS (EI) m/z 324 (M+ - H2O), 263, 249, 144, 129, 109, 91;
HRMS (EI) calcd for C21H24O3 (M+ - H2O) 324.1725, found
324.1733. 12b: 1H NMR (400 MHz, CDCl3) δ 1.64 (brs, 1H),
2.33-2.52 (m, 2H), 2.64 (brs, 1H), 3.38 (s, 3H), 3.49 (dd, J )
8.3, 9.0 Hz, 1H), 3.74 (s, 3H), 3.80 (s, 3H), 4.50 (s, 2H), 4.56-
4.66 (m, 1H), 4.66 (s, 2H), 4.72 (d, J ) 8.3 Hz, 1H), 5.62 (ddd,
J ) 6.2, 8.6, 15.2 Hz, 1H), 5.92 (dd, J ) 9.0, 15.2 Hz, 1H),
6.72 (d, J ) 8.5 Hz, 2H), 6.86 (d, J ) 8.5 Hz, 2H), 7.03 (d, J )
8.5 Hz, 2H), 7.11 (d, J ) 8.5 Hz, 2H), 7.21 (d, J ) 8.5 Hz, 2H),
7.26 (d, J ) 8.5 Hz, 2H); 13C NMR (67.5 MHz, CDCl3) δ 43.2,
55.2, 55.3, 55.4, 58.3, 68.9, 72.6, 76.8, 95.5, 113.2, 113.6, 126.7,
127.6, 127.8, 128.0, 129.9, 133.6, 133.9, 135.7, 135.8, 140.3,
i
M in toluene, 0.2 mL, 0.20 mmol) in the presence of Bu2Al-
acac (1.0 M in toluene, 0.55 mL, 0.55 mmol) at room temper-
ature for 19 h, was purified by column chromatography on
silica gel (hexane-AcOEt, 10/1, 7/1, 5/1, and 2/1) to give 10a
(95.3 mg, 61%), 11a (35.5 mg, 22%), and 12a (3.0 mg, 1%).
Ta ble 1, Ru n 3. Following the general procedure (Method
C), a crude product, which was obtained from the coupling
reaction of 5a (102.8 mg, 0.50 mmol) and 6a (0.052 mL, 0.51
mmol) using a Ni complex generated from Ni(cod)2 (27.4 mg,
0.10 mmol) and PPh3 (52.6 mg, 0.20 mmol) in the presence of
iBu2Al-acac (1.0 M in toluene, 0.75 mL, 0.75 mmol) at room
temperature for 22 h, was purified by column chromatography
on silica gel (hexane-AcOEt, 10/1, 5/1, and 2/1) to give 10a
(95.3 mg, 61%) and 11a (30.4 mg, 19%).
158.5, 158.6; IR (neat) 3420, 1612, 1514, 1248, 1038 cm-1
;
LRMS (EI) m/z 460 (M+ - H2O), 442 (M+ - 2H2O), 412, 380,
324, 262, 137, 121; HRMS (EI) calcd for C29H30O4 (M+ - 2H2O)
442.2144, found 442.2142.
(4E)-1-(4-Meth oxyca r bon ylp h en yl)-5-(4-m eth oxym eth -
oxym eth ylp h en yl)-p en t-4-en -1-ol (10c) a n d 1-(4-Meth -
oxycar bon ylph en yl)-2-(4-m eth oxym eth oxym eth ylph en yl)-
p en t-4-en -1-ol (11c): (Ta ble 1, Ru n 5). Following the general
procedure (Method A), a crude product, which was obtained
from the coupling reaction of 5a (102.6 mg, 0.50 mmol) and
6c (82.5 mg, 0.51 mmol) using a Ni complex generated from
NiCl2(PPh3)2 (65.4 mg, 0.10 mmol) and BuLi (1.52 M in hexane,
0.13 mL, 0.20 mmol) in the presence of iBu2Al-acac (1.0 M in
toluene, 0.75 mL, 0.75 mmol) at room temperature for 22 h,
was purified by column chromatography on silica gel (hexane-
AcOEt, 10/1, 7/1, 5/1, and 2/1) to give 10c (62.8 mg, 34%) and
11c (27.9 mg, 15%). 10c: 1H NMR (270 MHz, CDCl3) δ 1.85-
2.09 (m, 2H), 1.97 (d, J ) 3.6 Hz, 1H), 2.31 (dt, J ) 7.1, 7.4
Hz, 2H), 3.41 (s, 3H), 3.92 (s, 3H), 4.57 (s, 2H), 4.69 (s, 2H),
4.82 (m, 1H), 6.21 (dt, J ) 15.8, 7.1 Hz, 1H), 6.40 (d, J ) 15.8
Hz, 1H), 7.26-7.34 (m, 4H), 7.44 (d, J ) 8.3 Hz, 2H), 8.03 (d,
J ) 8.3 Hz, 2H); 13C NMR (67.5 MHz, CDCl3) δ 29.1, 38.5,
(4E)-5-(4-Met h oxym et h oxym et h ylp h en yl)-1-(4-m et h -
oxyp h en yl)p en t-4-en -1-ol (10b), 2-(4-Meth oxym eth oxy-
m eth ylp h en yl)-1-(4-m eth oxyp h en yl)p en t-4-en -1-ol (11b)
a n d (3E)-2-(4-Meth oxym eth oxym eth ylp h en yl)-1,6-bis-(4-
m eth oxyp h en yl)p en t-3-en e-1,6-d iol (12b): (Ta ble 1, Ru n
4). Following the general procedure (Method A), a crude
product, which was obtained from the coupling reaction of 5a
(102.2 mg, 0.50 mmol) and 6b (0.062 mL, 0.51 mmol) using a
Ni complex generated from NiCl2(PPh3)2 (65.4 mg, 0.10 mmol)
and BuLi (1.52 M in hexane, 0.13 mL, 0.20 mmol) in the

Coupling of 1,3-Dienes and Aldehydes via Transmetalation
J . Org. Chem., Vol. 67, No. 3, 2002 661
52.0, 55.3, 68.9, 73.4, 95.5, 125.8, 126.0, 128.1, 129.3, 129.7,
129.8, 130.3, 136.6, 137.0, 149.8, 166.9; IR (neat) 3462, 1722,
1610, 1280, 1046 cm-1; LRMS (EI) m/z 370 (M+), 322, 308, 293,
275, 231, 163, 144, 130, 92; HRMS (EI) calcd for C22H26O5
m/z 217 (M+ - CH2OCH3), 206, 175, 144, 129, 105; HRMS (EI)
calcd for C17H26O3 278.1882, found 278.1856.
(7E)-8-(4-Met h oxym et h oxym et h ylp h en yl)oct -7-en -4-
ol (10f) a n d 5-(4-Meth oxym eth oxym eth ylp h en yl)oct-7-
en -4-ol (11f): (Ta ble 1, Ru n 8). Following the general
procedure (Method A), a crude product, which was obtained
from the coupling reaction of 5a (102.5 mg, 0.50 mmol) and 6f
(0.046 mL, 0.51 mmol) using a Ni complex generated from
NiCl2(PPh3)2 (65.6 mg, 0.10 mmol) and BuLi (1.52 M in hexane,
0.13 mL, 0.20 mmol) in the presence of iBu2Al-acac (1.0 M in
toluene, 0.75 mL, 0.75 mmol) at room temperature for 15 h,
was purified by column chromatography on silica gel (hexane-
AcOEt, 10/1, 7/1, 5/1, and 2/1) to give 10f (36.1 mg, 26%) and
11f (85.0 mg, 61%). 10f: 1H NMR (270 MHz, CDCl3) δ 0.94 (t,
J ) 6.7 Hz, 3H), 1.31-1.53 (m, 5H), 1.54-1.69 (m, 2H), 1.62
(dt, J ) 7.0, 7.2 Hz, 2H), 3.41 (s, 3H), 3.62-3.72 (brs, 1H),
4.56 (s, 2H), 4.69 (s, 2H), 6.23 (dt, J ) 15.8, 7.0 Hz, 1H), 6.41
(d, J ) 15.8 Hz, 1H), 7.28 (d, J ) 8.2 Hz, 2H), 7.32 (d, J ) 8.2
Hz, 2H); 13C NMR (67.5 MHz, CDCl3) δ 14.0, 18.7, 29.2, 36.9,
39.7, 55.2, 68.8, 71.0, 95.5, 125.9, 128.1, 129.7, 130.6, 136.4,
137.2; IR (neat) 3438, 1046 cm-1; LRMS (EI) m/z 278 (M+),
260, 216, 205, 199, 173, 130; HRMS (EI) calcd for C17H26O3
1
370.1780, found 370.1787. 11c: H NMR (270 MHz, CDCl3) δ
2.05 (d, J ) 4.0 Hz, 1H), 2.54-2.65 (m, 2H), 3.06 (dt, J ) 9.7,
6.1 Hz, 1H), 3.39 (s, 3H), 3.89 (s, 3H), 4.53 (s, 2H), 4.69 (s,
2H), 4.87-4.90 (m, 2H), 4.96 (dd, J ) 2.0, 17.0 Hz, 1H), 5.59
(ddt, J ) 10.3, 17.0, 6.3 Hz, 1H), 7.04 (d, J ) 8.3 Hz, 2H), 7.21
(d, J ) 3.4 Hz, 2H), 7.24 (d, J ) 3.4 Hz, 2H), 7.90 (d, J ) 8.3
Hz, 2H); IR (neat) 3462, 1722, 1610, 1280, 1046 cm-1; LRMS
(EI) m/z 352 (M+ - H2O), 322, 291, 252, 231, 219,144, 129,
105; HRMS (EI) calcd for C22H26O5 370.1780, found 370.1787.
(4E)-1-Cycloh exyl-5-(4-m eth oxym eth oxym eth ylph en yl)-
p en t-4-en -1-ol (10d ) a n d 1-Cycloh exyl-2-(4-m eth oxym eth -
oxym eth ylp h en yl)p en t-4-en -1-ol (11d ): (Ta ble 1, Ru n 6).
Following the general procedure (Method A), a crude product,
which was obtained from the coupling reaction of 5a (102.6
mg, 0.50 mmol) and 6d (0.062 mL, 0.51 mmol) using a Ni
complex generated from NiCl2(PPh3)2 (65.6 mg, 0.10 mmol) and
BuLi (1.52 M in hexane, 0.13 mL, 0.20 mmol) in the presence
of iBu2Al-acac (1.0 M in toluene, 0.75 mL, 0.75 mmol) at room
temperature for 24 h, was purified by column chromatography
on silica gel (hexane-AcOEt, 10/1, 7/1, 5/1, and 2/1) to give
10d (99.1 mg, 62%) and 11d (35.0 mg, 22%). 10d : 1H NMR
(270 MHz, CDCl3) δ 0.99-1.38 (m, 6H), 1.37 (d, J ) 4.7 Hz,
1H), 1.51-1.84 (m, 7H), 2.34 (dt, J ) 6.8, 6.8 Hz, 2H), 3.41 (s,
3H), 3.41-3.46 (m, 1H), 4.56 (s, 2H), 4.69 (s, 2H), 6.24 (dt, J
) 15.8, 6.8 Hz, 1H), 6.42 (d, J ) 15.8 Hz, 1H), 7.27 (d, J ) 8.5
Hz, 2H), 7.33 (d, J ) 8.3 Hz, 2H); 13C NMR (67.5 MHz, CDCl3)
δ 26.0, 26.1, 26.3, 27.7, 29.0, 29.4, 33.5, 43.6, 55.0, 68.6, 75.2,
95.2, 125.7, 127.9, 129.4, 130.6, 136.1, 137.1; IR (Nujol) 3316,
1060 cm-1; LRMS (EI) m/z 318 (M+), 300, 256, 238, 217, 204,
173, 142, 130; HRMS (EI) calcd for C20H30O3 318.2195, found
318.2202. 11d : 1H NMR (270 MHz, CDCl3) δ 1.05-1.26 (m,
6H), 1.47 (d, J ) 5.1 Hz, 1H), 1.54-1.82 (m, 5H), 2.47 (m, 1H),
2.65 (m, 1H), 2.85 (ddd, J ) 3.8, 7.1, 10.3 Hz, 1H), 3.42 (s,
3H), 3.48 (m, 1H), 4.57 (s, 2H), 4.72 (s, 2H), 4.86 (dd, J ) 2.2,
10.3 Hz, 1H), 4.95 (dd, J ) 2.2, 17.4 Hz, 1H), 5.61 (ddt, J )
10.3, 17.4, 7.0 Hz, 1H), 7.15 (d, J ) 8.3 Hz, 2H), 7.30 (d, J )
8.3 Hz, 2H); 13C NMR (67.5 MHz, CDCl3) δ 25.9, 26.3, 26.4,
26.5, 30.3, 35.1, 39.8, 48.4, 55.3, 69.2, 79.9, 95.8, 115.8, 128.1,
128.5, 135.8, 137.2, 142.2; IR (neat) 3484, 1640, 1514, 1046
cm-1; LRMS (EI) m/z 300 (M+ - H2O), 259, 238, 215, 144, 129;
HRMS (EI) calcd for C20H30O3 318.2195, found 318.2193.
(6E)-2-Meth yl-7-(4-m eth oxym eth oxym eth ylph en yl)h ept-
6-en -3-ol (10e) a n d 2-Meth yl-4-(4-m eth oxym eth oxym eth -
ylp h en yl)oct-7-en -4-ol (11e): (Ta ble 1, Ru n 7). Following
the general procedure (Method A), a crude product, which was
obtained from the coupling reaction of 5a (102.7 mg, 0.50
mmol) and 6e (0.046 mL, 0.51 mmol) using a Ni complex
generated from NiCl2(PPh3)2 (65.4 mg, 0.10 mmol) and BuLi
(1.52 M in hexane, 0.13 mL, 0.20 mmol) in the presence of
iBu2Al-acac (1.0 M in toluene, 0.75 mL, 0.75 mmol) at room
temperature for 16 h, was purified by column chromatography
on silica gel (hexane-AcOEt, 10/1, 7/1, 5/1, and 2/1) to give
10e (79.0 mg, 57%) and 11e (30.8 mg, 22%). 10e: 1H NMR
(270 MHz, CDCl3) δ 0.92 (d, J ) 1.7 Hz, 3H), 0.94 (d, J ) 1.7
Hz, 3H), 1.34 (d, J ) 5.3 Hz, 1H), 1.51-1.74 (m, 3H), 2.17-
2.46 (m, 2H), 3.39-3.47 (m, 1H), 3.41 (s, 3H), 4.57 (s, 2H), 4.67
(s, 2H), 6.24 (dt, J ) 15.8, 6.8 Hz, 1H), 6.43 (d, J ) 15.8 Hz,
1H), 7.26-7.35 (m, 4H); 13C NMR (67.5 MHz, CDCl3) δ 17.1,
18.7, 29.6, 33.6, 33.6, 55.2, 68.8, 76.0, 95.5, 125.9, 128.1, 129.7,
130.7, 136.4, 137.2; IR (neat) 3448 cm-1; LRMS (EI) m/z 278
(M+), 260, 205, 173, 159, 155, 142, 130; HRMS (EI) calcd for
1
278.1882, found 278.1886. 11f: H NMR (270 MHz, CDCl3) δ
0.86 (t, J ) 7.0 Hz, 3H), 1.17-1.51 (m, 4H), 1.44 (d, J ) 5.9
Hz, 1H), 2.42-2.52 (m, 1H), 2.64-2.74 (m, 2H), 2.75 (m, 1H),
3.42 (s, 3H), 3.71-3.77 (brs, 1H), 4.57 (s, 2H), 4.72 (s, 2H),
4.89 (dd, J ) 1.7, 10.2 Hz, 1H), 4.98 (dd, J ) 1.7, 17.0 Hz,
1H), 5.65 (ddt, J ) 10.2, 17.0, 6.9 Hz, 1H), 7.14-7.32 (m, 4H);
13C NMR (67.5 MHz, CDCl3) δ 13.9, 19.0, 35.5, 36.8, 55.0, 55.3,
69.1, 75.2, 95.8, 116.0, 128.1, 128.6, 136.0, 137.0, 141.6; IR
(neat) 3450, 1640, 1514, 1048 cm-1; LRMS (EI) m/z 260 (M+
- H2O), 217, 199, 175, 144, 129, 105; HRMS (EI) calcd for
C
17H24O2 (M+ - H2O) 260.1795, found 260.1776.
(4E)-1,7-Dip h en ylh ep t-4-en -1-ol (23a ) a n d 2-(2-P h en yl-
et h yl)-1-p h en ylp en t -4-en -1-ol (24a ): (Ta b le 2, R u n 1).
Following the general procedure (Method B), a crude product,
which was obtained from the coupling reaction of E-5b (78.2
mg, 0.50 mmol) and 6a (0.052 mL, 0.51 mmol) using a Ni
complex generated from Ni(acac)2 (25.8 mg, 0.10 mmol), PPh3
(52.9 mg, 0.20 mmol), and DIBAL-H (1.01 M in toluene, 0.2
mL, 0.2 mmol) in the presence of iBu2Al-acac (1.0 M in
toluene, 0.55 mL, 0.55 mmol) at room temperature for 21 h,
was purified by column chromatography on silica gel (hexane,
hexane-AcOEt, 20/1, 10/1, and 5/1) to give 23a (40.5 mg, 30%)
1
and 24a (55.9 mg, 42%). 23a : H NMR (500 MHz, CDCl3) δ
1.73-1.85 (m, 3H), 2.03-2.07 (m, 2H), 2.31 (dt, J ) 6.1, 7.4
Hz, 2H), 2.66 (t, J ) 7.4 Hz, 2H), 4.60-4.63 (m, 1H), 5.44 (dt,
J ) 15.4, 6.1 Hz, 1H), 5.48 (dt, J ) 15.4, 6.1 Hz, 1H), 7.15-
7.35 (m, 10H); 13C NMR (67.5 MHz, CDCl3) δ 28.8, 34.3, 36.0,
38.7, 73.9, 125.9, 126.0, 128.1, 127.5, 128.2, 128.4, 130.2, 142.0,
144.7; IR (neat) 3374, 3026, 2926, 2852, 1602, 1494, 1452 cm-1
;
LRMS (EI) m/z 248 (M+ - H2O), 170, 157, 144, 129, 120, 107,
104, 91; HRMS (EI) calcd for C19H20 (M+ - H2O) 248.1565,
found 248.1568. 24a : 1H NMR (270 MHz, CDCl3) δ 1.43-1.69
(m, 2H), 1.76-1.92 (m, 1H), 1.83 (d, J ) 3.5 Hz, 1H), 2.27 (t,
J ) 6.3 Hz, 2H), 2.46-2.69 (m, 2H), 4.68 (dd, J ) 3.5, 6.4 Hz,
1H), 5.03-5.13 (m, 2H), 5.84 (ddt, J ) 10.0, 17.1, 7.1 Hz, 1H),
7.05-7.37 (m, 10H); 13C NMR (100 MHz, CDCl3) δ 31.3, 33.2,
33.5, 44.2, 76.1, 116.5 (CH2), 125.6, 126.4, 127.2, 128.2, 128.2,
128.2, 136.8, 142.2, 143.2; IR (neat) 3420, 1602, 1494 cm-1
;
LRMS (EI) m/z 248 (M+ - H2O), 219, 206, 157, 144, 129, 107,
91; HRMS (EI) calcd for C19H20 (M+ - H2O) 248.1565, found
248.1561.
(4E)-1-Cycloh exyl-7-p h en ylh ep t -4-en -1-ol (23d ) a n d
1-Cycloh exyl-2-(2-ph en yleth yl)-pen t-4-en -1-ol (24d): (Table
2, Ru n 2). Following the general procedure (Method B), a
crude product, which was obtained from the coupling reaction
of E-5b (78.1 mg, 0.49 mmol) and 6d (0.062 mL, 0.51 mmol)
using a Ni complex generated from Ni(acac)2 (25.9 mg, 0.10
mmol), PPh3 (52.8 mg, 0.20 mmol), and DIBAL-H (1.01 M in
C
17H26O3 278.1882, found 278.1904. 11e: 1H NMR (270 MHz,
CDCl3) δ 0.84 (d, J ) 6.7 Hz, 3H), 0.91 (d, J ) 6.7 Hz, 3H),
1.43-1.56 (m, 1H), 1.48 (d, J ) 5.3 Hz, 1H), 2.36-2.48 (m,
1H), 2.75 (m, 1H), 2.68-2.81 (m, 2H), 3.42 (s, 3H), 3.54 (ddd,
J ) 4.0, 5.3, 6.3 Hz, 1H), 4.56 (s, 2H), 4.72 (s, 2H), 4.87 (dd, J
) 1.4, 10.1 Hz, 1H), 4.95 (dd, J ) 1.4, 17.1 Hz, 1H), 5.62 (ddt,
J ) 10.1, 17.1, 6.9 Hz, 1H), 7.14 (d, J ) 8.1 Hz, 2H), 7.30 (d,
J ) 8.1 Hz, 2H); 13C NMR (67.5 MHz, CDCl3) δ 15.2, 20.2,
29.8, 36.1, 49.4, 55.3, 69.1, 80.1, 95.8, 115.9, 128.1, 128.4, 135.9,
137.1, 142.1; IR (neat) 3488, 1640, 1514, 998 cm-1; LRMS (EI)
i
toluene, 0.2 mL, 0.20 mmol) in the presence of Bu2Al-acac
(1.0 M in toluene, 0.55 mL, 0.55 mmol) at room temperature
for 21 h, was purified by column chromatography on silica gel
(hexane, hexane-AcOEt, 20/1, 10/1, and 5/1) to give 23d (65.5
mg, 48%) and 24d (25.9 mg, 19%). 23d : 1H NMR (500 MHz,

662 J . Org. Chem., Vol. 67, No. 3, 2002
Sato et al.
CDCl3) δ 1.00-1.77 (m, 14H), 2.05 (m, 1H), 2.15 (m, 14H), 2.31
(dt, J ) 6.3, 7.3 Hz, 2H), 2.67 (t, J ) 7.3 Hz, 2H), 3.32-3.33
(m, 1H), 5.46 (dt, J ) 15.4, 6.3 Hz, 1H), 5.50 (dt, J ) 15.4, 6.3
Hz, 1H), 7.16-7.19 (m, 3H), 7.26-7.29 (m, 2H); 13C NMR (67.5
MHz, CDCl3) δ 26.2, 26.3, 26.5, 27.7, 29.1, 29.2, 33.8, 34.3,
36.0, 43.7, 75.6, 125.7, 128.2, 128.4, 129.9, 130.7, 142.0; IR
(neat) 3374, 3026, 2924, 2850, 1602, 1496, 1450 cm-1; LRMS
(EI) m/z 272 (M+), 254 (M+ - H2O), 171, 143, 129, 104, 95, 91;
HRMS (EI) calcd for C19H26 (M+ - H2O) 254.2035, found
254.2017. 24d : 1H NMR (400 MHz, CDCl3) δ 0.94-1.75 (m,
14H), 1.78-1.88 (m, 2H), 2.05-2.13 (m, 1H), 2.27-2.30 (m,
1H), 2.54-2.69 (m, 2H), 3.34 (m, 1H), 5.02 (d, J ) 10.3 Hz,
1H), 5.07 (d, J ) 17.3 Hz, 1H), 5.79-5.89 (m, 1H), 7.15-7.29
(m, 5H); 13C NMR (67.5 MHz, CDCl3) δ 26.1, 26.3, 26.5, 28.5,
29.7, 32.1, 32.9, 33.3, 38.9, 40.6, 77.6, 116.0, 125.7, 128.3, 137.7,
1H), 5.44 (dt, J ) 15.4, 6.3 Hz, 1H), 5.49 (dt, J ) 15.4, 6.3 Hz,
1H), 7.17 (m, 3H), 7.27 (m, 2H); 13C NMR (100 MHz, CDCl3)
δ 14.2, 18.9, 34.4, 36.1, 37.1, 39.7, 71.2, 125.6, 128.1, 128.3,
129.8, 130.5, 141.9; IR (neat) 3382, 1638, 1496 cm-1; LRMS
(EI) m/z 214 (M+ - H2O), 189, 171, 160, 158, 130, 104, 91;
HRMS (EI) calcd for C16H22 (M+ - H2O) 214.1721, found
1
214.1742. 24f: H NMR (270 MHz, CDCl3) δ 0.93 (t, J ) 6.9
Hz, 3H), 1.26-1.81 (m, 7H), 1.29 (d, J ) 5.2 Hz, 1H), 2.11-
2.33 (m, 2H), 2.65 (t, J ) 8.0 Hz, 2H), 3.67 (dt, J ) 5.2, 5.2
Hz, 1H), 5.00-5.13 (m, 2H), 5.84 (ddt, J ) 10.0, 17.1, 7.2 Hz,
1H), 7.13-7.31 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 14.2,
18.9, 28.9, 34.4, 36.1, 37.1, 39.7, 71.2, 125.6, 128.1, 128.3, 129.8,
130.5, 141.9; IR (neat) 3356, 1604, 1496 cm-1; LRMS (EI) m/z
214 (M+ - H2O), 189, 171, 160, 158, 130, 104, 91; HRMS (EI)
calcd for C16H22 (M+ - H2O) 214.1721, found 214.1742.
142.6; IR (neat) 3404, 2924, 2852, 1602, 1496, 1450 cm-1
;
Registr y Nu m ber . (3E)-6-Phenyl-1,3-hexadiene (E-5b),
77605-16-4; (3Z)-6-phenyl-1,3-hexadiene (Z-5b), 77605-17-5.
LRMS (EI) m/z 254 (M+ - H2O), 213, 160, 149, 143, 117, 104,
95, 91; HRMS (EI) calcd for C19H26 (M+ - H2O) 254.2035, found
254.2012.
Ack n ow led gm en t. This work was supported in part
by a grant from the Research Foundation for Pharma-
ceutical Sciences and by the Uehara Memorial Founda-
tion, which are gratefully acknowledged. N.S. thanks
Research Fellowships of the J apan Society for the
Promotion of Science for Young Scientists for support.
(7E)-10-P h en yld ec-7-en -4-ol (23f) a n d 5-(2-P h en yleth -
yl)oct-7-en -4-ol (24f): (Ta ble 2, Ru n 3). Following the
general procedure (Method B), a crude product, which was
obtained from the coupling reaction of E-5b (78.5 mg, 0.50
mmol) and 6f (0.046 mL, 0.51 mmol) using a Ni complex
generated from Ni(acac)2 (25.6 mg, 0.10 mmol), PPh3 (52.4 mg,
0.20 mmol), and DIBAL-H (1.01 M in toluene, 0.2 mL, 0.20
i
mmol) in the presence of Bu2Al-acac (1.0 M in toluene, 0.55
Su p p or tin g In for m a tion Ava ila ble: Experimental Pro-
cedures and spectral data for the synthesis of substrate 5a
and for preparations of 21 (from 11f) and 25 (from a n ti-24a )
and an ORTEP diagram of 25. This material is available free
of charge via the Internet at http://pubs.acs.org.
mL, 0.55 mmol) at room temperature for 21 h, was purified
by column chromatography on silica gel (hexane, hexane-
AcOEt, 20/1, 10/1, and 5/1) to give 23f (39.5 mg, 34%) and 24f
(44.0 mg, 38%). 23f: 1H NMR (500 MHz, CDCl3) δ 0.92 (t, J )
7.0 Hz, 3H), 1.35-1.48 (m, 7H), 2.07-2.12 (m, 2H), 2.31 (dt, J
) 6.3, 7.2 Hz, 2H), 2.66 (t, J ) 7.2 Hz, 2H), 3.57-3.60 (m,
J O0106086