Palladium-Catalyzed Carbonylation of Allyl Alcohols in the Presence of Phenols

Full text of DOI:10.1021/jo962387n

2662
J . Org. Chem. 1997, 62, 2662-2664
benzene (5 mL) under CO (5 atm) at 100 °C for 18 h,
(E)-phenyl 4-phenyl-3-butenoate (3) was produced in a
yield of 24% (entry 1 in Table 1). An increase in the
amount of PPh3 to 0.4 mmol remarkably enhanced the
ester yield (76%) (entry 2), and in this case alcohol 1 was
completely consumed. The yield was further improved
up to 80% by the use of a slight excess of 2 (2.4 mmol)
(entry 4). It was observed that Pd(PPh3)4 was less
efficient than the combination of Pd(OAc)2 and PPh3
(entry 5 vs 2). This may suggest that acetic acid derived
from Pd(OAc)2 acts as a promoter. Indeed, the reaction
of 1 with 2 using Pd(PPh3)4 in the presence of acetic acid
(0.1 mmol) gave a better yield of 3 compared with that
using Pd(PPh3)4 alone (entry 6). Interestingly, the phen-
oxycarbonylation of 1 was found to proceed efficiently
even under atmospheric pressure of CO (entry 7). Polar
solvents, DMF and 2-methoxyethyl ether, could not be
used in the present reaction (entries 8 and 9). The
reaction of 1 should be accompanied by the formation of
water. Addition of molecular sieves (4A, 200 mg) for its
removal, however, somewhat reduced the yield of 3 (entry
10).
Phenoxycarbonylation of a number of allyl alcohols was
also performed using Pd(OAc)2 and PPh3 under CO (1 or
5 atm) in toluene or benzene (Table 2). The reaction of
R- or γ-arylated allyl alcohols proceeded smoothly to give
the corresponding phenyl esters selectively in fair to good
yields. The reaction of 2-hexen-1-ol (15) or 1-hexen-3-ol
(17) was, however, less efficient, giving a mixture of (E)-
and (Z)-isomers of ester 16 in low yield. The fact that 1
and 4 gave the same product as that in the case of 15
and 17 may suggest that the reaction process involves
π-allylpalladium intermediates.
P a lla d iu m -Ca ta lyzed Ca r bon yla tion of Allyl
Alcoh ols in th e P r esen ce of P h en ols
Tetsuya Satoh, Masahiro Ikeda, Yuichi Kushino,
Masahiro Miura,* and Masakatsu Nomura
Department of Applied Chemistry, Faculty of Engineering,
Osaka University, Suita, Osaka 565, J apan
Received December 20, 1996
Palladium-catalyzed carbonylation of allylic compounds
is one of the most promising methods for the preparation
of synthetically useful â,γ-unsaturated carboxylic acid
derivatives.1 Effective methods for the reaction of allylic
carbonates,2 esters,3 halides,4 amines,5 and ethers6 under
reasonably mild conditions have so far been developed.
However, carbonylation of allyl alcohols has been less
explored in spite of the ready availability of the starting
materials, as the reaction requires a high pressure of
carbon monoxide.7 Recently, we have shown that allyl
alcohols can be carbonylated efficiently in the presence
of titanium(IV) alkoxides and lithium chloride under
medium CO pressure (25 atm) to give alkyl 3-butenoates.8
Meanwhile, we have also reported that palladium-
catalyzed carbonylation of terminal alkynes9a and aryl
iodides9b,c in the presence of phenols and intramolecular
carbonylative cyclization of 2-hydroxybenzyl alcohols9d
proceeds smoothly under considerably mild conditions.
We herein demonstrate our new findings that the direct
carbonylation of allyl alcohols bearing an aryl substituent
at the R- or γ-position can also be attained in the presence
of phenols using a palladium catalyst to afford the
corresponding â,γ-unsaturated esters even under atmo-
spheric pressure of CO (eq 1).
Meanwhile, the carbonylation of 1 using 4-methoxy-
and 3-chlorophenols in place of 2 also gave esters 18 and
19 in good yields (eq 2).
Resu lts a n d Discu ssion
When a mixture of (E)-3-phenyl-2-buten-1-ol (1) (2
mmol) and phenol (2) (2 mmol) was heated in the
presence of Pd(OAc)2 (0.1 mmol) and PPh3 (0.2 mmol) in
A probable mechanism for the formation of 3 from 1
and 2 is illustrated in Scheme 1 where neutral ligands
are omitted. Alcohol 1 reacts with Pd0 species generated
in situ in the presence of phenol (2) to afford a π-allyl-
palladium intermediate (I). Subsequently, insertion of
CO to I followed by reductive elimination gives product
3.10 In the early stage of the reaction of 1 under CO (1
atm) (conversion of 1 ) 30%), formation of phenyl ether
20 (9%) as well as 3 (5%) was detected in the reaction
medium, while the former disappeared in the end (entry
7 in Table 1). It was confirmed that treatment of ether
20 under the present carbonylation conditions gave 3 in
a yield of 87%. These facts suggest that the ester 3 may
be produced, at least in part, via 20. In contrast to our
observation, ether 20 has recently been reported to be
inactive toward carbonylation using palladium species
in relatively polar solvents such as THF and CH2Cl2.11
(1) (a) Heck, R. F. Palladium Reagents in Organic Syntheses;
Academic Press: New York, 1985. (b) Tsuji, J . Palladium Reagents
and Catalysts; J ohn Wiley & Sons Ltd.: Chichester, 1995.
(2) Tsuji, J .; Sato, K.; Okumoto, H. J . Org. Chem. 1984, 49, 1341.
(3) (a) Matsuzaka, H.; Hiroe, Y.; Iwasaki, M.; Ishii, Y.; Koyasu, Y.;
Hidai, M. J . Org. Chem. 1988, 53, 3832. (b) Murahashi, S.-I.; Imada,
Y.; Taniguchi, Y.; Higashiura, S. J . Org. Chem. 1993, 58, 1538. (c)
Yamamoto, A. Bull. Chem. Soc. J pn. 1995, 68, 433.
(4) Okano, T.; Okabe, N.; Kiji, J . Bull. Chem. Soc. J pn. 1992, 65,
2589.
(5) Murahashi, S.-I.; Imada, Y.; Nishimura, K. Tetrahedron 1994,
50, 453.
(6) (a) Neibecker, D.; Poirier, J .; Tkatchenko, I. J . Org. Chem. 1989,
54, 2459. (b) Bonnet, M. C.; Coombes, J .; Manzano, B.; Neibecker, D.;
Tkatchenko, I. J . Mol. Catal. 1989, 52, 263.
(7) (a) Tsuji, J .; Kiji, J .; Imamura, S.; Morikawa, M. J . Am. Chem.
Soc. 1964, 86, 4350. (b) Knifton, J . F. J . Organomet. Chem. 1980, 188,
223. (c) Sakamoto, M.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc.
J pn. 1996, 69, 1065. (d) Naigre, R.; Alper, H. J . Mol. Catal. A: Chem.
1996, 111, 11.
(8) Itoh, K.; Hamaguchi, N.; Miura, M.; Nomura, M. J . Mol. Catal.
1992, 75, 117.
(9) (a) Itoh, K.; Miura, M.; Nomura, M. Tetrahedron Lett. 1992, 33,
5369. (b) Satoh, T.; Kokubo, K.; Miura, M.; Nomura, M. Organo-
metallics 1994, 13, 4431. (c) Satoh, T.; Ikeda, M.; Miura, M.; Nomura,
M. J . Mol. Catal. A: Chem. 1996, 111, 25. (d) Satoh, T.; Tsuda, T.;
Kushino, Y.; Miura, M.; Nomura, M. J . Org. Chem. 1996, 61, 6476.
(10) However, another pathway via (phenoxycarbonyl)(σ-allyl)pal-
ladium intermediates cannot be excluded:4 (a) Milstein, D. Organo-
metallics 1982, 1, 888. (b) Milstein, D. Acc. Chem. Res. 1988, 21, 428.
S0022-3263(96)02387-0 CCC: $14.00 © 1997 American Chemical Society

Notes
J . Org. Chem., Vol. 62, No. 8, 1997 2663
Ta ble 1. P h en oxyca r bon yla tion of 3-P h en yl-2-bu ten -1-ol
(1)a
Ta ble 2. P h en oxyca r bon yla tion of Allyl Alcoh olsa
recovery (%)b
entry
Pd catalyst
1
2
yield of 3 (%)b
1
2
Pd(OAc)2 + 2PPh3
Pd(OAc)2 + 4PPh3
Pd(OAc)2 + 4PPh3
Pd(OAc)2 + 4PPh3
Pd(PPh3)4
Pd(PPh3)4 + CH3COOH
Pd(OAc)2 + 4PPh3
22
74
24
76
66
80 (75)
49
20
32
37
49
29
23
3c
4d
5
19
6
64
76 (70)
7e,f
8e,g Pd(OAc)2 + 4PPh3
∼100 ∼100
9e,h Pd(OAc)2 + 4PPh3
95
95
28
5
70
10i
Pd(OAc)2 + 4PPh3
a
Reaction conditions: 1 (2 mmol), 2 (2 mmol), and Pd catalyst
(0.1 mmol) in benzene (5 mL) under CO (5 atm) at 100 °C for 18
b
h. Determined by GLC analysis based on 1 used. Value in
parentheses indicates yield after purification. c Pd(OAc)2 (0.05
d
mmol) was used. 2 (2.4 mmol) was used. e Under CO (1 atm) at
g
h
80 °C for 20 h. f In toluene. In DMF. In 2-methoxyethyl ether.
i
Molecular sieves (4A, 200 mg) was added.
The carbonylation of alcohol 1 using n-butanol as the
nucleophile and Pd(OAc)2 and PPh3 under 5 atm of CO
in benzene gave (E)-butyl 4-phenyl-3-butenoate (21) in
a low yield (27%).12 Thus, phenol appears to act as a good
nucleophile in the reaction (cf. entry 2 in Table 1), so that
it can be carried out under mild and nearly neutral
conditions, as for the carbonylation of terminal alkynes.9a
Consistently, in the stoichiometric carbonylation of [Pd(η3-
1-phenylallyl)(OAc)]2 (22) (0.1 mmol) with phenol (1
mmol) in the presence of PPh3 (0.2 mmol) in toluene (5
mL) under CO (1 atm) at 80 °C, ester 3 was smoothly
formed (3 h, 77%; 22 h, 91%) (eq 3). By contrast, the
reaction using n-butanol (2 mmol) gave ester 21 in a low
yield (22 h, 19%).
a
Reaction conditions: allyl alcoholb (2 mmol), 2 (2.4 mmol),
Pd(OAc)2 (0.1 mmol), and PPh3 (0.4 mmol) in benzene (5 mL) under
b
CO (5 atm) at 100 °C for 18 h. Unless otherwise noted, E:Z was
>98:2. c GLC yield based on amount of allyl alcohols used. Value
in parentheses indicates yield in the reaction under 1 atm of CO
in toluene at 80 °C for 20 h.
Sch em e 1
While the exact role of acetic acid derived from
Pd(OAc)2 or added is not definitive at the present stage,
it would promote the first step, oxidative addition of 1 to
Pd0 species (Scheme 1).6 On the other hand, one of the
possible reasons for the less efficiency of the reaction of
aliphatic allyl alcohols such as 15 and 17 seems to be
attributable to involvement of a side reaction leading to
the corresponding dienes, since â-hydride elemination
from a π-allylpalladium species is known.1 Indeed, in the
treatment of (E)-2-decenol under the carbonylation condi-
tions, 1,3-decadiene (21%) was formed along with the
corresponding phenyl ester (24%).
Exp er im en ta l Section
1H NMR spectra were recorded at 400 MHz with CDCl3 as
solvent. MS data were obtained by EI. GLC analysis was
carried out using a silicon OV-17 column (i.d. 2.6 mm × 1.5 m)
or with a CBP-1 capillary column (i.d. 0.5 mm × 25 m).
The complexes Pd(PPh3)4 and [Pd(η3-1-phenylallyl)(OAc)]2
1a
(22)3b were prepared by the methods reported previously. Allyl
alcohols 413 and 1713 and ether 2011 were prepared according to
the published procedures. Allyl alcohols 5, 7, 9, 11, and 13 were
prepared by the reduction of the corresponding alkynols with
(11) Goux, C.; Lhoste, P.; Sinou, D.; Masdeu, A. J . Organomet. Chem.
1996, 511, 139. The origin of the observed remarkable solvent effect,
however, is not definitive at the present stage.
(12) Even in this case as well as in the reaction with phenols,
formation of a self-esterification product, 3-phenyl-2-butenyl 4-phenyl-
3-butenoate, was not detected.
(13) Hwa, J . C. H.; Sims, H. Organic Syntheses; Wiley: New York,
1973; Collect. Vol. V, p 608.

2664 J . Org. Chem., Vol. 62, No. 8, 1997
Notes
LiAlH4.14 Other starting materials were commercially available.
Solvents were purified by standard methods before use.
7.3 Hz), 6.73 (d, 1H, J ) 15.6 Hz), 6.95-6.98 (m, 2H), 7.09-
7.12 (m, 2H), 7.16-7.17 (m, 1H), 7.21-7.25 (m, 1H), 7.36-7.40
(m, 2H); MS m/z 244 (M+). Anal. Calcd for C14H12O2S: C, 68.83;
H, 4.95; S, 13.12. Found: C, 68.59; H, 5.02; S, 13.04.
Ca t a lyt ic P h en oxyca r b on yla t ion of Allyl Alcoh ols.
A
mixture of a substituted allyl alcohol (2 mmol), 2 (226 mg, 2.4
mmol), Pd(OAc)2 (22 mg, 0.1 mmol), PPh3 (52 mg, 0.2 mmol),
and benzene (5 mL) was placed in a 50 mL stainless steel
autoclave. Then, carbon monoxide (5 atm at room temperature)
was charged, and the mixture was magnetically stirred at 100
°C for 18 h. In the reaction under a normal pressure of carbon
monoxide, a 100 mL two-necked flask equipped with a balloon
and a rubber cup was used. After cooling, the reaction mixture
was poured into dilute hydrochloric acid, extracted with ether,
and dried over sodium sulfate. The product was isolated by
column chromatography on silica gel using hexane-methylene
chloride as eluent.
(E)-P h en yl 4-(2-n a p h th yl)-3-bu ten oa te (14): mp 104-105
1
°C; H NMR δ 3.56 (dd, 2H, J ) 1.5, 6.8 Hz), 6.53 (dt, 1H, J )
15.6, 6.8 Hz), 6.77 (d, 1H, J ) 15.6 Hz), 7.11-7.14 (m, 2H), 7.22-
7.26 (m, 1H), 7.37-7.47 (m, 4H), 7.62-7.64 (m, 1H), 7.75-7.82
(m, 4H); MS m/z 288 (M+). Anal. Calcd for C20H16O2: C, 83.31;
H, 5.59. Found: C, 82.92; H, 5.60.
P h en yl 3-h ep ten oa te (16) (E:Z ) 87:13):11 1H NMR δ 0.92
(t, 3H, J ) 7.3 Hz), 1.39-1.46 (m, 2H), 2.03-2.08 (m, 2H), 3.27
(dd, 2H, J ) 1.0, 5.4 Hz, E), 3.34 (d, 2H, J ) 5.4 Hz, Z), 5.64-
5.68 (m, 2H), 7.07-7.39 (m, 5H); MS m/z 204 (M+).
(E)-(4-Meth oxyp h en yl) 4-p h en yl-3-bu ten oa te (18): mp
82-83 °C; 1H NMR δ 3.48 (dd, 2H, J ) 1.5, 7.3 Hz), 3.79 (s,
3H), 6.40 (dt, 1H, J ) 15.6, 7.3 Hz), 6.55 (d, 1H, J ) 15.6 Hz),
6.87-6.91 (m, 2H), 7.00-7.03 (m, 2H), 7.23-7.42 (m, 5H); MS
m/z 268 (M+). Anal. Calcd for C17H16O3: C, 76.10; H, 6.01.
Found: C, 76.08; H, 6.01.
(E)-P h en yl 4-p h en yl-3-bu ten oa te (3):11 1H NMR δ 3.50 (dd,
2H, J ) 1.5, 6.8 Hz), 6.40 (dt, 1H, J ) 15.6, 6.8 Hz), 6.61 (d, 1H,
J ) 15.6 Hz), 7.09-7.42 (m, 10H); MS m/z 238 (M+).
(E)-P h en yl 4-(4-m eth oxyp h en yl)-3-bu ten oa te (6): mp 65-
67 °C; 1H NMR δ 3.47 (dd, 2H, J ) 1.5, 7.3 Hz), 3.81 (s, 3H),
6.25 (dt, 1H, J ) 15.6, 7.3 Hz), 6.54 (d, 1H, J ) 15.6 Hz), 6.84-
6.88 (m, 2H), 7.09-7.12 (m, 2H), 7.21-7.25 (m, 1H), 7.32-7.40
(m, 4H); MS m/z 268 (M+). Anal. Calcd for C17H16O3: C, 76.10;
H, 6.01. Found: C, 75.74; H, 6.07.
(E)-P h en yl 4-(4-m eth ylp h en yl)-3-bu ten oa te (8): mp 34-
36 °C; 1H NMR δ 2.34 (s, 3H), 3.48 (dd, 2H, J ) 1.5, 6.8 Hz),
6.34 (dt, 1H, J ) 15.6, 6.8 Hz), 6.57 (d, 1H, J ) 15.6 Hz), 7.08-
7.14 (m, 4H), 7.22-7.26 (m, 1H), 7.30 (d, 2H, J ) 7.8 Hz), 7.36-
7.40 (m, 2H); MS m/z 252 (M+). Anal. Calcd for C17H16O2: C,
80.93; H, 6.39. Found: C, 80.53; H, 6.43.
(E)-(3-Ch lor op h en yl) 4-p h en yl-3-bu ten oa te (19): mp 59-
60 °C; 1H NMR δ 3.49 (dd, 2H, J ) 1.5, 7.3 Hz), 6.37 (dt, 1H, J
) 15.6, 7.3 Hz), 6.61 (d, 1H, J ) 15.6 Hz), 7.01-7.04 (m, 1H),
7.14-7.16 (m, 1H), 7.21-7.37 (m, 5H), 7.40-7.42 (m, 2H); MS
m/z 272, 274 (M
+). Anal. Calcd for C16H13O2Cl: C, 70.46; H,
4.80; Cl, 13.00. Found: C, 70.38; H, 4.83; Cl, 12.98.
(E)-Bu tyl 4-p h en yl-3-bu ten oa te (21):8 1H NMR δ 0.94 (t,
3H, J ) 7.3 Hz), 1.39 (tq, 2H, J ) 7.3, 7.3 Hz), 1.60-1.67 (m,
2H), 3.24 (dd, 2H, J ) 1.5, 7.3 Hz), 4.12 (t, 2H, J ) 6.8 Hz), 6.30
(dt, 1H, J ) 15.6, 7.3 Hz), 6.49 (d, 1H, J ) 15.6 Hz), 7.20-7.38
(m, 5H); MS m/z 218 (M+).
(E)-P h en yl 4-(4-ch lor op h en yl)-3-bu ten oa te (10): mp 63-
1
64 °C; H NMR δ 3.49 (dd, 2H, J ) 1.5, 7.3 Hz), 6.38 (dt, 1H, J
) 15.6, 7.3 Hz), 6.56 (d, 1H, J ) 15.6 Hz), 7.21-7.40 (m, 9H);
MS m/z 272, 274 (M+). Anal. Calcd for C16H13O2Cl: C, 70.46;
H, 4.80; Cl, 13.00. Found: C, 70.39; H, 4.85; Cl, 13.08.
(E)-P h en yl 4-(2-th ien yl)-3-bu ten oa te (12): mp 54-55 °C;
1H NMR δ 3.46 (dd, 2H, J ) 1.5, 7.3 Hz), 6.23 (dt, 1H, J ) 15.6,
Stoich iom etr ic Ca r bon yla tion of [P d (η3-1-p h en yla llyl)-
(OAc)]2 (22) in th e P r esen ce of P P h 3. A mixture of ROH (1
or 2 mmol), 22 (57 mg, 0.1 mmol), PPh3 (52 mg, 0.2 mmol),
bibenzyl (ca. 10 mg) as an internal standard, and toluene (5
mL) was stirred under CO (1 atm) at 80 °C. The time course of
the reaction was monitored by GLC.
(14) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett.
1975, 16, 4467.
J O962387N