Reversible carbon-carbon bond formation between 1,3-dienes and aldehyde or ketone on nickel(0)

Article abstract of DOI:10.1021/ja060580l

The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give η³:η¹-allylalkoxynickel complexes. The treatment of these complexes with carbon monoxide led to the formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant with the formation of Ni(CO)₃(PCy ₃). The scission of the nickel-oxygen bond of the allylalkoxy complexes with ZnMe₂ leading to η³-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated η³-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the η³-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me₃SiCl to η³:η¹-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting η³-1-siloxyethylallylnickel complex was treated with carbon monoxides followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even for the η³: η¹-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo the reverse reaction hampering its isolation. The isolation of the η³:η¹-allylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadiene and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the η³: η¹-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide.

Full text of DOI:10.1021/ja060580l

Published on Web 05/05/2006
Reversible Carbon-Carbon Bond Formation between
1,3-Dienes and Aldehyde or Ketone on Nickel(0)
Sensuke Ogoshi,* Kei-ichi Tonomori, Masa-aki Oka, and Hideo Kurosawa
Contribution from the Department of Applied Chemistry, Faculty of Engineering,
Osaka UniVersity, Suita, Osaka 565-0871, Japan
Received January 25, 2006; E-mail: ogoshi@chem.eng.osaka-u.ac.jp
Abstract: The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give
η3:η1-allylalkoxynickel complexes. The treatment of these complexes with carbon monoxide led to the
formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant
with the formation of Ni(CO)3(PCy3). The scission of the nickel-oxygen bond of the allylalkoxy complexes
with ZnMe2 leading to η3-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative
cyclization. The methylated η3-allylnickel compound underwent the reductive elimination. The carbonylative
coupling reaction of the η3-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere.
Similarly, the addition of Me3SiCl to η3:η1-allylalkoxynickel complexes was also efficient for the inhibition of
the reverse reaction. The resulting η3-1-siloxyethylallylnickel complex was treated with carbon monoxides
followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even
for the η3:η1-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo
the reverse reaction hampering its isolation. The isolation of the η3:η1-allylalkoxynickel complex containing
ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-
1,3-butadiene and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave
the η3:η1-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide.
ating or reducing reagents has been achieved in the past decade,4
in which the oxidative cyclization of dienes and carbonyl units
Introduction
The oligomerizations, co-oligomerizations, or polymerizations
of 1,3-dienes catalyzed by nickel(0) complexes and their reaction
mechanisms had been studied well.1 Most of these studies were
on the reaction of 1,3-butadienes with carbon-carbon double
or triple bonds. However, there have been only a limited number
of examples of the carbon-carbon formation between the 1,3-
butadiene and carbon-oxygen double bond. The stoichiometric
reaction of 1,3-butadiene with carbon dioxide gave the corre-
sponding η3:η1-allylcarboxynickel complexes by the oxidative
cyclization of CdC and CdO on nickel(0), of which structure
was determined by X-ray diffraction analysis.2 Similarly stoi-
chiometric reactions of 1,3-butadiene with aldehydes or ketones
have been reported, in which only organic compounds have been
isolated as reaction products.3 On the other hand, the formation
of a carbon-carbon bond between aldehydes or ketones and
1,3-butadienes in the presence of nickel(0) catalyst and alkyl-
on nickel(0) is proposed for a possible key step to form the
carbon-carbon bond.4b
Recently, we made the direct observation of the oxidative
cyclization of η2-alkene and η2-aldehyde or η2-ketone on nickel
to give nickeladihydrofurans.5,6 If the reaction of 1,3-butadienes
with aldehydes or ketones on nickel(0) proceeds via the
oxidative cyclization, the formation of an η3:η1-allylalkoxy
complex is expected. However, this step might compete with
the formation of η3:η1-allylalkylnickel complexes arising from
extremely facile diene dimerization on nickel(0) under catalytic
reaction conditions.7 In fact, in the presence of a catalytic amount
of Ni(0), the reaction of a diene with aldehyde or ketone
proceeded to give alcohols containing a diene and a carbonyl
compound in the ratio of 2:1, in which an η3:η1-allylalkylnickel
was proposed as a key intermediate.8 On the other hand, only
(4) (a) Takimoto, M.; Hiraga, Y.; Sato, Y.; Mori, M. Tetrahedron Lett. 1998,
4543-4546. (b) Kimura, M.; Ezoe, A.; Shibata, K.; Tamaru, Y. J. Am.
Chem. Soc. 1998, 120, 4033-4034. (c) Kimura, M.; Fujimatsu, H.; Ezoe,
A.; Shibata, K.; Shimizu, M.; Matsumoto, S.; Tamaru, Y. Angew. Chem,
Int. Ed. 1999, 38, 397-400. (d) Kimura, M.; Matuo, S.; Shibata, K.;
Tamaru, Y. Angew. Chem, Int. Ed. 1999, 38, 3386-3388. (e) Modern
Organonickel Chemistry; Tamaru, Y., Eds.; Wiley-VCH: Weinheim, 2005.
(5) Ogoshi, S.; Oka, M.; Kurosawa, H. J. Am. Chem. Soc. 2004, 126, 11082-
11083.
(6) Ogoshi, S.; Ueta, M.; Arai, T.; Kurosawa, H. J. Am. Chem. Soc. 2005,
127, 12810-12811.
(7) Jolly, P. W.; Tkatchenko, I.; Wilke, G. Angew. Chem., Int. Ed. Engl. 1971,
10, 329-330. Benn, B.; Bu¨ssemeier, B.; Holle, S.; Jolly, P. W.; Mynott,
R.; Tkatchenko, I. Wilke, G. J. Organomet. Chem. 1985, 279, 63-86.
(8) Baker, R.; Crimmin, M. J. J. Chem. Soc., Perkin Trans. I 1979, 1264-
1267. Akutagawa, S. Bull. Chem. Soc. Jpn. 1976, 49, 3646-3648.
(1) (a) Jolly, P. W.; Wilke, G. Organometallic Chemistry Series: The Organic
Chemistry of Nickel, Vol. 1: Organonickel Complexes; Academic Press:
New York, 1974. (b) Jolly, P. W.; Wilke, G. The Organic Chemistry of
Nickel, Vol. 2: Organic Synthesis; Academic Press: New York, 1975.
(2) (a) Walther, D.; Dinjus, E. Zeitschrift fuer Chemie 1982, 22, 228-229. (b)
Dinjus, E.; Walther, D.; Schuetz, H.; Schade, W. Zeitschrift fuer Chemie
1983, 23, 303-304. (c) Walther, D.; Dinjus, E. Zeitschrift fuer Chemie
1984, 24, 63. (d) Hoberg, H.; Oster, B. W. J. Organomet. Chem. 1984,
266, 321-326. (e) Hoberg, H.; Apotecher, B. J. Organomet. Chem. 1984,
270, C15-C17. (f) Walther, D.; Dinjus, E.; Goerls, H.; Sieler, J.; Lindqvist,
O.; Andersen, L. J. Organomet. Chem. 1985, 286, 103-114. (g) Hoberg,
H.; Peres, Y.; Milchereit, A. J. Organomet. Chem. 1986, 307, C38-C40.
(3) The stoichiometric reaction of 1,3-butadienes and acetone with Ni(cod)2
was reported very briefly in a review without details: Wilke. G. Angew.
Chem., Int. Ed. Engl. 1988, 27, 185-206.
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J. AM. CHEM. SOC. 2006, 128, 7077-7086
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A R T I C L E S
Ogoshi et al.
Scheme 1. Formation of η3:η1-Allylalkoxynickel Complex 1a
Scheme 2. Formation of η3:η1-Allylalkoxynickel Complex 1b and
1b′
a few reaction products via η3:η1-allylalkylnickel had been
reported in the presence of alkyl metals.4d Thus, it seems of
particular interest to gain deep insight into the behavior of
dienes, carbonyl compounds, and alkyl metals on nickel, which
might be complementary to the missing part of the nickel-
butadiene chemistry. Here, we report the formation and the
structure of η3:η1-allylalkoxynickel complexes by the reaction
of an aldehyde or a ketone with dienes in the presence of
nickel(0) for the first time and their feasible reverse reaction
accompanying the carbon-carbon cleavage. Moreover, the role
of the third component, such as ZnMe2 and Me3SiCl, to suppress
the reverse reaction is also discussed.
min prior to benzaldehyde led to an incomplete formation of
1a (80%) after 16 h with a homocoupling product η3:η1-
allylalkylnickel (2, 20%) present. This might be due to the rapid
formation of 2 and the slow transformation from 2 to 1a. In
fact, the isolated 2 reacted with benzaldehyde slowly to give
1a (80%, 48 h) and 2,3-dimethyl-1,3-butadiene. Such a carbon-
carbon bond cleavage had been also observed in the reaction
of 2 with PPh3.7 On the other hand, the formation of 1a by the
reaction of (η2-PhCHO)Ni(PCy3)29 with 2,3-dimethyl-1,3-buta-
diene was faster (2 h, 75%), although the reaction did not
proceed completely due to the reverse reaction accompanying
the carbon-carbon bond cleavage to give an equilibrium
mixture. This might be caused by the presence of an excess
amount of PCy3 in solution. In fact, the addition of PCy3 (1
equiv) to a solution of 1a in C6D6 led to the formation of an
equilibrium mixture with the regeneration of (η2-PhCHO)Ni-
(PCy3)2 and 2,3-dimethyl-1,3-butadiene (25% each), which is
consistent with the observation mentioned above.
Similarly, the addition of 5 equiv of 1,3-butadiene to a
solution of benzaldehyde, PCy3 and Ni(cod)2 led to the
formation of the η3:η1-allylalkoxynickel complex as a mixture
of two isomers (1b/1b′ ) 85/15) (Scheme 2). The molecular
structure of 1b was confirmed by X-ray diffraction analysis
(Figure 2). The complex shows a slightly different η3-allyl
structure from that of the normal η3-allyl ligand. The bond length
between C2-C3 (1.37(2) Å) is significantly shorter than C1-
C2 (1.45(2) Å). This observation suggests a larger contribution
of sp2 hybridization on C3 than C1, although Ni-C1 (2.00(1)
Å) and Ni-C3 (2.01(1) Å) are comparable. The 13C NMR
spectra show the consistent trend; the resonance of C3 (δ 97.4)
in 1b appears at a much lower magnetic field than that of C1
(δ 31.3). A similar NMR trend was also reported in η3-
allylpalladium complexes.10
Results and Discussion
Reaction of Diene with Aldehyde. The addition of 5 equiv
of 2,3-dimethyl-1,3-butadiene to a solution of benzaldehyde,
PCy3, and Ni(cod)2 gave the corresponding η3:η1-allylalkoxy-
nickel complex (1a) (Scheme 1) as a sole product. The molecular
structure of 1a was also confirmed by the X-ray diffraction
analysis (Figure 1), which is consistent with that in a solution
determined by the NOE measurement between an Me group
bound to C3 and the hydrogen on C5. Furthermore, the
stereochemistry of the only product in the nickel-catalyzed
homoallylation of PhCHO with 2,3-dimethyl-1,3-butadiene in
the presence of Et3B was consistent with that assumed to be
derived from an intermediate corresponding to 1a.1b Both the
order of the addition of substrates and the ratio of nickel and
phosphine are important for the efficient formation of the η3:
η1-allylalkoxynickel complex. Although 1a was generated
quantitatively in 10 min by the addition of 2,3-dimethyl-1,3-
butadiene (5 equiv) to the solution of benzaldehyde, PCy3, and
Ni(cod)2 in C6D6, the addition of 2,3-dimethyl-1,3-butadiene 5
Figure 1. Molecular structure 1a.
Figure 2. Molecular structure 1b.
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Reaction of 1,3-Diene and Aldehyde/Ketone on Ni(0)
A R T I C L E S
Scheme 3. Reaction of η3:η1-Allylalkoxynickel Complex 1a To
Form 7a
Scheme 4. Reaction of η3:η1-Allylalkoxynickel Complex 1a or
1b,1b′ To Form 9a,9b
Scheme 5. Reaction of Isoprene with PhCHO
The treatment of a mixture of 1b and 1b with carbon
monoxide (5 atm) gave a carbonylated compound, 3-(E)-
ethylidene-5-phenyl-dihydrofuran-2(3H)-one (3b) generated by
the isomerization of initial carbonylation product, 5-phenyl-3-
vinyl-dihydrofuran-2(3H)-one, in 50% yield, as well as 1,3-
butadiene and benzaldehyde concomitant with the formation of
Ni(CO)3(PCy3) (Scheme 2). However, 1a gave no carbonylated
compound, but only quantitative regeneration of 2,3-dimethyl-
butadiene and benzaldehyde was observed under the same
condition. Moreover, the addition of 5 equiv of COD to the
solution of 1a in C6D6 also led to the regeneration of Ni(cod)2,
PCy3, 2,3-dimethyl-1,3-butadiene, and benzaldehyde in 10%
yield for each, with 90% of 1a remaining intact. Thus, the
carbon-carbon bond cleavage to regenerate diene and aldehyde
might occur very easily in the presence of suitable ligands, such
as PCy3, carbon monoxide, and COD, which can stabilize a
nickel(0) species generated in situ.
of 4a was confirmed by the transformation into organic
compounds. In the presence of 2 equiv of TMSCHdCH2
, 4a
underwent the reductive elimination at 60 °C to give the
corresponding organozinc compound (5a) and Ni(TMSCHd
CH2)2(PCy3) (6).12 Moreover, although the treatment of 1a with
carbon monoxide regenerated diene and PhCHO quantita-
tively, the reaction of 4a with carbon monoxide under the
same condition occurred to give the acylated compound (7a)
via the insertion of carbon monoxide followed by the reductive
elimination.
The treatment 1a with Me3SiCl is also efficient for the
carbonylation of 1a without the occurrence of the carbon-
carbon bond cleavage. The η3-1-siloxyethylallylnickel (8a)
prepared from 1a and Me3SiCl reacted with carbon monoxide
to give an acid chloride determined as its methyl ester in 87%
yield (Scheme 4).13 The mixture of 1b and 1b′ also gave the
corresponding methyl ester in 70% yield as well. These results
suggest that the cleavage of the nickel-oxygen bond would be
a key role of the reducing or alkylating reagent having Lewis
acidic character, promoting the catalytic reaction by preventing
the nicklacycle from undergoing the backward carbon-carbon
bond cleavage.
We were interested in confirming if dialkylzinc compounds
can generate a nickel-alkyl bond and oxygen-zinc bond by
the reaction with 1a, since the multicomponent coupling
reactions proceeded in the presence of alkylmetal compounds,
such as dialkylzinc.4c,d,11 In fact, ZnMe2 reacted with 1a very
rapidly to give η3-(allyl)Ni(Me)(PCy3) (4a) (Scheme 3), al-
though the reaction of ZnMe2 with 2 did not occur at all under
the same reaction conditions. This result, together with the
reversibility of formation of 2, rationalizes why the dimeriza-
tion of dienes does not inhibit the catalytic multicomponent
reaction. Unfortunately 4a could not be isolated in pure form
due to the decomposition during concentration under reduced
The reaction of isoprene and PhCHO with Ni(cod)2 and PCy3
proceeded very rapidly to give a mixture of three isomers
(Scheme 5). As the reaction proceeded, the ratio of isomers
changed from 1c/1c′/1c′′ ) 87/13/0 to 18/73/9, which suggests
that the kinetic compound 1c isomerizes to 1c′ and 1c′′ to give
an equilibrium mixture of these three complexes. In the nickel-
catalyzed reaction of the three component coupling reaction of
1
pressure. The H NMR and 31P NMR spectra indicate that 4a
is a mixture of isomers, which might be caused by the difference
of the aggregation of the -OZnMe moiety. Thus, the formation
(9) Walther, D. J. Organomet. Chem. 1980, 190, 393-401.
(10) Lloyed-Jones, G. C.; Stephen, S. C.; Murray, M.; Butts, C. P.; Vyskocˇil,
Sˇ.; Koc´ovskyˆ, P. Chem.sEur. J. 2000, 6, 4348-4357.
(12) Olefin-promoted reductive elimination of η3-allylnickel(II): Kurosawa, H.;
Ohnishi, H.; Emoto, M.; Chatani, N.; Kawasaki, Y.; Murai, S.; Ikeda, I.
Organometallics 1990, 9, 3038-3042.
(11) Calculation for the role of ZnMe2 in nickel(0)-catalyzed couping reaction
of enone, alkyne with ZnMe2: Hratchian, H. P.; Chowdhury, S. K.;
Gutie´rrez-Garc´ıa, V. M.; Amarasinghe, K. K. D.; Heeg, M. J.; Schlegel,
H. B.; Montgomery, J. Organometallics 2004, 23, 4636-4646.
(13) The carbonylation of η3-allylnickel chloride to give the corresponding acyl
chloride had been reported: Heck, R. F. J. Am. Chem. Soc. 1963, 85, 2013-
2014.
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Scheme 6. Reaction of 2,3-Dimethyl-1,3-butadiene with Butanal
Scheme 8. Reaction of 2,3-Benzyl-1,3-butadiene with
Benzophenone
Scheme 9. Reaction of 2,3-Dimethyl-1,3-butadiene with
Cyclobutanone
of Ni(cod)2 and PCy3 occurred during concentration of the
reaction mixture under reduced pressure. By the use of 2 as a
starting material, 1e could be isolated. However, the reaction
with carbon monoxide gave the expected compound 3e in poor
yield (8%). Thus, the addition of TMSCl to the reaction mixture,
as described in Scheme 4, was applied to suppress the
proceeding of the reverse reaction. This method was efficient
as well even for the transformation of 1e into an ester derivative
(9e), containing diene and ketone in its structure, by carbonyl-
ation followed by the treatment with MeOH.
Scheme 7. Reaction of 2,3-Dimethyl-1,3-butadiene with Acetone
The failure of the isolation of 1e by the general method might
be due to the removal of more volatile 2,3-dimethyl-1,3-
butadiene and acetone generated by the reverse reaction prior
to COD under reduced pressure. If a much heavier diene and
ketone were employed as the coupling components, it would
be easier to isolate cyclized complexes. The reaction of 2,3-
dibenzyl-1,3-butadine with benzophenone proceeded cleanly to
give expected η3:η1-allylalkoxynickel (1f) quantitatively, and
the reverse reaction did not occur under reduced pressure to
allow us to isolate 1f (Scheme 8). The molecular structure of
1f was determined by the X-ray diffraction analysis. The
treatment of carbon monoxide (5 atm) regenerated the diene
and ketone quantitatively. The η3:η1-allylalkoxynickel complex
(1g) formed by the reaction of 2,3-dimethyl-1,3-butadiene with
cyclobutanone could be also isolated (Scheme 9), and its
molecular structure is shown in Figure 3. No occurrence of the
reverse reaction under reduced pressure might be owing to the
release of the steric strain energy of the cyclobutane ring by
the change of hybridization of carbonyl carbon from sp2 to sp3.
Moreover, even under carbon monoxide pressure (5 atm), 1g
isoprene with PhCHO and Et3B reported by Tamaru, only one
regioisomer derived from an intermediate corresponding to 1c
was obtained.4c This isomer might be obtained by the rapid
transmetalation of 1c with an alkylzinc compound prior to the
isomerization. The reaction of the mixture of 1c, 1c′, and 1c′′
(10/76/14) with carbon monoxide gave a mixture of 3c′ and
3c′′ in 51% and 13%, respectively. However, the carbonylated
compound of 1c was not observed in the reaction mixture, which
might be due to the requirement of the less favorable formation
of a quaternary carbon.
The reaction of 2,3-dimethyl-1,3-butadiene with butanal
proceeded smoothly to give a mixture of two isomers in 84%
isolated yield (1d/1d′ ) 95/5) (Scheme 6). The treatment of
the mixture of 1d and 1d′ with carbon monoxide (5 atm) led to
the formation of a mixture of carbonylated compounds (3d/3d′
) 95/5), although 1a, the corresponding PhCHO analogue, gave
no carbonylated compound. The reaction of 1d with ZnMe2 also
gave 4d, which could be isolated as a mixture of two isomers.
The elemental analysis showed the expected composition. The
reductive elimination occurred at 60 °C to give 5d in 77% yield.
The treatment with carbon monoxide (5 atm) gave 7d in 86%
yield.
Reaction of Diene with Ketone. The reaction of 2,3-
dimethyl-1,3-butadiene with acetone (10 equiv) generated the
corresponding η3:η1-allylalkoxynickel complex (1e) in 94%
yield in C6D6 (Scheme 7). Unfortunately, the isolation of 1e by
the general method failed, since the quantitative regeneration
Figure 3. Molecular structure 1g.
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Reaction of 1,3-Diene and Aldehyde/Ketone on Ni(0)
A R T I C L E S
chemical shifts in the 13C spectra were recorded relative to Me4Si. The
chemical shifts in the 31P spectra were recorded using 85% H3PO4 as
Scheme 10. Reaction of 2,3-Dimethyl-1,3-butadiene with Styrene
Oxide
1
external standard. Assignment of the resonances in H and 13C NMR
spectra was based on 1H-1H COSY, HMQC, and HMBC experiments.
HMQC and HMBC experiments are inverse detection heterocorrelated
1
NMR experiments recorded at the H frequency of the spectrometer,
probing one-bond (CH) and multiple-bond (CCH and CCCH) con-
nectivity. The relative stereochemistry about the η3-allylnickel moiety
and -ONi moiety (1a, 1b, 1c, 1c′, 1d, and 1h) was determined by the
NOE measurement between substituent groups bound to C3 and C5 as
indicated in Figure 1. Elemental analyses were performed at the
Instrumental Analysis Center, Faculty of Engineering, Osaka Uni-
versity. For some compounds, accurate elemental analyses were
precluded by extreme air or thermal sensitivity and/or systematic
problems with elemental analysis of organometallic compounds. X-ray
crystal data were collected by a Rigaku RAXIS-RAPID Imaging Plate
diffractometer.
Scheme 11. Formation of (η2-Phenylacetoaldehyde)nickel
Materials: The degassed and distilled solvents (THF, toluene, and
hexane) used in this work were commercially available. C6D6 was
distilled from sodium benzophenone ketyl. All commercially available
reagents were distilled and degassed prior to use.
Caution: It is possible that the treatment of nickel compounds with
carbon monoxide might give Ni(CO)4 (extremely toxic) by short of
amounts of PR3, careless handling, or an accident. The reaction mixture
must be handled in a well ventilated fume hood.
resisted the release of the diene and ketone to some extent and
underwent the carbonylation to give 3g in 38% yield.
Reaction of Diene with Oxirane. The reaction of 2,3-
dimethyl-1,3-butadiene with styrene oxide was examined to
study if a ring-expanded η3:η1-allylalkoxynickel can be obtained
or not. The reaction occurred at 60 °C in toluene to not give a
ring-expanded complex (10h) but an unexpected complex (1h)
derived from 2,3-dimethyl-1,3-butadiene and phenylaceto-
aldehyde, an isomer of styrene oxide (Scheme 10). This result
indicates that styrene oxide isomerized to phenylacetoaldehyde
under the reaction conditions. In fact, the isomerization occurred
at 60 °C for 5 h to give (η2-PhCH2CHO)Ni(PCy3)2 in 60% yield
(Scheme 11).14 Thus, styrene oxide can be employed as a
precursor of phenylacetoaldehyde.
Isolation of 1a: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
PCy3 (240 mg, 0.80 mmol), and 81.3 µL of PhCHO (84.9 mg, 0.80
mmol) in 5 mL of THF was added 0.45 mL of 2,3-dimethyl-1,3-
butadiene (328.6 mg, 4.00 mmol) at room temperature. The solution
changed from orange to yellow. The reaction mixture was stirred for
2 h followed by concentration in vacuo to give yellow solids (1a, 382
mg, 91%). An analytical sample and a single crystal for X-ray
diffraction analysis were prepared by recrystallization from hexane at
-20 °C. 1H NMR (C6D6): δ 1.00-2.00 (m, 36H including 1H of
CH2CH(Ph)ONi at δ 1.15, 2H of NiCH2C(CH3) at δ 1.57 and δ 1.75),
1.46 (d, J ) 2.9 Hz, NiCH2C(CH3)C(CH3), 2.52 (t, J ) 11.0 Hz, 1H,
CH2CH(Ph)ONi), 2.19 (s, 3H, NiCH2C(CH3)), 6.28 (dd, J ) 10.50
Hz, 4.00 Hz, 1H, CH(Ph)ONi, 7.19 (d, J ) 6.90 Hz, para in
C6H5), 7.37 (t, J ) 7.26 Hz, 2H of meta in C6H5), 7.72 (d, J ) 7.26
Hz, 2H of ortho in C6H5). 31P NMR (C6D6): δ 42.3 (s). 13C NMR
(C6D6): δ 20.2 (d, JCP ) 2.3 Hz), 21.8 (s), 27.3 (s, Cy), 28.3 (d,
JCP ) 5.3 Hz, Cy), 30.9 (s, Cy), 33.7 (d, JCP ) 17.5 Hz, Cy), 34.2 (d,
JCP ) 6.1 Hz), 94.8 (d, JCP ) 10.7 Hz, CH(Ph)(ONi)), 101.2 (d,
JCP ) 15.2 Hz), 113.7 (s), 126.0 (s), 126.4 (s), 128.2 (s), 152.8 (s).
Anal. Calcd for C31H49Ni1O1P1: C, 70.60; H, 9.36. Found: C, 70.50;
H, 9.69.
Reaction of (η2-PhCHO)Ni(PCy3)2 with 2,3-Dimethyl-1,3-
butadiene: To a solution of (η2-PhCHO)Ni(PCy3)2 (14.6 mg, 0.02
mmol) in 0.5 mL of C6D6 were added 2.3 µL of 2,3-dimethyl-1,3-
butadiene (1.6 mg, 0.02 mmol) at room temperature. The solution
changed from orange to red orange immediately to give 1a (80%,
2 h).
Reaction of 2 with PhCHO: To a solution of 2 (10.1 mg, 0.02
mmol) in 0.5 mL of C6D6 were added 2.0 µL of PhCHO (2.0 mg, 0.02
mmol) at room temperature. The reaction proceeded slowly to give 1a
(80%, 48 h).
Conclusion
The reversible oxidative cyclization of dienes and aldehydes
or ketones on nickel(0) proceeded to give η3:η1-allylalkoxynickel
complexes. The structures of some complexes were determined
by the X-ray diffraction analysis. Consideration of the isomer-
ization of the kinetic complex to the thermodynamic complexes
at room temperature during the oxidative cyclization between
isoprene, PhCHO, and nickel(0) and the structure of the reported
three component coupling product suggests that a relatively rapid
transmetalation step between the kinetic intermediate complex
and alkyl metals might occur in a catalytic reaction. Moreover,
the role of alkyl metals having Lewis acidic character was also
revealed to be the cleavage of the nickel-oxygen bond to
suppress the reverse reaction. The reaction with styrene oxide
resulted in the formation of the η3:η1-allylalkoxynickel contain-
ing phenylacetoaldehyde as a component. This result suggests
that oxiranes could be potential precursors to their isomeric
aldehydes or ketones.
Experimental Section
Reaction of 1a with Carbon Monoxide: A pressure tight NMR
tube containing 0.5 mL of C6D6 (0.5 mL) solution of 1a (5.3 mg, 0.01
mmol) was treated with carbon monoxide (5 atm). The solution changed
from orange to colorless immediately to give 2,3-dimethyl-1,3-
butadiene, benzaldehyde, and Ni(CO)3(PCy3) quantitatively.
Reaction of 1a with COD: To a solution of 1a (5.3 mg, 0.01 mmol)
in 0.5 mL of C6D6 were added 6.1 µL of COD (5.4 mg, 0.05 mmol) at
room temperature. The reaction proceeded immediately to give 2,3-
dimethyl-1,3-butadiene, benzaldehyde, PCy3, and Ni(cod)2 (10% each).
90% of 1a remained intact.
General: All manipulations were conducted under a nitrogen
atmosphere using standard Schlenk or drybox techniques. 1H, 31P, and
13C nuclear magnetic resonance spectra were recorded on JEOL GSX-
270S and JEOL AL-400 spectrometers. The chemical shifts in 1H
nuclear magnetic resonance spectra were recorded relative to Me4Si or
residual protiated solvent (C6D5H (δ 7.16) or CHCl3 (δ 7.27)). The
(14) Palladium-catalyzed isomerization of oxirans to aldehydes was reported:
Vanker, Y. D.; Chandhuri, N. C.; Singh, S. D. Synth. Commun. 1986, 16,
1621-1626.
9
J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006 7081

A R T I C L E S
Ogoshi et al.
Isolation of 1b: A solution of Ni(cod)2 (275 mg, 1.0 mmol), PCy3,
(289 mg, 1.0 mmol), and 101.6 µL of PhCHO (106.1 mg, 1.0 mmol)
in 5 mL of toluene was cooled to -10 °C, and 270.5 mg of
1,3-butadiene (122.5 mL (gas), 5.0 mmol) were added and the mixture
was stirred for 10 min. The solution changed from red to red-purple.
The cooling bath was removed, and the reaction mixture was stirred at
room temperature for 1 h followed by concentration in vacuo. The
residue was washed with hexane to give orange solids (336.2 mg, 68%)
as a mixture of two isomers (1b/1b′ ) 85/15). An analytical sample
and a single crystal for X-ray diffraction analysis were prepared by
recrystallization from hexane at -20 °C. 1b: 1H NMR (C6D6): δ 0.99
(d, J ) 12.4 Hz, 1H, NiCH2CH), 1.15-2.15 (m, 36H, including 1H of
NiCH2CH at δ 1.86 and 2H of CH2CH(Ph)ONi), 4.14 (t, J ) 12.0, 4.0
Hz, 1H, NiCH2CHCH), 5.50 (td, J ) 6.4 Hz, 12.0 Hz, 1H, NiCH2CH),
6.17 (dd, J ) 4.0 Hz, 9.8 Hz, 1H, CH(Ph)ONi), 7.19 (m, 1H, para in
C6H5), 7.36 (t, J ) 7.6 Hz, 2H of meta in C6H5), 7.69 (d, J ) 7.6 Hz,
2H of ortho in C6H5). 31P NMR (C6D6): δ 35.9 (s). 13C NMR(C6D6):
δ 27.2 (s, Cy), 28.2 (d, JCP ) 3.0 Hz, Cy), 28.3 (d, JCP ) 2.3 Hz, Cy),
30.8 (s, Cy), 31.3 (d, JCP ) 6.9 Hz, NiCH2CH), 34.0 (s, Cy), 34.2 (s,
Cy), 48.5 (s, CH2CH(Ph)ONi), 97.1 (d, JCP ) 13.8 Hz, CH(Ph)ONi),
97.4 (d, JCP ) 10.7 Hz, NiCH2CHCH), 109.8 (s, NiCH2CH), 126.2
(s), 126.4 (s), 128.1 (s), 152.1 (s). 1b′: 1H NMR (C6D6): δ 4.27 (m,
1H, NiCH2CHCH), 5.72 (m, 1H, NiCH2CH), 6.36 (d, J ) 6.4 Hz, 1H,
CH(Ph)ONi), 7.45 (t, J ) 7.6 Hz, 2H of meta in C6H5), 7.94 (d, J )
7.6 Hz, 2H of ortho in C6H5). The other resonances are hidden by those
of 1b. 31P NMR (C6D6): δ 34.35 (s). The resonances of the minor
isomer could not be observed in a 13C NMR spectrum. Anal. Calcd for
C29H45O1P1Ni1 (a mixture of 1b and 1b′): C, 69.76; H, 9.08. Found:
C, 69.41; H, 9.17.
Reaction of 1b with Carbon Monoxide: A pressure tight NMR
tube containing 0.5 mL of a C6D6 solution of a mixture of 1b and 1b
(10.1 mg, 0.02 mmol) was treated with carbon monoxide (5 atm). The
solution changed from orange to yellow immediately to give the
carbonylation product15(3b: 50%), 1,3-butadiene (50%), benzaldehyde
(50%), and Ni(CO)3(PCy3) (100%).
Reaction of 1a with ZnMe2: To a solution of 1a (10.5 mg, 0.02
mmol) in 0.5 mL of C6D6 was added ZnMe2 (0.02 mmol, 20 µL, 1
M/hexane) at room temperature. The reaction proceeded immediately
to give 4a quantitatively. 4a could not be isolated in pure form due to
the decomposition during concentration under a reduced pressure. The
1H NMR and 31P NMR spectra indicate that 4a is a mixture of isomers.
Selected spectral data for 4a: 1H NMR (C6D6): δ -0.30 (brm, 3H,
OZnCH3), -0.20 (brd, JHP ) 3.2 Hz, 3H, NiCH3), 3.05 (brm, 2H,
CH2CH(Ph)OZnMe), 5.79 (dd, JHH ) 2.7, 10.8 Hz, 1H, CH(Ph)-
OZnMe). 31P NMR (C6D6): δ 50.5 (m).
Reaction of 4a with TMSCHdCH2: To a solution of 4a generated
by the reaction of 1a (20.9 mg, 0.04 mmol) with ZnMe2 (0.04 mmol,
40 µL, 1 M/hexane) in 0.5 mL of C6D6 was added TMSCHdCH2 (0.08
mmol, 8.0 mg), and the mixture was heated at 60 °C for 18 h. The
formation of Ni(TMSCHdCH2)2(PCy3) (6) was confirmed by the
comparison of the 31P NMR spectrum with that of an authentic sample.
5a was identified as an alcohol by protonation followed by separation
from nickel compound by the column. 1H NMR (CDCl3): δ 0.94
(t, J ) 7.6 Hz, 3H, sCH2CH3), 1.70 (s, 6H, sC(CH3)dC(CH3)s),
2.07 (m, 1H, sCH2CH3), 2.17 (q, J ) 7.6 Hz, 1H, sCH2CH3),
2.28 (dd, J ) 4.8, 9.4 Hz, 1H, sCH2CH(OH)Ph), 2.68 (dd,
J ) 9.6, 11.6 Hz, 1H, sCH2CH(OH)Ph), 4.79 (dd, J ) 11.6, 4.8 Hz,
1H, sCH2CH(OH)Ph), 7.25-7.41 (m, 5H, sPh). 13C NMR (CDCl3):
δ 13.21 (s, sCH2CH3), 18.33 (s, sC(CH3)dC(CH3)s), 18.78 (s,
sC(CH3)dC(CH3)s), 27.41 (s, sCH2CH3), 44.81 (s, sCH2CH-
(OH)Ph), 72.44 (s, sCH2CH(OH)Ph), 123.52 (s, sC(CH3)d
C(CH3)s), 125.91 (s, Ph), 127.50 (s, Ph), 128.52 (s, Ph), 135.29 (s,
sC(CH3)dC(CH3)s), 144.77 (s, Ph). HRMS Calcd for C14H20O1
204.3122, found m/z 204.1513.
Reaction of 4a with Carbon Monoxide: In a pressure tight NMR
tube, a solution of 4a in 0.5 mL of C6D6 generated by the reaction of
1a (20.9 mg, 0.04 mmol) with ZnMe2 (0.04 mmol, 40 µL, 1 M/hexane)
was treated with carbon monoxide (5 atm). The solution changed from
brown to colorless immediately to give 7a and Ni(CO)3(PCy3) (89%).
7a was identified as the corresponding alcohol by protonation separated
by a silica column.1H NMR (CDCl3): δ 1.68 (s, 6H, sC(CH3)d
C(CH3)s), 2.13 (s, 3H, sCOCH3), 2.37 (dd, J ) 5.1, 13.4 Hz, 1H,
sCH2CH(OH)Ph), 2.72 (dd, J ) 8.9, 13.2 Hz, 1H, sCH2CH(OH)Ph),
3.16 (d, J ) 16.3 Hz, 1H, sCH2COCH3), 3.27 (d, J ) 16.7 Hz, 1H,
sCH2COCH3), 4.82 (dd, J ) 8.9, 5.1 Hz, 1H, sCH2CH(OH)Ph),
7.33-7.41 (m, 5H, sPh). 13C NMR (CDCl3): δ 19.64 (s, sC(CH3)d
C(CH3)s), 20.49 (s, sC(CH3)dC(CH3)s), 30.06 (s, sCH2COCH3),
45.61 (s, sCH2CH(OH)Ph), 50.77 (s, sCH2COCH3), 73.02 (s, s
CH2CH(OH)Ph), 126.44(s, Ph), 126.88 (s, sC(CH3)dC(CH3)s),
128.06 (s, Ph), 129.01 (s, Ph), 129.67 (s, sC(CH3)dC(CH3)s), 145.02
(s, Ph), 207.48 (s, sCH2COCH3). HRMS Calcd for C15H18O1 (sH2O)
214.3073, Found m/z 214.1353.
Reaction of 1a with TMSCl: To a solution of 1a (5.3 mg, 0.01
mmol) in 0.5 mL of C6D6 was added TMSCl (1.1 mg, 0.01 mmol, 1.3
µL) at room temperature. The reaction proceeded gradually to give an
η3-1-siloxyethylallylnickel quantitatively for 4 h as a mixture of two
isomers (8a: 60%, 8a′: 40%). These are diastereomers via η1-allyl
species as an intermediate. 8a: 1H NMR (C6D6): δ 0.07 (s, 9H,
-OSi(CH3)3), 1.01-2.05 (m, 38H, including 1H of NiCH2C(CH3) at
δ 1.51, 3H of NiCH2C(CH3)C(CH3) at δ 1.59 and 1H of NiCH2C-
(CH3) at δ 1.92), 2.21 (s, 3H, NiCH2C(CH3)), 2.62 (dd, J ) 14.5, 5.8
Hz, 1H, -CH2CH(Ph)OTMS), 2.79 (dd, J ) 14.5, 7.2 Hz, 1H,
-CH2CH(Ph)OTMS), 5.08 (m, 1H, CH(Ph)OTMS), 7.09 (d, J ) 6.9
Hz, 1H of para in C6H5), 7.16 (hidden by C6D6 peak, 2H of meta in
C6H5), 7.33 (d, J ) 6.9 Hz, 2H of ortho in C6H5). 31P NMR (C6D6):
δ 41.9 (s). 13C NMR (C6D6): δ 0.52 (s, -OSi(CH3)3), 21.0 (s, NiCH2C-
(CH3)), 23.3 (d, JCP ) 2.3 Hz, NiCH2C(CH3)C(CH3)), 27.2 (s, Cy),
28.2 (s, Cy), 28.3 (s, Cy), 30.7 (d, JCP ) 3.8 Hz, Cy), 30.9 (s, Cy),
34.3 (d, JCP ) 18.3 Hz, Cy), 40.0 (d, JCP ) 6.8 Hz, NiCH2C(CH3)),
48.8 (d, JCP ) 2.3 Hz, -CH2CH(Ph)OTMS), 73.5 (d, JCP ) 5.3 Hz,
-CH2CH(Ph)OTMS), 98.1 (d, JCP ) 16.8 Hz, NiCH2C(CH3)C(CH3),
114.5 (s, NiCH2C(CH3), 126.5 (s, Ph), 127.6 (s, Ph), 128.7 (s, Ph),
146.2 (s, Ph). An analytical sample was not obtained due to gradual
decomposition in a solution. 8a′: 1H NMR (C6D6): δ 0.02 (s, 9H,
-OSi(CH3)3), 1.01-2.05 (m, 38H, including 3H of NiCH2C(CH3)C-
(CH3) at δ 1.44, 1H of NiCH2C(CH3) at δ 1.62 and 3H of NiCH2C-
(CH3)C(CH3) at δ 1.72), 2.12 (1H, s, NiCH2C(CH3)), 2.48 (d, J )
14.5 Hz, 1H, -CH2CH(Ph)OTMS), 2.70 (d, J ) 10.5 Hz, 1H, -CH2-
CH(Ph)OTMS), 5.06 (m, 1H, CH(Ph)OTMS). The other resonances
are hidden by those of 8a. 31P NMR (C6D6): δ 41.5 (s). 13C NMR
(C6D6): δ 0.49 (s, -OSi(CH3)3), 20.9 (d, JCP ) 3.0 Hz, NiCH2C(CH3)C-
(CH3)), 22.1 (s, NiCH2C(CH3)), 34.4 (d, JCP ) 18.3 Hz, Cy), 40.9 (d,
JCP ) 6.1 Hz, NiCH2C(CH3)), 48.5 (d, JCP ) 3.3 Hz, -CH2CH(Ph)-
OTMS), 72.7 (d, JCP ) 3.8 Hz, -CH2CH(Ph)OTMS), 96.8 (d, JCP
)
16.8 Hz, NiCH2C(CH3)C(CH3)), 115.3 (s, NiCH2C(CH3)), 126.4 (s,
Ph), 127.5 (s, Ph), 128.8 (s, Ph), 146.6 (s, Ph). The other resonances
are hidden by those of 8a. An analytical sample was not obtained due
to gradual decomposition in a solution.
Reaction of a mixture of 1b and 1b′ with TMSCl: To a solution
of a mixture of 1b and 1b′ (9.9 mg, 0.02 mmol) in 0.5 mL of C6D6
was added TMSCl (2.2 mg, 0.02 mmol, 2.5 µL) at room temperature.
The reaction proceeded immediately to give an η3-1-siloxyethyl-
allylnickel quantitatively as a mixture of two isomers (8b: 60%, 8b′:
40%). These are diastereomers via η1-allyl species as an intermediate.
8b: 1H NMR (C6D6): δ 0.12 (s, 9H, -OSi(CH3)3), 1.05-2.03 (m,
34H, including 1H of NiCH2CH at δ 1.34), 2.17-2.21 (m, 2H,
including 1H of NiCH2CH and CH2CH(Ph)OTMS), 2.82 (m, 1H,
-CH2CH(Ph)OTMS), 3.77 (ddd, J ) 17.8, 9.1, 4.3 Hz, 1H, NiCH2-
CHCH), 4.82 (m, 1H, NiCH2CH), 5.16 (m, 1H, CH(Ph)OTMS), 7.08
(m, 1H, Ph), 7.18 (hidden by C6D6 peak, 2H, Ph) 7.45 (t, J ) 7.2 Hz,
(15) Haaima, G.; Lynch, M. J.; Routledge, A.; Weavers, R. Tetrahedron 1991,
47, 5203-5214.
9
7082 J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006

Reaction of 1,3-Diene and Aldehyde/Ketone on Ni(0)
A R T I C L E S
2H, Ph). 31P NMR (C6D6): δ 34.0 (s). 13C NMR (C6D6): δ 0.68 (s,
-OSi(CH3)3), 27.1 (s, Cy), 28.2 (d, JCP ) 1.5 Hz, Cy), 28.3 (s, Cy),
30.7 (s, Cy), 34.6 (d, JCP ) 19.0 Hz, Cy), 39.7 (d, JCP ) 6.9 Hz,
1c′: 1H NMR (C6D6): 1.00-2.00 (m, 36H, including 1H of NiCH2CH-
(CH3) at δ 1.08, 1H of NiCH2CH(CH3) at δ 1.63 and 1H of CH2CH-
(Ph)ONi at δ 1.91), 2.08 (s, 3H, NiCH2CH(CH3)), 2.20 (m, 1H,
CH2CH(Ph)ONi), 4.08 (dt, JHH ) 4.0 Hz, JHP ) 11.6 Hz, 1H, NiCH2-
CH(CH3)CH), 6.08 (dd, J ) 3.6 Hz, 10.5 Hz, 1H, CH(Ph)ONi), 7.17
(m, 1H of para-C6H5), 7.36 (t, J ) 7.6 Hz, 2H of meta-C6H5), 7.71 (d,
J ) 7.6 Hz, 2H of ortho-C6H5). 31P NMR (C6D6): δ 39.0 (s). 13C NMR
(C6D6): δ 20.5 (s, NiCH2CH(CH3)), 27.5 (s, Cy), 28.5 (d, JCP ) 6.1
Hz, Cy), 28.6 (d, JCP ) 6.8 Hz, Cy), 31.1 (s, Cy), 34.1 (d, JCP ) 17.5
Hz, Cy), 36.3 (d, JCP ) 6.1 Hz, NiCH2CH(CH3)), 44.6 (d, JCP ) 2.3
Hz, CH2CH(Ph)ONi), 93.5 (d, JCP ) 14.5 Hz, NiCH2CH(CH3)CH),
96.4 (d, JCP ) 10.7 Hz, CH(Ph)ONi), 105.3 (s, NiCH2CH(CH3)), 126.3
(s, Ph), 126.6 (s, Ph), 128.5 (s, Ph), 152.6 (s, Ph). 1c′′: 1H NMR
(C6D6): δ 4.22 (m, 1H, NiCH2CH(CH3)CH). The other resonances are
hidden by those of 1c′. 31P NMR (C6D6): δ 37.2 (s). Anal. Calcd for
C30H47O1P1Ni1 (a mixture of 1c, 1c′, and 1c′′): C, 70.19; H, 9.23.
Found: C, 69.67; H, 9.28.
NiCH2CH), 44.4 (d, JCP ) 2.3 Hz, CH2CH(Ph)OTMS), 73.9 (d, JCP
)
3.9 Hz, CH(Ph)OTMS), 91.0 (d, JCP ) 17.6 Hz, NiCH2CHCH), 109.7
(s, NiCH2CH), 126.5 (s, Ph), 127.4 (s, Ph), 128.3 (Ph, hidden by C6D6
peak), 146.2 (s, Ph). An analytical sample was not obtained due to
gradual decomposition in a solution. 8b′: 1H NMR (C6D6): δ 0.11 (s,
9H, -OSi(CH3)3), 1.05-2.03 (m, 34H, including 1H of NiCH2CH at
δ 1.27), 2.30 (m, 1H, -CH2CH(Ph)OTMS), 2.92 (m, 1H, -CH2CH-
(Ph)OTMS), 3.62 (ddd, J ) 18.1, 9.1, 4.3 Hz, 1H, NiCH2CHCH), 4.91
(m, 1H, NiCH2CH). The other resonances are hidden by those of 8b.
31P NMR (C6D6): δ 33.9 (s). 13C NMR (C6D6): δ 0.65 (s, -OSi(CH3)3),
27.1 (s, Cy), 30.7 (s, Cy), 34.6 (d, JCP ) 19.0 Hz, Cy), 39.9 (d, JCP
)
6.8 Hz, NiCH2CH), 43.6 (d, JCP ) 2.3 Hz, CH2CH(Ph)OTMS), 74.4
(d, JCP ) 3.8 Hz, CH(Ph)OTMS), 90.6 (d, JCP ) 17.6 Hz, NiCH2-
CHCH), 109.3 (s, NiCH2CH), 127.0 (s, Ph), 127.5 (s, Ph), 128.3 (Ph,
hidden by C6D6 peak), 145.7 (s, Ph). An analytical sample was not
obtained due to gradual decomposition in a solution.
Reaction of a Mixture of 1c, 1c′, and 1c′′ with Carbon Monoxide:
A pressure tight NMR tube containing a solution of a mixture of 1c,
1c′, and 1c′′ (1c/1c′/1c′′ ) 10/76/14) (10.3 mg, 0.02 mmol) in C6D6
(0.5 mL) was treated with carbon monoxide (5 atm). The solution
changed from orange to colorless immediately to give the carbonylation
products (64%) as a mixture of two isomers (3c′: 51%, 3c′′: 13%).
3c′: 1H NMR (CDCl3): δ 1.86 (s, 3H, sC(CH3)dCH2), 2.25 (ddd, J
) 2.2, 11.6, 12.7 Hz, 1H, sCH2CH(Ph)Os), 2.76 (m, 1H, sCH2CH-
(Ph)Os), 3.53 (dd, J ) 5.8, 8.4 Hz, 1H, sCH(COOs)s), 5.02 (s,
1H, sC(CH3)dCH2), 5.06 (s, 1H, sC(CH3)dCH2), 5.41 (dd, J ) 6.5,
8.7 Hz, 1H, sCH2CH(Ph)Os), 7.33-7.43 (m, 5H, Ph). 13C NMR
(CDCl3): δ 20.07 (s, sC(CH3)dCH2), 37.23 (s, sCH2CH(Ph)Os),
49.47 (s, sCH(COOs)s), 79.29 (s, sCH2CH(Ph)Os), 115.85 (s, s
C(CH3)dCH2), 125.66 (s, Ph), 128.80 (s, Ph), 129.00 (s, Ph), 139.42
(s, sC(CH3)dCH2), 176.07 (s, sCOOs). 3c′′: 1H NMR (CDCl3): δ
1.90 (s, 3H, sC(CH3)dCH2), 2.43 (m, 1H, sCH2CH(Ph)Os), 2.70
(m, 1H, sCH2CH(Ph)Os), 3.50 (dd, J ) 6.9, 4.7 Hz, 1H, s
CH(COOs)s), 4.99 (s, 1H, sC(CH3)dCH2), 5.05 (s, 1H, sC(CH3)d
CH2), 5.58 (t, J ) 6.9 Hz, 1H, sCH2CH(Ph)Os), 7.33-7.43 (m, 5H,
Ph). 13C NMR (CDCl3): δ 21.00 (s, sC(CH3)dCH2), 36.25 (s,
sCH2CH(Ph)Os), 47.26 (s, sCH(COOs)s), 79.24 (s, sCH2CH-
(Ph)Os), 114.62 (s, sC(CH3)dCH2), 125.30 (s, Ph), 128.56 (s, Ph),
128.99 (s, Ph), 139.82 (s, sC(CH3)dCH2), 176.72 (s, sCOOs).
HRMS Calcd for C13H14O2 202.0994, Found m/z 202.0998 (3c′),
202.1001 (3c′′)
Reaction of 1a with TMSCl Followed by Carbonylation:
A
pressure tight NMR tube containing a solution of 8a in C6D6 (0.5 mL)
generated by the reaction of 1a (21.1 mg, 0.04 mmol) with TMSCl
(4.3 mg, 0.04 mmol, 5.1 µL) was treated with carbon monoxide (5
atm). The solution changed from red to light blue gradually and was
1
quenched with methanol to give a hydroxyester (9a: 87%). H NMR
(CDCl3): δ 1.73 (s, 6H, sC(CH3)dC(CH3)s), 2.34 (dd, J ) 4.9, 13.4
Hz, 1H, sCH2COOCH3), 2.72 (dd, J ) 9.0, 13.4 Hz, 1H, s
CH2COOCH3), 3.04 (d, J ) 15.9 Hz, 1H, sCH2CH(OH)Ph), 3.20 (d,
J ) 15.9 Hz, 1H, -CH2CH(OH)Ph), 3.70 (s, 3H, sOCH3), 4.82 (m,
1H, sCH2CH(OH)Ph), 7.30-7.41 (m, 5H, sPh). 13C NMR (CDCl3):
δ 19.12 (s, sC(CH3)dC(CH3)s), 19.73 (s, sC(CH3)dC(CH3)s),
40.15 (s), 45.23 (s), 52.09 (s), 72.52 (s, sCH2CH(OH)Ph), 125.91 (s,
Ph), 126.25 (s, sC(CH3)dC(CH3)s), 127.54 (s, Ph), 128.50 (s, Ph),
129.26 (s, sC(CH3)dC(CH3)s), 144.44 (s, ipso-Ph), 172.58 (s,
sCH2COOCH3). HRMS (CI) Calcd for C15H21O3 (M + H) 249.1491,
Found m/z 249.1483.
Reaction of a Mixture of 1b and 1b′ with TMSCl Followed by
Carbonylation: In a pressure tight NMR tube, a solution of a mixture
of 8b and 8b′ in 0.5 mL of C6D6 generated by the reaction of a mixture
of 1b and 1b′ (9.9 mg, 0.02 mmol) with TMSCl (2.2 mg, 0.02 mmol,
2.5 µL) was treated with carbon monoxide (5 atm). The solution
changed from red brown to light blue gradually and was quenched with
methanol to give the corresponding hydroxyester (9b: 70%). 1H NMR
(CDCl3): δ 2.52 (m, 2H, sCH2COOCH3), 3.07 (d, J ) 6.8 Hz, 2H,
sCH2CH(OH)Ph), 3.69 (s, 3H, sOCH3), 4.73 (t, J ) 6.2 Hz, 1H,
sCH2CH(OH)Ph), 5.60-5.78 (m, 2H, sCHdCHs), 7.28-7.37 (m,
5H, sPh). 13C NMR (CDCl3): δ 38.03 (s), 42.67 (s), 52.08 (s), 73.59
(s, sCH2CH(OH)Ph), 125.86 (s), 127.00 (s), 127.76 (s), 128.63 (s),
130.55 (s), 144.04 (s, ipso-Ph), 172.50 (s, sCH2COOCH3). HRMS
Calcd for C13H16O3 220.1099, Found m/z 220.1095.
Isolation of 1d: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
n
PCy3 (240 mg, 0.80 mmol), and 72.1 µL of PrCHO (57.7 mg, 0.80
mmol) in 5 mL of toluene was added 0.45 mL of 2,3-dimethyl-1,3-
butadiene (328.6 mg, 4.00 mmol) at room temperature. The solution
changed from orange to red. The reaction mixture was stirred for 1 h
followed by concentration in vacuo to give yellow solids (1d, 414 mg,
84%) as a mixture of two isomers (1d/1d′ ) 95/5), which might be
caused by the stereochemistry about the η3-allylnickel moiety and
alkoxy carbon. An analytical sample was prepared by recrystallization
from hexane at -20 °C. The structure in a solution was determined by
the NOE measurement between an Me group bound to C3 and an alkoxy
proton (2%). 1d: 1H NMR (C6D6): δ 1.08-1.96 (m, 46H, including
1H of NiCH2C(CH3) at δ 1.10, 3H of -CH2CH2CH3 at δ 1.13, 3H of
NiCH2 C(CH3)C(CH3) at δ 1.43 (d, J ) 2.3 Hz), 1H of CH2CH(nPr)-
ONi at δ 1.49, 1H of NiCH2C(CH3) at δ 1.58, 2H of -CH2CH2CH3 at
δ 1.66 and 2H of CH(CH2CH2CH3)ONi at δ 1.68), 2.31 (s, 3H,
NiCH2C(CH3)), 5.20 (m, 1H, CH(nPr)ONi). 31P NMR (C6D6) δ 42.07
(s). 13C NMR (C6D6) δ 15.5 (s, -CH2CH3), 20.6 (d, JCP ) 3.0 Hz,
NiCH2C(CH3)C(CH3)), 20.7 (s, -CH2CH3), 21.9 (s, NiCH2C(CH3)),
27.3 (s, Cy), 28.3 (d, JCP ) 1.5 Hz, Cy), 28.4 (d, JCP ) 1.5 Hz, Cy),
Isolation of 1c: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
PCy3 (240 mg, 0.80 mmol), and 81.3 µL of PhCHO (84.9 mg, 0.80
mmol) in 10 mL of toluene was added 0.40 mL of isoprene (273 mg,
4.00 mmol) at room temperature. The solution changed from dark red
to red. The reaction mixture was concentrated under a reduced pressure.
The residue was washed with pentane to give yellow solids (297 mg,
72%) as a mixture of three isomers (1c/1c′/1c′′ ) 10/76/14). 1c: 1H
NMR (C6D6): δ 1.34 (d, JHP ) 3.6 Hz, 3H, NiCH2CHC(CH3)), 5.49
(dd, J ) 7.2 Hz, 12.7 Hz, 1H, NiCH2CH), 6.31 (brd, J ) 6.5 Hz, 1H,
CH(Ph)ONi), 7.46 (t, J ) 7.6 Hz, 2H of meta-C6H5), 7.98 (d, J ) 7.6
Hz, 2H of ortho-C6H5). The other resonances are hidden by those of
1c′. 31P NMR (C6D6): δ 39.9 (s). 13C NMR (C6D6): δ 18.6 (d, JCP
)
1.5 Hz, NiCH2CHC(CH3)), 34.2 (d, JCP ) 17.5 Hz, Cy), 35.7 (d, JCP
) 6.8 Hz, NiCH2CH), 56.6 (d, JCP ) 2.3 Hz, -CH2CH(Ph)ONi), 97.3
30.7 (d, JCP ) 1.5 Hz, Cy), 31.0 (d, JCP ) 2.3 Hz, Cy), 33.3 (d, JCP )
6.8 Hz, NiCH2C(CH3)), 33.6 (d, JCP ) 16.7 Hz, Cy), 44.6 (s, -CH2-
CH2CH3), 48.1 (d, JCP ) 2.3 Hz, CH2CH(nPr)ONi), 93.2 (d, JCP ) 10.0
Hz, CH2CH(nPr)ONi), 103.0 (d, JCP ) 15.3 Hz, NiCH2C(CH3)C(CH3)),
(d, JCP ) 11.4 Hz, CH(Ph)ONi), 105.3 (s, NiCH2CH), 107.6 (d, JCP
)
13.7 Hz, NiCH2CHC(CH3), 126.2 (s, Ph), 127.4 (s, Ph), 153.7 (s, Ph).
9
J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006 7083

A R T I C L E S
Ogoshi et al.
113.0 (s, NiCH2C(CH3)). 1d′: 31P NMR (C6D6) δ 42.08 (s). The
by the column.1H NMR (CDCl3): δ 0.94 (t, J ) 7.1 Hz, 3H, sCH2-
CH2CH3), 1.47 (m, 4H, sCH2CH2CH3), 1.64 (s, 3H, sC(CH3)d
C(CH3)s), 1.70 (s, 3H, sC(CH3)dC(CH3)s), 2.08 (dd, J ) 3.7, 13.4
Hz, 1H, sCH2CH(OH)nPr), 2.15 (s, 3H, sCOCH3), 2.41 (dd, J ) 9.6,
13.4 Hz, 1H, sCH2CH(OH)nPr), 3.15 (d, J ) 16.6 Hz, 1H, sCH2-
COCH3), 3.30 (d, J ) 16.6 Hz, 1H, sCH2COCH3), 3.74 (m, 1H, s
CH2CH(OH)nPr). 13C NMR (CDCl3): δ 14.37 (s), 19.14 (s), 19.32 (s),
20.20 (s), 29.68 (s), 39.59 (s), 42.85 (s), 50.24 (s), 69.70 (s), 125.74
(s), 129.81 (s), 207.03 (s). HRMS (CI) Calcd for C12H23O2 (M + H)
199.1698, found m/z 199.1685.
Formation of 1e: To a solution of Ni(cod)2 (5.5 mg, 0.02 mmol),
PCy3 (5.6 mg, 0.02 mmol), and 14.6 µL of acetone (11.6 mg, 0.20
mmol) in 5 mL of C6D6 were added 11.3 µL of 2,3-dimethyl-1,3-
butadiene (16.4 mg, 0.20 mmol) at room temperature. The reaction
proceeded gradually to generate 1e for 4 h (94%). The reaction mixture
was concentrated under reduced pressure to regenerate Ni(cod)2 and
PCy3 (50%).
1
resonances of 1d′ in H and 13C spectra are hidden by those of 1d.
Anal. Calcd for C28H51O1P1Ni1 (a mixture of 1d and 1d′): C, 68.16;
H, 10.42. Found: C, 67.87; H, 10.48.
Reaction of a Mixture of 1d and 1d′ with Carbon Monoxide: A
pressure tight NMR tube containing a solution of 1d (19.7 mg, 0.04
mmol) in C6D6 (0.5 mL) was treated with carbon monoxide (5 atm).
The solution changed from orange to colorless immediately to give
the carbonylation products (85%) as a mixture of two isomers (3d/3d′
) 95/5). 3d: 1H NMR (CDCl3): δ 0.97 (t, J ) 6.8 Hz, 3H, sCH2-
CH2CH3), 1.43 (s, 3H, sC(CH3)(COOs)s), 1.47-1.78 (m, 4H), 1.83
(s, 3H, sC(CH3)dCH2), 2.09 (d, J ) 7.3 Hz, 2H, sCH2CH(nPr)Os),
4.47 (m, 1H, sCH2CH(nPr)Os), 5.00 (s, 1H, sC(CH3)dCH2, 5.03
(s, 1H, sC(CH3)dCH2). 13C NMR (CDCl3): δ 14.06 (s), 18.87 (s),
19.88 (s), 22.24 (s), 37.94 (s), 41.35 (s), 49.71 (s), 77.23 (hidden by
CDCl3 peak), 113.17 (s), 144.71 (s), 179.58 (s). 3d′: 1H NMR
(CDCl3): δ 2.44 (d, J ) 5.1 Hz, 1H, sCH2CH(nPr)Os), 2.48 (d, J )
5.1 Hz, 1H, sCH2CH(nPr)Os), 4.30 (m, 1H, sCH2CH(nPr)Os), 4.89
(s, 1H, sC(CH3)dCH2), 4.95 (s, 1H, sC(CH3)dCH2). The other
Attempt at Isolation of 1e by the General Method: To a solution
of Ni(cod)2 (220 mg, 0.80 mmol), PCy3 (240 mg, 0.80 mmol), and
0.59 mL of acetone (464 mg, 8.00 mmol) in 10 mL of toluene was
added 0.91 mL of 2,3-dimethyl-1,3-butadiene (657 mg, 8.00 mmol) at
room temperature. The solution changed from orange to red. The
reaction mixture was stirred for 4.5 h followed by concentration in
vacuo to regenerate Ni(cod)2 and PCy3 (420.5 mg, 91%).
1
resonances in H and 13C spectra are hidden by those of 3d. HRMS
Calcd for C11H18O2 182.1307, Found m/z 182.1316.
Isolation of 4d: To a solution of a mixture of 1d and 1d′ (394.7
mg, 0.8 mmol) in 10 mL of hexane was added ZnMe2 (0.8 mmol, 800
µL, 1 M/hexane) at room temperature. The reaction mixture was
concentrated under reduced pressure to give yellow solids (4d, 451.3
mg, 96%). 1H NMR (C6D6): δ -0.34 (d, JHP ) 4.4 Hz, 3H × 2, NiCH3
× 2), 0.27 (s, 3H, ZnCH3), 0.28 (s, 3H, ZnCH3), 1.13-2.05 (m, 45H
× 2, including 3H × 2 of -CH2CH2CH3 × 2 at δ 1.22 (t, J ) 7.2
Hz), 3H × 2 of NiCH2C(CH3)C(CH3) × 2 at δ 1.40, 1H × 2 of
NiCH2C(CH3) × 2 at δ 1.61, 1H × 2 of -CH2CH2CH3 × 2 at δ 1.89,
1H × 2 of -CH2CH2CH3 × 2 at δ 2.01 and 3H × 2 of NiCH2C-
(CH3)C(CH3) × 2 at δ 2.02 (s)), 2.32 (1H × 2, hidden by NiCH2C-
(CH3) peak), 2.33 (s, 1H × 2, NiCH2C(CH3) × 2), 2.44 (m, 1H × 2,
-CH2CH2CH3), 2.79 (m, 2H × 2, -CH2CH(nPr)O- × 2), 4.78 (brs,
1H × 2, -CH(nPr)O- × 2). 31P NMR (C6D6): δ 50.70 (s), 50.72 (s).
13C NMR (C6D6): δ -9.0 (s, ZnCH3), -8.7 (s, ZnCH3), -6.0 (d, JCP
) 3.0 Hz, NiCH3), -5.9 (d, JCP ) 3.8 Hz, NiCH3), 15.5 (s, -CH2CH3),
15.6 (s, -CH2CH3), 19.8 (s, -C(CH3)CH2CH(nPr)O-), 19.9 (s,
-C(CH3)CH2CH(nPr)O-), 20.7 (s, -CH2CH3), 20.8 (s, -CH2CH3),
23.0 (s, NiCH2C(CH3)- × 2), 27.3 (s, Cy), 28.3 (d, JCP ) 4.5 Hz,
Cy), 28.4 (d, JCP ) 4.5 Hz, Cy), 30.8 (s, Cy), 31.0 (s, Cy), 35.5 (s,
Cy), 35.7 (s, Cy), 42.9 (s, -CH2CH2CH3), 43.1 (s, -CH2CH2CH3),
46.8 (s, -CH2CH(nPr)O- × 2), 47.78 (s, NiCH2C(CH3)-), 47.80 (s,
NiCH2C(CH3)-), 75.4 (s, -CH(nPr)O-), 75.5 (s, -CH(nPr)O-), 79.1
(d, JCP ) 18.3 Hz, -C(CH3)CH2CH(nPr)O-), 79.3 (d, JCP ) 18.3 Hz,
-C(CH3)CH2CH(nPr)O-), 114.4 (s, NiCH2C(CH3)-), 114.5 (s,
NiCH2C(CH3)-). Anal. Calcd for C30H57O1P1Ni1Zn1: C, 61.19; H, 9.76.
Found: C, 60.64; H, 9.50.
Isolation of 1e by Reaction of 2a with Acetone: To a solution of
2a (503.4 mg, 1.0 mmol) in 30 mL of toluene was added acetone (10
mmol, 734.3 µL) at room temperature. The reaction mixture was stirred
for 4 day followed by concentration in vacuo. To a solution of the
residue in 30 mL of toluene was added acetone (1 mmol, 73.4 µL) at
room temperature. The reaction mixture was stirred for 4 day followed
by concentration under reduced pressure. The residue was washed with
hexane to give pink-yellow solids (1e, 326.2 mg, 65%). 1H NMR
(C6D6): δ 1.13-2.06 (m, 45H, including 1H of NiCH2C(CH3) at δ
1.18, 3H of NiCH2C(CH3)C(CH3) at δ 1.48 (d, J ) 3.3 Hz), 3H of
-CH2C(CH3)2ONi at δ 1.54, 1H of NiCH2C(CH3) at δ 1.59, 1H of
-CH2C(CH3)2ONi at δ 1.73 (dd, JHH ) 12.3 Hz and JHP ) 2.5 Hz)
and 3H of -CH2C(CH3)2ONi at 1.77), 2.39 (s, 3H, NiCH2C(CH3)),
2.74 (d, J ) 12.3 Hz, 1H, -CH2C(CH3)2ONi). 31P NMR (C6D6): δ
41.9 (s). 13C NMR (C6D6): δ 22.3 (s, NiCH2C(CH3)), 25.3 (d, JCP
)
2.3 Hz, NiCH2C(CH3)C(CH3)), 27.3 (s, Cy), 28.3 (d, JCP ) 10.7 Hz,
Cy), 30.7 (d, JCP ) 1.5 Hz, Cy), 30.9 (d, JCP ) 1.5 Hz, Cy), 33.5 (d,
JCP ) 16.8 Hz, Cy), 33.6 (d, JCP ) 6.1 Hz, NiCH2C(CH3)), 36.2 (s,
-CH2C(CH3)2ONi), 37.3 (s, -CH2C(CH3)2ONi), 52.1 (d, JCP ) 2.3
Hz, -CH2C(CH3)2ONi), 97.2 (d, JCP ) 10.7 Hz, -CH2C(CH3)2ONi),
101.6 (d, JCP ) 16.0 Hz, NiCH2C(CH3)C(CH3)), 114.2 (s, NiCH2C(CH3)).
Anal. Calcd for C27H49O1P1Ni1: C, 67.65; H, 10.30. Found: C, 66.81;
H, 10.23.
Reaction of 1e with Carbon Monoxide: A pressure tight NMR
tube containing a solution of 1e (9.6 mg, 0.02 mmol) in C6D6 (0.5
mL) was treated with carbon monoxide (5 atm). The solution changed
from orange to colorless immediately to give the carbonylation products
Reductive Elimination from 4d: A solution of 4d (11.8 mg, 0.02
mmol) in C6D6 (0.5 mL) was heated at 60 °C for 70 h. The solution
changed from yellow to dark brown, and black solids precipitated. The
decomposition of 4d was confirmed by 31P NMR spectrum. 5d was
identified as an alcohol by protonation followed by separation from
1
(3e: 8%). H NMR (CDCl3): δ 1.41 (s, 3H, sCH3), 1.43 (s, 3H, s
CH3), 1.46 (s, 3H, sCH3), 1.82 (s, 3H, sC(CH3)dCH2), 1.94 (d, J )
13.4 Hz, 1H, sCH2C(CH3)2Os), 2.40 (d, J ) 13.4 Hz, 1H, sCH2C-
(CH3)2Os), 4.96 (s, 1H, sC(CH3)dCH2), 5.01 (s, 1H, sC(CH3)d
CH2). 13C NMR (CDCl3): δ 19.60 (s), 25.44 (s), 28.49 (s), 30.41 (s),
47.23 (s), 51.46 (s), 81.41 (s), 112.89 (s), 145.38 (s), 179.39 (s). HRMS
Calcd for C10H16O2 168.1150, Found m/z 168.1146.
1
nickel compound by the column. H NMR (CDCl3): δ 0.96 (m, 6H,
sCH2CH2CH3 and dC(CH3)CH2CH3), 1.45 (m, 4H, sCH2CH2CH3),
1.69 (s, 6H, sC(CH3)dC(CH3)s), 2.06 (m, 3H, 1H of sCH2CH-
(OH)nPr and 2H of dC(CH3)CH2CH3), 2.34 (dd, J ) 9.3, 13.4 Hz,
1H, sCH2CH(OH)nPr), 3.74 (m, 1H, sCH2CH(OH)nPr). 13C NMR
(CDCl3): δ 12.85 (s), 14.37 (s), 18.21 (s), 18.36 (s), 19.30 (s), 27.99
(s), 39.46 (s), 42.83 (s), 69.80 (s), 124.08 (s), 134.68 (s). HRMS Calcd
for C11H22O1 170.1671, Found m/z 170.1670.
Isolation of 8e: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
PCy3 (240 mg, 0.80 mmol), 0.59 mL of acetone (465 mg, 8.00 mmol),
and 0.90 mL of 2,3-dimethyl-1,3-butadiene (657 mg, 8.00 mmol) in 5
mL of toluene were added 102 µL of chlorotrimethylsilane (86.9 mg,
0.80 mmol) at room temperature. The solution changed from red to
dark red. The reaction mixture was stirred for 4 h followed by
Reaction of 4d with Carbon Monoxide: A pressure tight NMR
tube containing a C6D6 (0.5 mL) solution of 4d (23.6 mg, 0.04 mmol)
was treated with carbon monoxide (5 atm). The solution changed from
orange to colorless immediately to give 7d and Ni(CO)3(PCy3) (86%).
7d was identified as an alcohol by protonation followed by separation
1
concentration in vacuo to give dark red solids (8e, 463 mg, 98%). H
NMR (C6D6): δ 0.16 (s, 9H, -OSi(CH3)3), 1.11-2.07 (m, 44H,
9
7084 J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006

Reaction of 1,3-Diene and Aldehyde/Ketone on Ni(0)
A R T I C L E S
including 3H of -C(CH3)2OTMS at δ 1.26, 3H of -C(CH3)2OTMS
at δ 1.27, 1H of NiCH2C(CH3) at δ 1.62, 3H of NiCH2C(CH3)C(CH3)
at δ 1.68 (d, J ) 2.4 Hz) and 1H of NiCH2C(CH3) at δ 2.07), 2.11 (s,
3H, NiCH2C(CH3)), 2.35 (d, J ) 14.9 Hz, 1H, -CH2C(CH3)2OTMS),
2.48 (dd, J ) 14.9, 1.5 Hz, 1H, -CH2C(CH3)2OTMS). 31P NMR
(C6D6): δ 42.6 (s). 13C NMR (C6D6): δ 3.07 (s, -OSi(CH3)3), 22.27
(s, NiCH2C(CH3)), 23.06 (d, JCP ) 3.0 Hz, NiCH2C(CH3)C(CH3)), 27.2
(s, Cy), 28.2 (s, Cy), 28.3 (s, Cy), 30.8 (s, Cy), 30.9 (s, Cy), 31.17 (s,
-C(CH3)2OTMS), 32.41 (s, -C(CH3)2OTMS), 34.4 (d, JCP ) 19.0 Hz,
Cy), 39.33 (d, JCP ) 6.9 Hz, NiCH2C(CH3)), 51.01 (d, JCP ) 3.0 Hz,
-CH2C(CH3)2OTMS), 74.51 (d, JCP ) 4.6 Hz, -CH2C(CH3)2OTMS),
100.54 (d, JCP ) 16.1 Hz, NiCH2C(CH3)C(CH3)), 114.22 (s, NiCH2C-
(CH3)). An analytical sample was not obtained due to gradual
decomposition in a solution.
of -CH2CH2CH2- at δ 2.02), 2.26 (m, 1H, -CH2CH2CH2-), 2.32
(s, 3H, NiCH2C(CH3)C(CH3)), 2.33 (m, 1H, -CH2CH2CH2-), 2.38
(m, 1H, -CH2CH2CH2-), 2.69 (d, J ) 12.4 Hz, 1H, -CH2C(cBu)-
ONi), 2.77 (m, 1H, -CH2CH2CH2-). 31P NMR (C6D6): δ 42.2 (s).
13C NMR (C6D6): δ 14.7 (s, -CH2CH2CH2-), 21.9 (s, NiCH2C(CH3)),
23.2 (s, NiCH2C(CH3)C(CH3)), 27.2 (s, Cy), 28.2 (d, JCP ) 1.5 Hz,
Cy), 28.3 (d, JCP ) 1.5 Hz, Cy), 30.7 (d, JCP ) 1.5 Hz, Cy), 30.8 (d,
JCP ) 2.3 Hz, Cy), 33.1 (d, JCP ) 6.1 Hz, NiCH2C(CH3)), 33.5 (d, JCP
) 16.7 Hz, Cy), 43.5 (s, -CH2CH2CH2-), 44.0 (s, -CH2CH2CH2-),
50.5 (d, JCP ) 2.3 Hz, -CH2C(cBu)ONi), 102.0 (d, JCP ) 10.7 Hz,
-CH2C(cBu)ONi), 103.7 (d, JCP ) 15.3 Hz, NiCH2C(CH3)C(CH3)),
114.1 (s, NiCH2C(CH3)). Anal. Calcd for C28H49O1P1Ni1: C, 68.44;
H, 10.05. Found: C, 67.90; H, 9.97.
Reaction of 1g with Carbon Monoxide: A pressure tight NMR
tube containing a solution of 1g (19.6 mg, 0.04 mmol) in C6D6 (0.5
mL) was treated with carbon monoxide (5 atm). The solution changed
from orange to colorless immediately to give the carbonylation products
Reaction of 8e with Carbon Monoxide: A pressure tight NMR
tube containing a solution of 8e (23.5 mg, 0.04 mmol) in C6D6 (0.5
mL) was treated with carbon monoxide (5 atm). The solution changed
from red to light blue gradually. The reaction mixture was quenched
with methanol to give an ester. It was isolated as a hydroxyester (9e:
74%) by a colum (silica). 1H NMR (CDCl3): δ 1.25 (s, 6H, sC(CH3)2-
OH), 1.77 (s, 3H, sC(CH3)dC(CH3)s), 1.79 (s, 3H, sC(CH3)d
C(CH3)s), 2.34 (s, 2H, sCH2COOCH3), 3.12 (s, 2H, sCH2C(CH3)2-
OH), 3.69 (s, 3H, sOCH3). 13C NMR (CDCl3): δ 20.63 (s, sC(CH3)d
C(CH3)s), 21.69 (s, sC(CH3)dC(CH3)s), 30.32 (s, sC(CH3)2OH),
40.20 (s), 47.92 (s), 51.98 (s), 72.62 (s), 126.29 (s, vinyl), 129.12 (s,
vinyl), 172.65 (s, sCH2COOCH3). HRMS (CI) Calcd for C11H21O3
(M + H) 201.1491, found m/z 201.1492.
Isolation of 1f: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
PCy3 (240 mg, 0.80 mmol), and benzophenone (146 mg, 0.80 mmol)
in 6 mL of toluene and 1 mL of benzene was added 2,3-dibenzyl-1,3-
butadiene (188 mg, 0.80 mmol) at room temperature. The solution
changed from orange to red. The reaction mixture was stirred for 10
min followed by concentration in vacuo to give yellow solids (1f, 585
mg, 97%). An analytical sample and a single crystal for X-ray
diffraction analysis were prepared by recrystallization from hexane at
-20 °C. 1H NMR (C6D6): δ 1.38 (s, 1H, NiCH2C(CH2Ph)C(CH2Ph)),
1.10-2.10 (m, 34H, including 1H of NiCH2C(CH2Ph)C(CH2Ph) at δ
1.80), 2.47 (d, J ) 14.4 Hz, 1H, NiCH2C(CH2Ph)C(CH2Ph)), 2.85 (d,
J ) 10.0 Hz, 1H, CH2C(Ph)2ONi), 2.97 (d, J ) 12.0 Hz, 1H,
NiCH2C(CH2Ph)C(CH2Ph)), 3.37 (d, J ) 12.8 Hz, 1H, CH2C(Ph)2-
ONi), 3.57 (d, J ) 14.4 Hz, 1H, NiCH2C(CH2Ph)), 4.43 (d, J ) 14.4
Hz, 1H, NiCH2C(CH2Ph)), 6.75 (d, J ) 6.0 Hz, 2H, Ph), 7.00-7.25
(m, 12H, Ph), 7.37 (t, J ) 7.6 Hz, 2H, Ph), 7.66 (d, J ) 7.2 Hz, 2H,
Ph), 8.00 (d, J ) 7.6 Hz, 2H, Ph). 31P NMR (C6D6): δ 37.9 (s). 13C
NMR (C6D6): δ 27.2 (s, Cy), 28.3 (d, JCP ) 3.8 Hz, Cy), 28.4 (d, JCP
) 4.6 Hz, Cy), 30.5 (s, Cy), 31.2 (d, JCP ) 1.5 Hz, Cy), 34.1 (d, JCP
) 16.7 Hz, Cy), 36.9 (d, JCP ) 24.4 Hz, NiCH2C(CH2Ph)), 39.1 (s,
NiCH2C(CH2Ph)C(CH2Ph)), 42.5 (s, NiCH2C(CH2Ph)), 48.8 (s,
CH2C(Ph)2ONi), 103.0 (d, JCP ) 42.8 Hz, CH2C(Ph)2ONi), 103.5 (d,
JCP ) 67.2 Hz, NiCH2C(CH2Ph)C(CH2Ph)), 125.4 (s, Ph), 125.7 (s,
Ph), 126.0 (s, Ph), 126.4 (s, Ph), 126.8 (s, Ph), 127.5 (s, Ph), 127.8 (s,
Ph), 127.9 (s, Ph), 128.5 (s, Ph), 129.0 (s, Ph), 129.80 (s, Ph), 129.83
(s, Ph), 139.2 (d, JCP ) 12.0 Hz, NiCH2C(CH2Ph-ipso)), 140.7 (s, Ph-
ipso), 156.1 (s, Ph-ipso), 157.7 (s, Ph-ipso). Anal. Calcd for
C49H61O1P1Ni1: C, 77.88; H, 8.14. Found: C, 77.63; H, 8.21.
1
(3g: 38%). H NMR (CDCl3): δ 1.37 (s, 3H, sC(CH3)(COOs)s),
1.68 (m, 1H, sCH2CH2CH2s), 1.81 (s, 3H, sC(CH3)dCH2),
1.87 (m, 1H, sCH2CH2CH2s), 2.19 (d, J ) 13.4 Hz, 1H, sCH2CH-
(Buc)Os), 2.16 (m, 2H, sCH2CH2CH2s), 2.41 (m, 1H, sCH2-
CH2CH2s), 2.57 (m, 1H, sCH2CH2CH2s), 2.59 (d, J ) 13.4 Hz,
1H, sCH2CH(Buc)Os), 4.93 (s, 2H, sC(CH3)dCH2). 13C NMR
(CDCl3): δ 12.79 (s, sCH2CH2CH2s), 19.39 (s, sC(CH3)dCH2),
23.41 (s, sC(CH3)(COOs)s), 35.63 (s, sCH2CH2CH2s), 35.85 (s,
sCH2CH2CH2s), 46.12 (s, sCH2CH(cBu)Os), 51.02 (s, sC(CH3)-
(COOs)s), 82.82 (s, sCH2CH(cBu)Os), 112.98 (s, sC(CH3)dCH2),
144.32 (s, sC(CH3)dCH2), 179.29 (s, sCOOs). HRMS Calcd for
C11H16O2 180.1150, Found m/z 180.1139.
Isolation of 1h: To a solution of Ni(cod)2 (220 mg, 0.80 mmol),
PCy3 (240 mg, 0.80 mmol), and 96.1 mg of styrene oxide (91.2 µL,
0.80 mmol) in 10 mL of toluene were added 328.6 mg of 2,3-dimethyl-
1,3-butadiene (0.45 mL, 4.00 mmol) at 60 °C. The solution changed
from orange to red. The reaction mixture was stirred for 18 h followed
by concentration in vacuo. The residue was washed with hexane to
1
give orange solids (1h: 312 mg, 88%). H NMR (C6D6): δ 1.00-
2.00 (m, 39H, including 1H of NiCH2C(CH3) at δ 1.11, 3H of NiCH2C-
(CH3)C(CH3) at δ 1.32 (d, J ) 2.8 Hz), 1H of CH2CH(CH2Ph)ONi at
δ 1.37 and 1H of NiCH2C(CH3) at δ 1.57), 2.21 (s, 3H, NiCH2C-
(CH3)), 2.39 (t, J ) 10.8 Hz, 1H, CH2CH(CH2Ph)ONi), 2.98 (m, 2H,
CH(CH2Ph)ONi), 5.36 (m, 1H, CH(CH2Ph)ONi), 7.11 (1H of para in
C6H5, hidden by C6D6 peak), 7.27 (t, J ) 7.6 Hz, 2H of meta in C6H5),
7.48 (d, J ) 7.2 Hz, 2H of ortho in C6H5). 31P NMR (C6D6) δ 42.4 (s).
13C NMR (C6D6) δ 20.5 (d, JCP ) 3.0 Hz, NiCH2C(CH3)C(CH3)), 21.8
(s, NiCH2C(CH3)), 27.2 (s, Cy), 28.1 (s, Cy), 28.3 (s, Cy), 30.7 (d, JCP
) 1.5 Hz, Cy), 30.8 (d, JCP ) 1.5 Hz, Cy), 33.4 (d, JCP ) 3.0 Hz,
NiCH2C(CH3)), 33.5 (d, JCP ) 17.5 Hz, Cy), 47.6 (d, JCP ) 2.3 Hz,
CH2CH(CH2Ph)ONi), 49.0 (s, -CH2Ph), 94.7 (d, JCP ) 10.7 Hz,
CH2CH(CH2Ph)ONi), 102.6 (d, JCP ) 14.5 Hz, NiCH2C(CH3)C(CH3)),
113.2 (s, NiCH2C(CH3)), 125.6 (s, Ph-para), 127.6 (Ph-meta), 130.5
(Ph-ortho), 143.4 (s, Ph-ipso).
Reaction of 1h with Carbon Monoxide: A pressure tight NMR
tube containing C6D6 (0.5 mL) solution of 1h (10.8 mg, 0.02 mmol)
was treated with carbon monoxide (5 atm). The solution changed
from orange to light yellow immediately to give the carbonyl-
ation product (3h: 90%). 1H NMR (CDCl3): δ 1.40 (s, 3H, sC(CH3)-
(COOs)s), 1.77 (s, 3H, sC(CH3)dCH2), 2.01 (m, 1H, sCH2CH-
(CH2Ph)Os), 2.20 (dd, J ) 9.2, 6.5 Hz, 1H, sCH2CH(CH2Ph)Os),
2.94 (m, 1H, sCH2Ph), 3.11 (dd, J ) 7.0, 6.5 Hz, 1H, sCH2Ph), 4.70
(m, 1H, sCH2CH(CH2Ph)Os), 5.00 (d, J ) 1.0 Hz, 1H, sC(CH3)d
CH2), 5.02 (s, 1H, sC(CH3)dCH2), 7.23-7.36 (m, 5H, Ph). 13C NMR
(CDCl3): δ 19.70 (s), 22.22 (s), 40.33 (s), 41.44 (s), 49.70 (s), 77.54
(s), 113.30 (s), 127.18 (s), 128.83 (s), 129.72 (s), 136.18 (s), 144.57
(s), 179.34(s). HRMS Calcd for C15H18O2 230.1307, Found m/z
230.1289.
Isolation of 1g: To a solution of Ni(cod)2 (275 mg, 1.0 mmol), PCy3
(289 mg, 1.0 mmol), and 74.7 µL of cyclobutanone (70.1 mg, 1.0 mmol)
in 10 mL of toluene were added 411 mg of 2,3-dimethyl-1,3-butadiene
(0.57 mL, 5.0 mmol) at room temperature. The solution changed from
orange to dark orange. The reaction mixture was stirred for 4 h followed
by concentration in vacuo to give yellow solids (1g, 376 mg, 76%). A
single crystal for X-ray diffraction analysis was prepared by recrys-
tallization from hexane at -20 °C. 1H NMR (C6D6): δ 1.10-2.20 (m,
41H, including 1H of NiCH2C(CH3) at δ 1.22, 3H of NiCH2C(CH3)C-
(CH3) at δ 1.43 (d, J ) 8.4 Hz), 1H of NiCH2C(CH3) at δ 1.56, 1H of
-CH2CH2CH2- at δ 1.68, 1H of -CH2C(cBu)ONi at δ 1.91 and 1H
9
J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006 7085

A R T I C L E S
Ogoshi et al.
Isomerization of Styrene Oxide: To a solution of Ni(cod)2 (5.5
mg, 0.02 mmol) and PCy3 (11.2 mg, 0.04 mmol) in 0.5 mL of C6D6
were added 2.3 µL of styrene oxide (2.4 mg, 0.02 mmol) at 60 °C.
The solution changed from light yellow to orange. The reaction
proceeded to give Ni(η2-PhCH2CHO)(PCy3) (60%, 5 h).
Research from Ministry of Education, Science, and Culture,
Japan, is gratefully acknowledged.
Supporting Information Available: Crystallographic infor-
mation files (CIF/PDF) for 1a, 1b, 1e, 1f, and 1g. This material
is available free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. Partial support of this work through the
Sumitomo Foundation (S.O.), Grants-in-Aid for Scientific
JA060580L
9
7086 J. AM. CHEM. SOC. VOL. 128, NO. 21, 2006