Ru3(CO)12-Catalyzed Reaction of Pyridylbenzenes with Monoxide and Olefins. Carbonylation at a C-H Bond in the Benzene Ring

Article abstract of DOI:10.1021/jo970131r

A ruthenium-catalyzed carbonylation at a C-H bond in a benzene ring is described. The reaction of pyridylbenzenes with CO (20 atm) and ethylene in toluene at 160°C in the presence of a catalytic amount of Ru₃(CO)₁₂ results in propionylation at an ortho C-H bond in the benzene ring. Carbonylation does not occur at the pyridine ring, although this is necessary as a directing group to promote the reaction. Olefins such as trimethylvinylsilane and tert-butylethylene in place of ethylene can also be used in this reaction, however 1-hexene, cyclohexene, allyltrimethylsilane, styrene, methyl methacrylate, vinyl acetate, triethoxyvinylsilane, and isopropenyltrimethylsilane do not afford the coupling products. Transition metal complexes, other than ruthenium carbonyl, examined thus far, do not show catalytic activity. In the reaction of meto-substituted pyridylbenzenes, such as those having Me, OMe, CF₃, and COOMe group at the meta position in the benzene ring, carbonylation takes place at the less hindered C-H bond exclusively, irrespective of the electronic nature of the substituents. It is apparent that steric factors are more important for the control of regioselectivity. The reaction is also applicable to naphthyl and thienyl rings. Six-membered heterocycles, such as 2-pyrimidine and 4-pyrimidine, are also effective directing groups for carbonylation at a C-H bond in the benzene ring. The present reaction represents the first, effective catalytic carbonylation reaction involving cleavage of the benzene C-H bond.

Full text of DOI:10.1021/jo970131r

2
604
J . Org. Chem. 1997, 62, 2604-2610
Ru
3
(CO)12-Ca ta lyzed Rea ction of P yr id ylben zen es w ith Ca r bon
Mon oxid e a n d Olefin s. Ca r bon yla tion a t a C-H Bon d in th e
Ben zen e Rin g
Naoto Chatani, Yutaka Ie, Fumitoshi Kakiuchi, and Shinji Murai*
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita Osaka 565, J apan
Received J anuary 24, 1997X
A ruthenium-catalyzed carbonylation at a C-H bond in a benzene ring is described. The reaction
of pyridylbenzenes with CO (20 atm) and ethylene in toluene at 160 °C in the presence of a catalytic
amount of Ru (CO)12 results in propionylation at an ortho C-H bond in the benzene ring.
3
Carbonylation does not occur at the pyridine ring, although this is necessary as a directing group
to promote the reaction. Olefins such as trimethylvinylsilane and tert-butylethylene in place of
ethylene can also be used in this reaction, however 1-hexene, cyclohexene, allyltrimethylsilane,
styrene, methyl methacrylate, vinyl acetate, triethoxyvinylsilane, and isopropenyltrimethylsilane
do not afford the coupling products. Transition metal complexes, other than ruthenium carbonyl,
examined thus far, do not show catalytic activity. In the reaction of meta-substituted pyridylben-
3
zenes, such as those having Me, OMe, CF , and COOMe group at the meta position in the benzene
ring, carbonylation takes place at the less hindered C-H bond exclusively, irrespective of the
electronic nature of the substituents. It is apparent that steric factors are more important for the
control of regioselectivity. The reaction is also applicable to naphthyl and thienyl rings.
Six-membered heterocycles, such as 2-pyrimidine and 4-pyrimidine, are also effective directing
groups for carbonylation at a C-H bond in the benzene ring. The present reaction represents the
first, effective catalytic carbonylation reaction involving cleavage of the benzene C-H bond.
Transition-metal-catalyzed carbonylation of a benzene
benzene with ethylene under CO.11 Eisenberg reported
that IrH (CO)(dppe) and RhCl(CO)(PPh promoted the
carbonylation of benzene by photoirradiation to give
ring represents a useful synthetic route for the production
3
3 2
)
1
of aromatic carbonyl compounds. A variety of com-
2
3
4
12
pounds, such as PhI, PhOTf, PhN
2
BF
4
, PPh
4
Cl, (PhS)
2
,
benzaldehyde.
(PMe was much more effective for the irradiation-
catalyzed carbonylation of benzene.
Later Tanaka found that RhCl(CO)-
4
5
6
7
(
PhSe)
2
, PhB(OH)
2
, PhHg(OAc), PhTl(O
Pb,8 have been used as starting materials for the
2
CCF
3
)
2
, and
3 2
)
14
Ph
4
In contrast to a
transition-metal-catalyzed carbonylation of a benzene
ring. These reactions involve cleavage of C-I, C-O,
C-N, C-P, C-S, C-Se, C-B, C-Hg, C-Tl, and C-Pb
bonds, respectively, although the mechanism of cleavage
of these bonds by transition metals is not the same for
each case. Carbonylation of a benzene ring involving
C-H bond fission has also been extensively studied. The
reactions can be classified into two types, depending on
the mechanism of cleavage of the C-H bond: (i) oxidative
addition (or its equivalent) of the C-H bond to a
transition metal and (ii) electrophilic substitution at the
benzene ring, heteroaromatic rings are known to undergo
facile carbonylation reactions. Catalytic carbonylation
of pyridine rings involving the cleavage of a C-H bond
R to the ring nitrogen was reported by Moore.1 We also
found that carbonylation at a 4-position C-H bond in 1,2-
disubstituted imidazole derivatives is achieved by the
5
1
6
3
presence of a catalytic amount of Ru (CO)12.
To attain both high efficiency and high regioselectivity
in the cleavage of a C-H bond in a benzene ring, the
presence of a directing group17 at an appropriate position
is effective, in order to position the metal close to the
benzene ring by a transition metal complex. Many
(
9) For Pd(II)-catalyzed carbonylation of a benzene ring, see: Fuji-
examples have been reported for the latter case.9
,10
In
wara, Y.; Kawauchi, T.; Taniguchi, H. J . Chem. Soc., Chem. Commun.
1980, 220. Taniguchi, Y.; Yamaoka, Y.; Nakata, K.; Takai, K.;
Fujiwara, Y. Chem. Lett. 1995, 345. For
Fujiwara, Y.; Takaki, K.; Taniguchi, Y. Synlett 1996, 591.
(10) For recent examples of transition metal-catalyzed carbonylative
cyclization, see: J oh, T.; Doyama, K.; Fujiwara, K.; Maeshima, K.;
Takahashi, S. Organometallics 1991, 10, 508. Ishii, Y.; Hidai, M. J .
Organomet. Chem. 1992, 428, 279. Takeuchi, R.; Yasue, H. J . Org.
Chem. 1993, 58, 5386. Kokubo, K.; Matsumasa, K.; Miura, M.;
Nomura, M. J . Org. Chem. 1996, 61, 6941.
contrast, examples of the former type are rare. Hong and
Yamasaki reported that propiophenone was obtained as
a minor product in the Rh (CO)12-catalyzed reaction of
4
a recent review, see:
X
Abstract published in Advance ACS Abstracts, March 15, 1997.
(1) For recent reviews on carbonylation, see: Colquhoun, H. M.;
Thompson, D. J .; Twigg, M. V. Carbonylation; Plenum Press: New
York, 1991. Tkatchenko, I. Comprehensive Organometallic Chemistry;
Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press:
Oxford, 1982; pp 101-223.
(11) Hong, P.; Yamazaki, H. Chem. Lett. 1979, 1335.
(12) Fisher, B. J .; Eisenberg, R. Organometallics 1983, 2, 764.
Kunin, A. J .; Eisenberg, R. J . Am. Chem. Soc. 1986, 108, 535. Kunin,
A. J .; Eisenberg, R. Organometallics 1988, 7, 2124. Gordon, E. M.;
Eisenberg, R. J . Mol. Catal. 1988, 45, 57.
(
2) Nagira, K.; Kikukawa, K.; Wada, F.; Matsuda, T. J . Org. Chem.
1
980, 45, 2365.
(
(
3) Sakamoto, M.; Shimizu, I.; Yamamoto, A. Chem. Lett. 1995, 1101.
4) Antebi, S.; Alper, H. Tetrahedron Lett. 1985, 26, 2609. Uemura,
(13) Sakakura, T.; Tanaka, M. Chem. Lett. 1987, 249. Sakakura,
T.; Tanaka, M. J . Chem. Soc., Chem. Commun. 1987, 758. Sakakura,
T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J . Am. Chem. Soc.
1990, 112, 7221.
S.; Takahashi, H.; Ohe, K.; Sugita, N. J . Organomet. Chem. 1989, 361,
3.
6
(
5) Miyaura, N.; Suzuki, A. Chem. Lett. 1981, 879. Cho, C. S.; Ohe,
K.; Uemura, S. J . Organomet. Chem. 1995, 496, 221.
6) Barlow, L. R.; Davidson, J . M. Chem. Ind. 1965, 1656. Heck, R.
F. J . Am. Chem. Soc. 1986, 90, 5546.
7) Larock, R. C.; Fellows, C. A. J . Org. Chem. 1980, 45, 363. Larock,
R. C.; Fellows, C. A. J . Am. Chem. Soc. 1982, 104, 1900.
8) Henry, P. M. Tetrahedron Lett. 1968, 2285.
(14) Boyd, S. E.; Field, L. D.; Partridge, M. G. J . Am. Chem. Soc.
1994, 116, 9492. Rosini, G. P.; Boese, W. T.; Goldman, A. S. J . Am.
Chem. Soc. 1994, 116, 9498.
(15) Moore, E.; Pretzer, W. R.; O’Connell, T. J .; Harris, J .; LaBounty,
L.; Chou, L.; Grimmer, S. S. J . Am. Chem. Soc. 1992, 114, 5888.
(16) Chatani, N.; Fukuyama, T.; Kakiuchi, F.; Murai, S. J . Am.
Chem. Soc. 1996, 118, 493.
(
(
(
S0022-3263(97)00131-X CCC: $14.00 © 1997 American Chemical Society

Ru
3
(CO)12-Catalyzed Carbonylation of Pyridylbenzenes
J . Org. Chem., Vol. 62, No. 8, 1997 2605
Sch em e 1
Prolonged reaction times (40 h) gave 3a as a main
product in 62% yield, along with 2a in 14% yield. The
catalytic activity of other complexes was then examined.
Complexes such as RhCl(PPh
3 3 2 2 6
) , [RhCl(CO) ] , Rh (CO)16
and Ir (CO)12 proved to be totally inactive.
4
C-H bond (Scheme 1). Indeed, several functional groups,
1
8
19
20,21
22
such as ketones, esters, pyridine,
diazo, and
imine23 have been found to promote C-C bond formation
with the regioselective cleavage of C-H bonds. We wish
to report that carbonylation at a C-H bond in the
3
benzene ring takes place during the Ru (CO)12-catalyzed
reaction of pyridylbenzenes with CO and olefins. The
pyridine ring has a dramatic effect on both reactivity and
selectivity on the carbonylation at a C-H bond in the
benzene ring. The present reaction represents the first,
effective catalytic carbonylation reaction involving cleav-
age of the benzene C-H bond.
The reaction of 1 with 3,3-dimethylbutene was very
slow, even when 0.1 mmol of Ru (CO)12 was used, but
interestingly, the mono coupling product 2b was obtained
as the sole product (34% yield). A reaction with trim-
ethylvinylsilane gave 2c in 50% yield, along with 2a in
3
Resu lts a n d Discu ssion
1
4% yield. Two possibilities exist for the formation of
The reaction of 2-phenylpyridine (1, 2 mmol) with
ethylene (initial pressure 7 atm at 25 °C in 50-mL
stainless autoclave) at 20 atm (initial pressure at 25 °C)
ethyl ketone 2a for trimethylvinylsilane: (1) protodesi-
lylation of the regioisomer of 2c (R-silylethyl ketone) or
(2) the coupling of 1, CO, and ethylene, which could be
formed by silyl group scrambling of the starting vinyl-
silane.24 Although we have no detailed experimental
evidence for the mechanism of the formation of ethyl
ketone, the latter seems to be the more reasonable.
When butyl vinyl ether was used as the olefin, 2a was
also obtained in 30% yield as the sole product, and no
corresponding product 2d was detectable. Reaction of 1
with CO and olefins, such as 1-hexene, cyclohexene,
allyltrimethylsilane, styrene, methyl methacrylate, vinyl
acetate, triethoxyvinylsilane, and isopropenyltrimethyl-
silane did not afford the coupling products, and 1 was
recovered.
3
of CO at 160 °C in toluene in the presence of Ru (CO)12
(
(
0.05 mmol) for 20 h gave 2-(2-propionylphenyl)pyridine
2a ) in 51% isolated yield and 2-(2,6-dipropionylphenyl)-
pyridine (3a ) in 31% isolated yield (eq 1). The benzene
C-H bond reacted more rapidly. No carbonylation
occurred at a C-H bond R to the aromatic nitrogen,
3
although Ru (CO)12 is known to catalyze the coupling of
1
5
pyridine, CO, and olefins. Carbonylation does not occur
at a meta C-H bond or at a para C-H bond. The
reaction proceeded beyond the mono propionylation.
(17) Bruce, M. I. Angew. Chem., Int. Ed. Engl. 1977, 16, 73.
Newkome, G. R.; Puckett, W. E.; Gupta, V. K.; Kiefer, G. E. Chem.
Rev. 1986, 86, 451. Ryabov, A. D. Chem. Rev. 1990, 90, 403.
(18) (a) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani,
A.; Sonoda, M.; Chatani, N. Nature 1993, 366, 529. (b) Murai, S.;
Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.;
Chatani, N. Pure Appl. Chem. 1994, 66, 1527. (c) Tapsak, M. A.;
Weber, W. P. Polym. Bull. 1994, 33, 417. (d) Guo, H.; Weber, W. P.
Polym. Bull. 1994, 32, 525. (e) Murai, S.; Kakiuchi, F.; Sekine, S.;
Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Bull. Chem. Soc.
J pn. 1995, 68, 62. (f) Guo, H.; Tapsak, M. A.; Weber, W. P. Polym.
Bull. 1995, 34, 49. (g) Kakiuchi, F.; Tanaka, Y.; Sato, T.; Chatani, N.;
Murai, S. Chem. Lett. 1995, 679. (h) Kakiuchi, F.; Yamamoto, Y.;
Chatani, N.; Murai, S. Chem. Lett. 1995, 781. (i) Sonoda, M.; Kakiuchi,
F.; Chatani, N.; Murai, S. J . Organomet. Chem. 1995, 504, 151. (j)
Guo, H.; Weber, W. P. Polym. Bull. 1995, 35, 259. (k) Guo, H.; Tapsak,
M. A.; Weber, W. P. Macromolecules 1995, 28, 4714, (l) Wang, G.; Guo,
H.; Weber, W. P. J . Organomet. Chem. 1996, 521, 351.
A cyclometalated complex, such as 4, would be expected
to play a key role for the formation of 2. While no report
of a stoichiometric reaction of 1 with Ru (CO)12 has yet
3
(
19) Trost, B. M.; Imi, K.; Davies, I. W. J . Am. Chem. Soc. 1995,
17, 5371. Sonoda, M.; Kakiuchi, F.; Chatani, N.; Murai, S. Chem.
Lett. 1996, 109.
20) Usefulness of a pyridine ring as a directing group for formation
of C-C bond has been described. Murai, S. J . Synth. Org. Chem. J pn.
994, 52, 992.
21) Lim, Y.-G.; Kim, Y. H.; Kang, J .-B. J . Chem. Soc., Chem.
1
appeared, the related cyclometalated mononuclear ru-
thenium complexes were isolated as a result of a reaction
(
1
25
26
of a benzaldehyde imine or a benzo[h]quinoline with
(
Commun. 1994, 2267. Lim, Y.-G.; Kim, Y. H.; Kang, J .-B. J . Chem.
Soc., Perkin Trans. 1 1996, 2201. Lim, Y.-G.; Kang, J .-B.; Kim, Y. H.
J . Chem. Soc., Chem. Commun. 1996, 585. Fujii, N.; Kakiuchi, F.;
Chatani, N.; Murai, S. Chem. Lett. 1996, 939.
(24) The ruthenium-catalyzed conversion of vinylsilanes to ethylene
and disilylethylene is known. Wakatuki, Y.; Yamazaki, H.; Nakano,
M.; Yamamoto, Y. J . Chem. Soc., Chem. Commun. 1991, 703. Mar-
ciniec, B.; Pietraszuk, C. J . Organomet. Chem. 1991, 412, C1. See also
Seki, Y.; Takeshita, K.; Kawamoto, K. J . Organomet. Chem. 1989, 369,
117.
(25) Bennett, R. L.; Bruce, M. I.; Goodall, B. L.; Iqbal, M. Z.; Stone,
F. G. A. J . Chem. Soc., Dalton Trans. 1972, 1787.
(26) Bruce, M. I.; Goodall, B. L.; Stone, F. G. A. J . Organomet. Chem.
1973, 60, 343.
(22) Halbritter, G.; Knoch, F.; Wolski, A.; Kish, H. Angew. Chem.,
Int. Ed. Engl. 1994, 33, 1603. Halbritter, G.; Knoch, F.; Wolski, A.;
Kish, H. J . Organomet. Chem. 1995, 492, 87. Aulwurm, U. R.;
Melchinger, J . U.; Kisch, H. Organometallics 1995, 14, 3385. West-
ernacher, S.; Kisch, H. Monatsh. Chem. 1996, 127, 469.
(
23) Kakiuchi, F.; Yamauchi, M.; Chatani, N.; Murai, S. Chem. Lett.
1
996, 111.

2
606 J . Org. Chem., Vol. 62, No. 8, 1997
Chatani et al.
Sch em e 2
Ru
3
(CO)12. The hydride complex, 4, reacts with ethylene
troduction of a CF
3
group at the 5-position on a pyridine
to give the ethyl complex 5, which undergoes CO inser-
tion, followed by reductive elimination to give the final
product 2a (Scheme 2). No evidence exists to show that
CO insertion occurs into an ethyl-Ru bond or a phenyl-
Ru bond in 5.27
ring resulted in a slow reaction (47% yield, 20 h) with
the monocarbonylation product 13 being obtained exclu-
sively (eq 5). The presence of electron-withdrawing
groups, such as CF and propionylphenyl groups, in 13
3
inhibit the coordination of nitrogen to the ruthenium
The reaction of 2-(2-methylphenyl)pyridine (6) with CO
and ethylene proceeds smoothly to give the corresponding
mono ketone 7 in 80% yield (eq 3).
3
complex. Replacing a CF group with a COOMe group
also gave monocarbonylation product selectively (eq 6).
However, introduction of a COOMe group at the 4-posi-
tion on a pyridine ring or a Me group at the 6-position
did not undergo the carbonylation reaction, and the
starting materials were recovered. The lack of reactivity
illustrates the importance of coordination of the pyridine
nitrogen to a ruthenium complex.
As was shown in eq 1, carbonylation did not stop at
the monocarbonylation step when a phenyl ring was
used. Some attempts have been made to avoid the
formation of a dicarbonylation product in a phenyl ring.
It is noteworthy that the substitution of a methyl group
at the 3-position on a pyridine ring gave a monocarbo-
nylation product selectivity. The reaction of 8 with CO
and ethylene resulted in a clean reaction to exclusively
give the monocarbonylation product 9 in high yield, with
no dicarbonylation product being observed (eq 4). For 9
to be converted to the dicarbonylation product, it would
be required to adopt a conformation in which the plane
of phenyl ring and that of pyridine ring are coplanar
when the C-H bond undergoes cleavage. The presence
of the methyl and propionyl group, as substituents, in
We next examined the effect of substituent groups on
the regioselectivity for the case of meta-substituted
pyridylbenzenes (eq 7). When the reaction of 2-(3-
methylphenyl)pyridine (16) was run, coupling took place
selectively at the 6-position, and 17 was obtained in high
yield as a single product, with no dicarbonylation product
being observed. Similarly, the reaction of 2-(3-methox-
yphenyl)-3-methylpyridine (18) gave monocarbonylation
product 19 in 85% yield, along with its regioisomer
1
0 prevents the two rings from achieving coplanarity
(leading to 11) because of steric congestion.
(
structure not shown) in 1% yield,28 indicating a prefer-
ential cleavage of the less hindered C-H bond. The
reaction of 2-[3-(trifluoromethyl)phenyl]-3-methylpyri-
dine (20) also resulted in regioselective carbonylation to
give 21 exclusively. The reaction of 22 required more
catalyst (0.2 mmol) and a longer reaction time (40 h) to
achieve a high yield of product (76% yield), while the
(
27) Casey, C. P.; Scheck, D. M. J . Am. Chem. Soc. 1980, 102, 2723.
Casey, C. P.; Scheck, D. M. J . Am. Chem. Soc. 1980, 102, 2728.
28) GC analysis of the crude reaction mixture indicated that they
were formed in a ratio of 21:1.
It is found that the product distribution can also be
controlled by electronic effects on a pyridine ring. In-
(

Ru
3
(CO)12-Catalyzed Carbonylation of Pyridylbenzenes
J . Org. Chem., Vol. 62, No. 8, 1997 2607
reaction under standard conditions (0.05 mmol of the
catalyst, 20 h) led to the formation of 23 in 22% yield.
Carbonylation took place exclusively at the less hindered
C-H bond, irrespective of the nature of the substituents.
It is apparent that steric factors are more important for
the control of regioselectivity.
alkenes30 and alkynes31 and in the stoichiometric cleav-
3
2
age of C-H bonds in furan ring by an iridium complex.
The reaction of 2-(3-fluorophenyl)-3-methylpyridine
(24) gave the monocarbonylation product 25 and its
regioisomer 26 in a ratio of 2.5:1 (eq 8). This observation
might suggest that steric factors do not play an important
role in determining the degree of regioselectivity. In the
case of 24, the fluorine atom might show a directing
effect, which could be attributed to the coordinating
ability of the fluorine atom to the ruthenium.
Some six-membered heterocycles, other than pyridine,
were also found to be an effective directing group for the
carbonylation of a C-H bond in the benzene ring (eqs
1
3 and 14).
The present reaction can be applied to other aromatic
systems. For example, the reaction of 2-(1′-naphthyl)-
pyridine (27) gave the corresponding ketone 28 in high
yield (eq 9). Carbonylation of the â-isomer 29 took place
regioselectively to give 30 as a single product (eq 10). Of
the two different reaction sites in 29, the C-H bond at
the 3-position in the naphthalene ring underwent exclu-
sive cleavage and was carbonylated, presumably because
of the steric hindrance of the peri-hydrogen on the
naphthalene ring.29
The substitution of acetylenes, such as phenylacety-
lene, 1-hexyne, 3-hexyne, and 1-(trimethylsilyl)-1-pro-
pyne or dienes such as isoprene for olefins failed to give
any carbonylation products, and the starting pyridylben-
zenes were recovered.
The present carbonylation reaction at a C-H bond is
also applicable to heteroaromatic compounds, such as
thiophene derivatives. The reaction of 2-(2-thienyl)-
pyridine (31) gave the corresponding ethyl ketone 32 in
high yield (eq 11). The reaction of the â-isomer 33
afforded 34 exclusively, as a result of cleavage of a C-
R-H bond (eq 12). The same selectivity was obtained in
catalytic addition of a C-H bond in furan ring to
Con clu sion
Ru (CO)12 catalyzes the coupling of aromatic C-H
3
bonds in pyridylbenzenes to CO and olefins. The present
reaction represents the first clean example of effective
(
29) The reaction of 2-acetylnaphthalene with vinylsilane in the
presence of RuH (CO)(PPh resulted in formation of C-C bond at
-position (refs 18a and e). The difference between the two reactions
(30) Yamazaki, H.; Wakatsuki, Y. J . Organomet. Chem. 1978, 149,
377. Yamazaki, H.; Hong, P. J . Mol. Catal. 1983, 21, 133.
(31) Boese, R.; Harvey, D. F.; Malaska, M. J .; Vollhardt, K. P. C. J .
Am. Chem. Soc. 1994, 116, 11153.
2
3 3
)
1
in regioselectivity may suggest the difference in the mechanism of C-C
bond-forming step. This will be discussed in the future paper.
(32) Selnau, H. E.; Merola, J . S. Organometallics 1993, 12, 1583.

2
608 J . Org. Chem., Vol. 62, No. 8, 1997
Chatani et al.
carbonylation of a benzene ring with cleavage of the C-H
bonds. Carbonylation takes place selectively at the ortho
C-H bond in the phenyl ring. Carbonylation does not
occur at a meta C-H bond, a para C-H bond, nor at the
C-H bonds on the pyridine ring. Further studies are
underway to explore further applications of the chelation-
assisted carbonylation to other catalytic systems.
157.36, 208.23; IR (neat) 3386, 3056, 2956, 2894, 1692, 1588,
1
9
0
471, 1441, 1427, 1337, 1245, 1217, 1162, 1090, 1061, 1019,
74, 904, 856, 796, 752, 691; MS, m/z (rel intensity) 282 (M ,
+
+
), 267 (M - CH
3
, 0.4), 182 (100), 127 (10), 73 (16). Anal.
21NOSi: C, 72.04; H, 7.47; N, 4,94. Found: C,
1.91; H, 7.41; N, 5.09.
-[3-(1-P r o p i o n y l)-2-(2-p y r i d i n y l)p h e n y l]-1-p r o -
p a n on e (3a ). White solid; mp 102-104 °C (hexane); R ) 0.11
) δ 0.96 (t, J ) 7.3 Hz,
Calcd for C17
7
H
1
f
1
(
hexane/EtOAc ) 1/2); H NMR (CDCl
3
Exp er im en ta l Section
3H), 2.36 (d, J ) 7.3 Hz, 2H), 7.26-7.32 (m, 2H), 7.52-7.58
1
3
(
m, 3H), 7.72 (t, J ) 7.6 Hz, 1H), 8.62 (d, J ) 4.9 Hz, 1H);
C
2 3
Ma ter ia ls. Toluene was distilled over CaH . Ru (CO)12
was purchased from Aldrich Chemical Co. and used after
recrystallization from hexane. 2-Phenylpyridine (1), 3-methyl-
NMR (CDCl ) δ 8.29, 36.14, 122.71, 124.82, 128.45, 128.66,
3
1
2
1
1
36.32, 142.28, 149.58, 156.55, 206.94; IR (KBr) 3254, 2982,
940, 2904, 2880, 1697, 1590, 1567, 1476, 1457, 1427, 1408,
375, 1344, 1293, 1272, 1247, 1227, 1177, 1150, 1119, 1051,
022, 990, 903, 784, 755, 741, 659; MS, m/z (rel intensity) 267
2
-phenylpyridine (8), and 4-phenylpyrimidine (37) were pur-
chased from Aldrich Chemical Co. and used after distillation
or recrystallization. Substituted 2-arylpyridines such as 2-(2-
methylphenyl)pyridine (6), 2-phenyl-5-(trifluoromethyl)pyri-
dine (12), 6-phenyl-3-pyridinecarboxylic acid methyl ester (14),
+
+
+
(
1
5
M , 0), 252 (M - CH
3
, 1), 238 (M - CH
53 (10). Anal. Calcd for C17 17NO2:: C, 76.38; H, 6.41; N,
.24. Found: C, 76.17; H, 6.38; N, 5.52.
-[3-Met h yl-2-(2-p yr id in yl)p h en yl]-1-p r op a n on e (7).
Light yellow oil; bp 160 °C (5 mmHg); R ) 0.09 (hexane/EtOAc
) δ 0.94 (t, J ) 7.3 Hz, 3H), 2.18 (s,
H), 2.45 (q, J ) 7.3 Hz, 2H), 7.23-7.45 (m, 5H), 7.73 (td, J )
2 3
CH , 100), 181 (18),
H
2
-(3-methylphenyl)pyridine (16), 2-(3-methoxyphenyl)pyridine
1
(18), 2-[3-(trifluoromethyl)phenyl]pyridine (20), 2-[3-(meth-
f
oxycarbonyl)phenyl]pyridine (22), 2-(3-fluorophenyl)-3-meth-
ylpyridine (24), 2-(1-naphthyl)pyridine (27), 2-(2-naphthyl)-
pyridine (29), 2-(2-thienyl)pyridine (31), and 2-(2-methyl-
phenyl)pyrimidine (35) were obtained by the Ni-catalyzed
coupling reaction of the corresponding heteroaromatic bro-
mides with arylmagnesium bromides. Methyl 3-(2-pyridinyl)-
benzoate (22) was preapred from the Pd-catalyzed coupling
reaction of methyl 3-iodobenzoate with 2-(tributylstannyl)-
pyridine. 2-(3-Thienyl)pyridine (33) was prepared from the
Pd-catalyzed coupling of 2-bromopyridine with 3-thienylzinc
bromide.
1
)
1/1); H NMR (CDCl
3
3
7
7
1
13
.6, 1.6 Hz, 1H), 8.66 (d, J ) 4.9 Hz, 1H); C NMR (CDCl ) δ
3
.93, 19.70, 35.06, 121.60, 124.42, 124.67, 127.60, 132.27,
35.60, 136.37, 138.17, 140.50, 148.93, 158.11, 205.82; IR
(neat) 3148, 3050, 2980, 2940, 1778, 1733, 1692, 1589, 1564,
1
9
457, 1422, 1377, 1343, 1275, 1243, 1167, 1142, 1097, 1023,
87, 968, 850, 787, 749, 648, 618; MS, m/z (rel intensity) 225
+
+
+
(
M , 1), 210 (M - CH
67 (18), 84 (12). Anal. Calcd for C15
N, 6.22. Found: C, 79.86; H, 6.73; N, 6.50.
-[2-[2-(3-Meth ylp yr id in yl)]p h en yl]-1-p r op a n on e (9).
Colorless oil; bp 135-140 °C (1 mmHg); R ) 0.17 (hexane/
) δ 1.00 (t, J ) 7.3 Hz, 3H),
.16 (s, 3H), 2.58 (q, J ) 7.3 Hz, 2H), 7.19 (dd, J ) 7.6, 4.6
3
, 2), 197 (15), 196 (M - CH
2 3
CH , 100),
1
H
15NO: C, 79.97; H, 6.71;
Gen er a l P r oced u r es. In a 50-mL stainless autoclave were
placed Ru
3
(CO)12 (32 mg, 0.05 mmol), 2-phenylpyridine (1) (2
1
f
mmol), and toluene (6 mL). The autoclave was charged with
ethylene to 7 atm and carbon monoxide to 20 atm at 25 °C
and then heated in an oil bath at 160 °C for 20 h. The
autoclave was cooled and depressured. The solvent was
removed in vacuo, and the resulting residue was subjected to
column chromatography on silica gel with hexane/EtOAc as
eluant to give 1-[2-(2-pyridinyl)phenyl]-1-propanone (2a ) as
pale yellow oil. An analytical sample was obtained by bulb-
to-bulb distillation.
1
EtOAc ) 1/2); H NMR (CDCl
3
2
Hz, 1H), 7.33 (dd, J ) 7.6, 1.1 Hz, 1H), 7.44-7.58 (m, 3H),
7
NMR (CDCl ) δ 8.25, 19.36, 34.58, 122.35, 127.98, 128.10,
1
2
1
9
1
3
.72 (dd, J ) 7.6, 1.5 Hz, 1H), 8.43 (d, J ) 4.6 Hz, 1H);
C
3
30.01, 130.82, 131.43, 137.72, 139.26, 139.87, 146.49, 158.94,
04.58; IR (neat) 3296, 3056, 2982, 1687, 1576, 1450, 1424,
376, 1346, 1250, 1212, 1181, 1158, 1116, 1077, 1060, 1020,
88, 947, 877, 792, 754, 701, 641; MS, m/z (rel intensity) 225
1
-[2-(2-P yr id in yl)p h en yl]-1-p r op a n on e (2a ). Pale yellow
+
+
+
1
(M , 0), 210 (M - CH
1
3
, 2), 197 (14), 196 (M - CH
2 3
CH , 100),
oil; bp 120 °C (1 mmHg); R
NMR (CDCl ) δ 1.08 (t, J ) 7.3 Hz, 3H), 2.49 (q, J ) 7.3 Hz
H), 7.21-7.26 (m, 1H), 7.44-7.67 (m, 5H), 7.77 (td, J ) 7.6,
.6 Hz, 1H), 8.62 (d, J ) 4.9 Hz, 1H); 13C NMR (CDCl
) δ 8.50,
6.32, 122.10, 122.16, 127.24, 128.55, 128.73, 129.79, 136.66,
38.13, 141.78, 149.11, 157.18, 207.78; IR (neat) 3060, 2978,
940, 2878, 2458, 1696, 1589, 1564, 1491, 1471, 1441, 1428,
372, 1345, 1299, 1271, 1212, 1150, 1118, 1080, 1056, 1018,
f
) 0.31 (hexane/EtOAc ) 1/2); H
67 (23), 83 (16). Anal. Calcd for C15
H
15NO: C, 79.97; H, 6.71;
3
N, 6.22. Found: C, 79.97; H, 6.83; N, 6.31.
1-[2-[2-[5-(Tr iflu or om et h yl)p yr id in yl]]p h en yl]-1-p r o-
2
1
3
1
2
1
9
3
p a n on e (13). Yellow oil; bp 140 °C (1 mmHg); R
f
) 0.34
) δ 1.14 (t, J ) 7.3 Hz,
H), 2.67 (d, J ) 7.3 Hz, 2H), 7.50-7.59 (m, 3H), 7.59-7.66
1
(
3
hexane/EtOAc ) 5/1); H NMR (CDCl
3
(
m, 1H), 7.71 (d, J ) 8.3 Hz, 1H), 7.99 (dd, J ) 8.3, 2.3 Hz,
1
3
+
1H), 8.86 (brs, 1H); C NMR (CDCl ) δ 8.39, 36.14, 121.87,
89, 946, 797, 753; MS, m/z (rel intensity) 211 (M , 0), 196
3
+
123.00 (q, J ) 272 Hz), 124.90 (q, J ) 33 Hz), 127.39, 129.27,
(
C
M
- CH
3
, 3), 182 (100), 154 (8), 127 (19). Anal. Calcd for
1
29.45, 130.12, 133.89, 137.04, 141.83, 145.90, 160.99, 206.97;
14
H13NO: C, 79.60; H, 6.20; N, 6.63. Found: C, 79.36; H,
IR (neat) 3062, 2980, 2942, 2884, 2506, 2324, 2030, 1966, 1871,
6
.34; N, 6.67.
,4-Dim eth yl-1-[2-(2-pyr idin yl)ph en yl]-1-pen tan on e (2b).
Colorless oil; bp 200 °C (1 mmHg); R ) 0.09 (hexane/EtOAc
) δ 0.74 (s, 9H), 1.50-1.56 (c, 2H), 2.38-
.44 (c, 2H), 7.22-7.27 (m, 1H), 7.45-7.67 (m, 5H), 7.77 (td, J
6.3, 1.9 Hz, 1H), 8.62 (d, J ) 3.8 Hz, 1H); 13C NMR (CDCl
δ 28.95, 29.60, 37.95, 38.98, 122.17, 122.25, 127.35, 128.59,
28.79, 129.85, 136.69, 138.19, 141.94, 149.24, 157.30, 207.78;
IR (neat) 3196, 3060, 2962, 2872, 1691, 1589, 1564, 1472, 1442,
1
1
694, 1606, 1580, 1564, 1498, 1479, 1462, 1445, 1413, 1385,
4
330, 1301, 1274, 1213, 1162, 1127, 1080, 1013, 945, 849, 787,
f
+
1
747, 668, 631, 613; MS, m/z (rel intensity) 279 (M , 0), 264
)
2
)
5/1); H NMR (CDCl
3
+
+
(M
- CH
3
, 2), 251 (14), 250 (M - CH
2 3
CH , 100), 202 (11),
75 (11). Anal. Calcd for C H
15 12
NOF : C, 64.52; H, 4.33; N,
3
3
)
5
.08. Found: C, 64.44; H, 4.49; N, 5.08.
6-[2-(1-P r op a n oyl)p h en yl]-3-p yr id in eca r boxylic Acid
Meth yl Ester (15). Light red oil; bp 180-185 °C (1 mmHg);
1
1
1
1
2
428, 1394, 1365, 1296, 1248, 1213, 1186, 1150, 1090, 1069,
3
H NMR (CDCl ) δ 1.13 (t, J ) 7.3 Hz, 3H), 2.62 (q, J ) 7.3
018, 987, 951, 909, 797, 751, 731, 643; MS, m/z (rel intensity)
Hz, 2H), 3.97 (s, 3H) 7.46-7.57 (c, 3H), 7.67-7.71 (c, 2H), 8.36
(dd, J ) 8.2, 2.3 Hz, 1H), 9.20 (d, J ) 2.3 Hz, 1H); C NMR
+
+
13
67 (M , 0), 252 (M - CH
21NO: C, 80.86; H, 7.92; N, 5.24. Found
C, 81.16; H, 7.85; N, 5.49.
-[2-(2-P yr id in yl)p h e n yl]-3-(t r im e t h ylsilyl)-1-p r o-
3
, 4), 183 (17), 182 (100), 127 (11).
Anal. Calcd for C18
H
3
(CDCl ) δ 8.43, 36.25, 52.35, 121.60, 124.26, 127.31, 129.04,
129.36, 129.96, 137.20, 137.83, 142.05, 150.19, 161.01, 165.57,
207.20; IR (neat) 3648, 3374, 3062, 2978, 1927, 1725, 1694,
1596, 1559, 1493, 1475, 1437, 1412, 1373, 1348, 1287, 1212,
1190, 1120, 1080, 1018, 947, 856, 832, 794, 754; MS, m/z (rel
1
p a n on e (2c). Colorless oil; bp 185-190 °C (1 mmHg); R
f
)
1
0
0
.15 (hexane/EtOAc ) 3/1); H NMR (CDCl
3
) δ -0.15 (s, 9H),
+
+
.75-0.81 (c, 2H), 2.34-2.41 (c, 2H), 7.23 (m, 1H), 7.45-7.67
intensity) 269 (M , 0), 241, (17), 240 (M - CH
(11), 126 (10), 104 (14), 90 (13), 76 (34). Anal. Calcd for C16
NO : C, 71.36; H, 5.61; N, 5.20. Found: C, 71.29; H, 5.69; N,
5.39.
2 3
CH , 100), 153
(
1
1
m, 5H), 7.76 (td, J ) 7.6, 1.6 Hz, 1H), 8.62 (d, J ) 4.6 Hz,
15
H -
1
3
H); C NMR (CDCl
3
) δ -2.06, 10.95, 37.72, 122.21, 122.32,
3
27.48, 128.61, 128.81, 129.87, 136.69, 138.24, 141.69, 149.24,

Ru
3
(CO)12-Catalyzed Carbonylation of Pyridylbenzenes
J . Org. Chem., Vol. 62, No. 8, 1997 2609
1
-[4-Meth yl-2-(2-p yr id in yl)p h en yl]-1-p r op a n on e (17).
Light yellow oil; bp 185 °C (1 mmHg); R ) 0.34 (hexane/EtOAc
) δ 1.05 (t, J ) 7.3 Hz, 3H), 2.44 (s,
1449, 1377, 1345, 1299, 1269, 1208, 1174, 1123, 1079, 1061,
f
1036, 1014, 951, 898, 878, 830, 794, 695, 629; MS, m/z (rel
1
+
+
)
3
7
1/1); H NMR (CDCl
3
3
intensity) 25: 243 (M , 0), 228 (M - CH , 2.0), 215 (14), 214
+
+
H), 2.47 (q, J ) 7.3 Hz, 2H), 7.22-7.27 (m, 2H), 7.40 (d, J )
.8 Hz, 1H), 7.44 (s, 1H), 7.53 (d, J ) 8.1 Hz, 1H), 7.75 (td, J
(M - CH
2
CH
, 2), 215 (14), 214 (M - CH
14FNO: C, 74.06; H, 5.80; N,
3
, 100), 185 (16), 92 (17); 26: 243 (M , 0), 228
+
+
(M - CH
3
2 3
CH , 100), 185 (12),
)
7.7, 1.9 Hz, 1H), 8.63 (d, J ) 4.6 Hz, 1H); 13C NMR (CDCl
3
)
92 (12). Anal. Calcd for C15
H
δ 8.65, 21.33, 36.16, 122.12, 122.44, 127.66, 129.16, 129.79,
36.53, 138.63, 138.78, 140.25, 149.22, 157.77, 207.38; IR
neat) 3282, 3228, 2976, 2936, 1691, 1609, 1588, 1564, 1473,
5.76. Found: C, 74.01; H, 5.93; N, 5.85.
1
(
1-[2-[1-(2-P yr id in yl)]n a p h th yl]-1-p r op a n on e (28). Col-
1
orless oil; R
f
) 0.10 (hexane/EtOAc ) 3/1); H NMR (CDCl
3
) δ
1
1
461, 1429, 1373, 1345, 1308, 1293, 1271, 1218, 1189, 1149,
080, 1054, 1039, 1014, 990, 948, 889, 824, 791, 746, 642; MS,
0.98 (t, J ) 7.3 Hz, 3H), 2.46 (q, J ) 7.3 Hz, 2H), 7.34-7.39
(m, 1H), 7.42-7.48 (m, 2H), 7.54 (td, J ) 7.4, 1.4 Hz, 1H), 7.64
(d, J ) 8.6 Hz, 1H), 7.66 (d, J ) 8.6 Hz, 1H), 7.83 (td, J ) 7.8,
1.9 Hz, 1H), 7.91 (d, J ) 7.9 Hz, 1H), 7.95 (d, J ) 8.6 Hz, 1H),
+
+
m/z (rel intensity) 225 (M , 0), 210 (M - CH
3
, 2), 197 (14),
, 100), 167 (11). Anal. Calcd for C15
NO: C, 79.97; H, 6.71; N, 6.22. Found: C, 80.10; H, 6.76; N,
.30.
-[4-Met h oxy-2-(3-m et h yl-2-p yr id in yl)p h en yl]-1-p r o-
p a n on e (19). Yellow oil; bp 175-180 °C (1 mmHg); R ) 0.17
) δ 1.00 (t, J ) 7.3 Hz,
H), 2.07 (s, 3H), 2.61 (d, J ) 7.3 Hz, 2H), 3.86 (s, 3H, OCH ),
.79 (d, J ) 2.7 Hz, 1H), 6.96 (dd, J ) 8.6, 2.7 Hz, 1H), 7.20
+
1
96 (M - CH
2
CH
3
15
H -
8.79 (d, J ) 4.3 Hz, 1H); 13C NMR (CDCl
) δ 8.02, 35.56,
3
6
122.16, 123.59, 125.66, 126.24, 126.70, 126.77, 127.71, 128.48,
131.18, 134.02, 135.81, 136.51, 137.48, 149.27, 157.12, 205.98;
IR (neat) 2986, 2942, 1691, 1622, 1589, 1566, 1474, 1431, 1377,
1350, 1214, 1147, 1091, 1035, 993, 955, 867, 819, 792, 748,
1
f
1
(
hexane/EtOAc ) 1/2); H NMR (CDCl
3
+
+
3
6
3
663; MS, m/z (rel intensity) 261 (M , 0), 233 (19), 232 (M
-
CH CH , 100), 204 (10), 203 (14), 176 (12), 115 (13), 101 (37),
2
3
+
(
dd, J ) 7.6, 4.6 Hz, 1H), 7.54 (d, J ) 7.6 Hz, 1H), 7.81 (d, J
88 (19). HRMS calcd for C18
Found: 260.1079.
H14NO (M - 1) 260.1075.
)
8
1
8.4 Hz, 1H), 8.44 (d, J ) 4.6 Hz, 1H); 13C NMR (CDCl
3
) δ
.32, 19.10, 33.55, 55.44, 113.24, 115.40, 122.25, 130.53,
30.94, 131.14, 137.36, 142.75, 146.27, 159.48, 161.80, 201.62;
1-[2-[3-(2-P yr id in yl)]n a p h th yl]-1-p r op a n on e (30). Col-
1
orless oil; R
f
) 0.29 (hexane/EtOAc ) 1/1); H NMR (CDCl ) δ
3
IR (neat) 3150, 3058, 2974, 2942, 2840, 1681, 1603, 1563, 1461,
432, 1377, 1346, 1320, 1301, 1260, 1220, 1172, 1135, 1113,
079, 1060, 1026, 950, 883, 795, 694; MS, m/z (rel intensity)
55 (M , 0), 240 (M - CH
00), 211 (11), 183 (16), 154 (17). Anal. Calcd for C16
1.14 (t, J ) 7.3 Hz, 3H), 2.62 (q, J ) 7.3 Hz, 2H), 7.26-7.29
(m, 1H), 7.53-7.61 (m, 2H), 7.74 (brd, J ) 7.8 Hz, 1H), 7.82
1
1
2
1
(dt, J ) 7.8, 4.3 Hz, 1H), 7.90-7.94 (m, 2H), 7.98 (s, 1H), 8.11
+
+
+
13
3
, 1), 227 (15), 226 (M - CH
2
CH
17NO
3
,
:
(s, 1H), 8.61 (d, J ) 4.9 Hz, 1H); C NMR (CDCl ) δ 8.72,
3
H
2
36.28, 122.07, 122.26, 127.24, 127.55, 127.60, 128.14, 128.39,
128.75, 132.51, 133.57, 136.03, 136.77, 139.53, 149.18, 157.57,
207.19; IR (neat) 3058, 2978, 2938, 2822, 1730, 1693, 1630,
1591, 1568, 1480, 1462, 1443, 1428, 1373, 1346, 1289, 1272,
1244, 1179, 1148, 1128, 1079, 1050, 1023, 995, 934, 892, 876,
C, 75.27; H, 6.71; N, 5.49. Found: C, 75.56; H, 6.74; N, 5.62.
-[2-(2-P yr id in yl)-4-(t r iflu or om et h yl)p h en yl]-1-p r o-
p a n on e (21). Yellow oil; mp 150-155 °C (hexane); R ) 0.24
) δ 1.12 (t, J ) 7.6 Hz,
1
f
1
(
hexane/EtOAc ) 5/1); H NMR (CDCl
3
+
+
3
7
1
H), 2.52 (d, J ) 7.6 Hz, 2H), 7.28 (dd, J ) 7.9, 4.6 Hz, 1H),
3
788, 743; MS, m/z (rel intensity) 261 (M , 0), 246 (M - CH ,
+
.52 (d, J ) 7.9 Hz, 1H), 7.66-7.73 (m, 2H), 7.81 (td, J ) 7.9,
2), 233 (18), 232 (M - CH
2
CH
3
, 100), 176 (12), 115 (22), 101
15NO: C, 82.73; H, 5.79;
.7 Hz, 1H), 7.94 (s, 1H), 8.63 (d, J ) 4.6 Hz, 1H); 13C NMR
(14), 87 (20). Anal. Calcd for C18
H
(
CDCl
3
) δ 8.34, 36.48, 122.12, 122.95, 123.85 (q, J ) 270 Hz),
N, 5.36. Found: C, 82.40; H, 5.82; N, 5.42.
1
1
1
1
6
2
25.46, 127.71, 131.78 (q, J ) 33 Hz), 137.11, 138.62, 145.03,
49.34, 155.49, 206.83; IR (neat) 3064, 2982, 2944, 1704, 1617,
590, 1497, 1477, 1414, 1375, 1334, 1304, 1285, 1263, 1212,
167, 1132, 1084, 1034, 1015, 991, 949, 902, 833, 792, 745,
1-[3-[2-(2-P yr id in yl)]th ien yl]-1-p r op a n on e (32). Yellow
1
oil; bp 125 °C (1 mmHg); R
NMR (CDCl
2H), 7.22-7.27 (m, 1H), 7.32-7.37 (m, 2H), 7.67-7.75 (m, 2H),
f
) 0.13 (hexane/EtOAc ) 5/1); H
3
) δ 1.15 (t, J ) 7.3 Hz, 3H), 2.76 (q, J ) 7.3 Hz,
+
+
13
52, 618; MS, m/z (rel intensity) 279 (M , 0), 264 (M - CH
3
,
8.61 (d, J ) 5.1 Hz, 1H); C NMR (CDCl ) δ 8.29, 35.94,
3
+
), 251 (15), 250 (M - CH
NO: C, 64.52; H, 4.33; N, 5.02. Found: C,
4.76; H, 4.38; N, 5.16.
-(2-P yr id in yl)-4-(1-p r op a n on yl)ben zoic Acid Meth yl
Ester (23). Colorless oil; bp 190-195 °C (1 mmHg); R ) 0.11
) δ 1.12 (t, J ) 7.3 Hz,
H), 2.53 (q, J ) 7.3 Hz, 2H), 3.97 (s, 3H), 7.25-7.29 (m, 1H),
.47 (d, J ) 7.8 Hz, 1H), 7.73 (d, J ) 7.6 Hz, 1H), 7.82 (td, J
7.6, 1.6 Hz, 1H), 8.11 (dd, J ) 7.8, 1.6 Hz, 1H), 8.37 (d, J )
.6 Hz, 1H), 8.61 (d, J ) 4.6 Hz, 1H); 13C NMR (CDCl
) δ 8.38,
2
CH
3
, 100), 153 (11), 125 (10). Anal.
122.82, 123.41, 126.25, 128.77, 136.39, 138.67, 146.56, 149.36,
151.90, 199.89; IR (neat) 3074, 2980, 2940, 1686, 1585, 1568,
1521, 1467, 1439, 1422, 1377, 1334, 1267, 1212, 1159, 1119,
1089, 1048, 995, 868, 779, 731, 652 m; MS, m/z (rel intensity)
Calcd for C15
12 3
H F
6
3
+
+
+
f
217 (M , 0.3), 202 (M - CH
3
, 12), 189 (16), 188 (M - CH
2
-
-
1
(
3
7
hexane/EtOAc ) 3/1); H NMR (CDCl
3
CH , 100), 116 (16), 89 (20), 78 (10). Anal. Calcd for C12H
3
11
NOS: C, 66.33; H, 5.10; N, 6.45. Found: C, 66.14; H, 5.24;
N, 6.51.
)
1-[2-[3-(2-P yr id in yl)]th ien yl]-1-p r op a n on e (34). Yellow
1
1
3
1
3
1
8
3
oil; bp 165 °C (1 mmHg); R
NMR (CDCl
2H), 7.22-7.26 (m, 1H), 7.33-7.37 (m, 2H, Ar), 7.65-7.75 (m,
2H, Ar), 8.62 (d, J ) 4.6 Hz, 1H); 13C NMR (CDCl
) δ 8.29,
f
) 0.43 (hexane/EtOAc ) 5/1); H
6.46, 52.36, 121.98, 122.64, 127.28, 129.69, 131.20, 136.98,
38.06, 145.86, 149.13, 155.88, 166.13, 207.33; IR (neat) 3230,
058, 2980, 1729, 1611, 1589, 1575, 1475, 1431, 1408, 1372,
347, 1310, 1253, 1209, 1148, 1111, 1041, 992, 970, 950, 915,
3
) δ 1.15 (t, J ) 7.3 Hz, 3H), 2.76 (q, J ) 7.3 Hz
3
35.94, 122.82, 123.41, 126.24, 128.70, 136.37, 138.65, 146.59,
149.38, 151.91, 199.91; IR (neat) 3104, 3054, 2980, 2938, 1684,
1584, 1568, 1519, 1467, 1438, 1422, 1377, 1333, 1265, 1215,
1150, 1118, 1087, 1046, 996, 868, 779, 733, 655, 614; MS, m/z
+
49, 793, 763, 748; MS, m/z (rel intensity) 269 (M , 0), 254
+
+
(
7
5
M
- CH
6 (16). Anal. Calcd for C13
.20. Found: C, 71.39; H, 5.72; N, 5.27.
-[4-F lu or o-2-[2-(3-m e t h ylp yr id in yl)]p h e n yl]-1-p r o-
3
, 2), 241 (15), 240 (M - CH
2 3
CH , 100), 153 (12),
: C, 71.36; H, 5.61; N,
22 2 2
H N O
+
+
(rel intensity) 217 (M , 0), 202 (M - CH
3
, 12), 189 (14), 188
, 100), 134 (10), 133 (10), 116 (22), 94 (10), 89
(32), 77 (17), 63 (19). Anal. Calcd for C12 11NOS: C, 66.33;
+
1
2 3
(M - CH CH
p a n on e (25) a n d 1-[2-flu or o-6-[2-(3-m eth ylp yr id in yl)]-
H
p h en yl]-1-p r op a n on e (26). Spectral data were obtained
H, 5.10; N, 6.45. Found: C, 66.48; H, 5.16; N, 6.50.
from a mixture of 25 and 26. Light yellow oil; bp 160-165 °C
1-[3-Meth yl-2-(2-pyr im idin yl)ph en yl]-1-pr opan on e (36).
1
(1 mmHg); R
f
) 0.34 (hexane/EtOAc ) 1/2); H NMR (CDCl
3
)
Red oil; bp 160 °C (1 mmHg); R
f
) 0.34 (hexane/EtOAc ) 1/2);
1
δ 0.97-1.06 (m, 3H, CH
3
CH
2
C(O)), [2.16 (s, 25), 2.25 (s, 26),
H NMR (CDCl ) δ 1.06 (t, J ) 7.3 Hz, 2H), 2.20 (s, 3H), 2.79
3
3
2
H], [2.57 (q, J ) 7.3 Hz, 25), 2.78 (qd, J ) 7.0, 1.8 Hz, 26),
(q, J ) 7.3 Hz, 2H), 7.26 (t, J ) 5.0 Hz, 1H), 7.37-7.45 (m,
2H), 7.63 (dd, J ) 6.8, 1.9 Hz, 1H), 8.81 (d, J ) 5.0 Hz, 2H);
H], [7.03 (dd, J ) 9.5, 2.7 Hz, 25), 7.12-7.24 (m), 7.39-7.47
1
3
(
(
(
(
m), 7.56-7.59 (m), 7.78 (dd, J ) 8.6, 5.7 Hz, 25), 5H], [8.39
3
C NMR (CDCl ) δ 8.20, 19.70, 33.95, 118.80, 125.80, 128.39,
1
3
d, J ) 4.6 Hz, 26), 8.44 (d, J ) 4.6 Hz, 25), 1H]; C NMR
CDCl ) δ [7.64 (26), 8.18 (25)], [19.14 (25), 19.39 (26)], [34.31
25), 37.94 (26)], 114.68, 114.99, 115.20, 115.53, 117.11, 117.43,
133.68, 137.30, 138.22, 138.56, 156.77, 168.10, 203.56; IR
(neat) 3034, 2978, 2936, 1692, 1621, 1558, 1445, 1408, 1377,
1344, 1285, 1236, 1168, 1101, 1039, 971, 951, 805, 772, 748,
3
+
+
1
1
1
22.62, 122.68, 125.23, 125.28, 130.35, 130.48, 130.71, 130.85,
31.23, 131.84, 135.08, 135.11, 137.79, 138.15, 142.79, 142.91,
46.31, 146.52, 157.77, 161.83, 165.55, [202.64 (25), 203.65
3
714, 655; MS, m/z (rel intensity) 226 (M , 0), 211 (M - CH ,
+
2), 198 (15), 197 (M - CH
Calcd for C13 O: C, 74.31; H, 6.24; N, 12.38. Found: C,
74.36; H, 6.27; N, 12.53.
2 3
CH , 100), 169 (11), 89 (13). Anal.
14 2
H N
(26)]; IR (neat) 3212, 3058, 2982, 2940, 2884, 1693, 1608, 1581,

2
610 J . Org. Chem., Vol. 62, No. 8, 1997
Chatani et al.
1
-[2-(4-P yr im id in yl)p h en yl]-1-p r op a n on e (38). Light
red oil; bp 135 °C (1 mmHg); R ) 0.34 (hexane/EtOAc ) 1/4);
) δ 1.18 (t, J ) 7.3 Hz, 3H), 2.72 (q, J ) 7.3
Hz, 2H), 7.48-7.61 (m, 4H), 7.66-7.69 (m, 1H), 8.79 (d, J )
Anal. Calcd for C13
Found: C, 73.38; H, 5.73; N, 13.22.
H
12
N
2
O: C, 73.57; H, 5.70; N, 13.20.
f
1
H NMR (CDCl
3
Ack n ow led gm en t. This work was supported, in
part, by grants from the Ministry of Education, Science,
Sports, and Culture, J apan. Thanks are given to the
Instrumental Analysis Center, Faculty of Engineering,
Osaka University, for assistance in obtaining MS,
HRMS, 600-MHz NMR, and elemental analyses.
5
1
1
2
1
7
.1 Hz, 1H), 9.19 (s, 1H); 13C NMR (CDCl
3
) δ 8.27, 36.03,
18.92, 127.28, 129.04, 130.01, 130.08, 135.45, 141.74, 151.27,
58.10, 164.42, 206.56; IR (neat) 3192, 3154, 3036, 2980, 2938,
900, 1696, 1577, 1539, 1488, 1469, 1442, 1409, 1387, 1347,
306, 1274, 1214, 1160, 1116, 1079, 1012, 988, 947, 878, 846,
+
+
93, 753, 674; MS, m/z (rel intensity) 212 (M , 0), 197 (M
-
+
CH
3
, 2), 184 (13), 183 (M - CH
2
CH
3
, 100), 128 (18), 101 (12).
J O970131R