Synthesis of ketones from acyl chlorides and triorganoindium reagents by Pd-catalyzed cross-coupling

Article abstract of DOI:10.1080/00397910600910625

Triorganoindium reagents prepared from indium tribromide and 3 equiv of organolithium reagents react with acyl chlorides in palladium-catalyzed cross-coupling for preparation of new ketones. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910600910625

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Synthesis of Ketones from Acyl Chlorides and
Triorganoindium Reagents by Pd‐Catalyzed
Cross‐Coupling
C. Croix a , A. Balland‐Longeau a , A. Duchêne b & J. Thibonnet b
a CEA Le Ripault, Materials Department , Monts, France
b Laboratoire de Synthèse et Physicochimie Organique et Thérapeutique ,
Faculté des Sciences de Tours, Parc de Grandmont , Tours, France
Published online: 24 Nov 2006.
To cite this article: C. Croix , A. Balland‐Longeau , A. Duchêne & J. Thibonnet (2006) Synthesis of
Ketones from Acyl Chlorides and Triorganoindium Reagents by Pd‐Catalyzed Cross‐Coupling, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:21,
3261-3270, DOI: 10.1080/00397910600910625
To link to this article: http://dx.doi.org/10.1080/00397910600910625
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Synthetic Communicationsw, 36: 3261–3270, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600910625
Synthesis of Ketones from Acyl Chlorides
and Triorganoindium Reagents by
Pd-Catalyzed Cross-Coupling
C. Croix and A. Balland-Longeau
CEA Le Ripault, Materials Department, Monts, France
ˆ
A. Duchene and J. Thibonnet
` ´
Laboratoire de Synthese et Physicochimie Organique et Therapeutique,
´
Faculte des Sciences de Tours, Parc de Grandmont, Tours, France
Abstract: Triorganoindium reagents prepared from indium tribromide and 3 equiv of
organolithium reagents react with acyl chlorides in palladium-catalyzed cross-coupling
for preparation of new ketones.
Keywords: Indium, ketones, palladium catalyst, triorganoindium
The utilization of metals in organic synthesis, particularly to create
carbon–carbon bond(s), is an important ongoing research theme. Transition-
metal-catalyzed cross-coupling reactions of organic electrophiles with organo-
metallic coupling partners represent one of the most powerful methods for the
construction of carbon–carbon bonds.[1] Since the emergence of indium-
mediated organic reactions in aqueous media, indium has attracted considerable
attention from organic chemists[2] for various organic transformations such as
conjugate addition,[3] allylic substitution reactions,[4] and allylation of
carbonyl compounds.[5] This interest is due to specific properties of indium,
such as its low first oxidation potential, which makes it a very selective
Received in Poland April 4, 2006
Address correspondence to Jerome Thibonnet, Laboratoire de Synthese et Physico-
´ ´
chimie Organique et Therapeutique, EA 3857, Faculte des Sciences de Tours, Parc de
`
Grandmont, 37200 Tours, France. E-mail: jerome.thibonnet@univ-tours.fr
3261

3262
C. Croix et al.
Scheme 1. Synthesis of triorganoindium reagents.
reagent.[6] Furthermore, indium metal or salts such as InBr3 are resistant to air
and oxygen at an ambient temperature, as well as to boiling water and alkali
solutions. Consequently, there is no need for specific activation of indium by
´
heat, sonication, or acid catalysis as there is for other elements. Perez et al.
have recently reported the first Pd-catalyzed cross-coupling reactions of
triorganoindium compounds with organic halides.[7] On the basis of these
cross-coupling reactions, it was found that a variety of organoindiums could
be employed as nucleophilic coupling partners.[8] This reaction was extended
withindiumreagents, suchastetraorganoindates[9] inPd-catalyzedcarbonylative
cross-coupling reactions. We describe here a successful Pd-catalyzed cross-
coupling reaction with specific triorganoindium and acyl chlorides.
Triorganoindium compounds R3In were easily prepared as solutions in
tetrahydrofuran (THF) by reaction of InBr3 with 3 equiv of organolithium
reagents (Scheme 1).[10]
For the polymerization study,[11] these organoindiums were characterized
by 1H NMR and 13C NMR. However, these compounds are unstable in water
and insoluble after complete removal of solvents. After partial vacuum
evaporation of THF, the triorganoindiums were introduced in THF-d8,
1
where they could be characterized by H and 13C NMR. The yields of these
reactions were determined via iodolysis according to the following scheme,
with 60–77% yields of the iodo compound derivatives (Scheme 2).
After characterization of the triarylindiums, we engaged them in cross-
coupling reactions. The reaction of In-1 with benzoylchloride (entry 1,
Scheme 2. Iodolysis.

Synthesis of Ketones from Acyl Chlorides and Triorganoindium
3263
Table 1. Results of the palladium-catalyzed cross-coupling reaction of triorgano-
indium reagents with acyl chlorides
Isolated
yield
(%)
Entry R3In
RCOCl
Producta
No.
1
2
In-1
In-1
1[12]
80
2[13]
82
3
4
5
In-2
In-2
In-3
3[1]
65
70
56
4
5[15]
6
In-3
6
40
7
8
9
In-1
In-1
In-1
7[16]
55
74
52
8
9
10
In-2
10
85
1
aAll products were identified by their H NMR, 13C NMR, and MS spectral data.
Table 1) with 1% tetrakis(triphenylphosphine)palladium(0) allowed us to
obtain the corresponding ketone (80% yield). Other acyl chlorides were
engaged under similar conditions to determine the scope of the reaction
(Scheme 3). Reactions of triorganoindium reagents (In-1, 2, or 3) with a

3264
C. Croix et al.
wide range of acyl chorides provided fair to good yields of corresponding
ketones (Table 1, entries 2–8). The three styryl groups attached to the
indium metal were transferred in all cases, in contrast with all other metals
employed in cross-coupling reactions.
After the first series of reactions using triorganoindium, we decided to
explore the use of the two reactional sites of 4-bromobenzoyl chloride in a
one-pot Pd-catalyzed cross-coupling reaction to investigate whether it was
possible to transfer the two tristyryl groups (Scheme 4). The results are
reported in Table 1 (entries 9 and 10).
In conclusion, we describe the synthesis of new ketones by palladium-
catalyzed cross-coupling reaction with triarylindium compounds and acyl
chlorides. The study of polymerization of tristyrylindium compounds is in
progress in our laboratory.
EXPERIMENTAL
General Methods
All reactions were performed in oven-dried glassware under positive argon
pressure. Toluene was dried and freshly distilled from sodium. 1H NMR
spectra were recorded at 200 MHz or at 300 MHz using CDCl3 as solvent.
Results, reported using the residual proton resonance of CDCl3
(dH ¼ 7.25 ppm) as the internal reference, were as follows (in order): chemical
shift (d in ppm relative to Me4Si), multiplicity (s, d, t, q, quint, m, b for singlet,
doublet, triplet, quartet, quintuplet, multiplet, and broad), and coupling
constants (J in Hz). 13C NMR spectra were recorded at 50 MHz or 75 MHz
using CDCl3 solvent peak at dC ¼ 77.0 ppm as the reference. Electron impact
mass spectra (EIMS) were measured at 70 eV by gas chromatography/mass
spectrometry systems (GC/MS) or direct introduction mode. IR spectra were
recorded on a Perkin Elmer Spectrum One FT-IR spectrophotometer. Melting
points were taken on a Bu¨chi B-540 and are uncorrected. Standard column chrom-
˚
atography was performed on Merck silica gel (60 A, 230–400 mesh silica gel) by
flash column chromatography techniques. Analytical thin-layer chromatography
(TLC) was conducted on Merck precoated silica-gel 60 F254 plates.
Scheme 3. Palladium-catalyzed cross-coupling reaction of triorganoindium reagents
with acyl chlorides.

Synthesis of Ketones from Acyl Chlorides and Triorganoindium
3265
Scheme 4. Palladium-catalyzed twofold cross-coupling reactions with triorgano-
indium reagents.
Typical Procedure for the Preparation of Triorganoindium
Reagents
BuLi (2.5 M) in hexane (2.88 mL, 7.20 mmol) was added to a solution of
p-bromostyrene (1.29 g, 7.08 mmol) in dry THF (13 mL) at 2788C under
an argon atmosphere. After 10 min of stirring, indium tribromide (0.84 g,
2.36 mmol) in dry THF (15 mL) was added dropwise, and the reaction
mixture was allowed to warm to rt over 15 h. The mixture was not hydrolyzed,
but 5–6 mL of this solution was concentrated in vacuo to obtain a viscous
solution. The product obtained was then immediately mixed in solution in a
minimum of THF-d8 for NMR analysis.
Data
1
Tri(p-vinylphenyl)indium(III) (In-1). H NMR (THF-d8, 200 MHz): d 5.00
(dd, J ¼ 11/1.3 Hz, 3H), 5.64 (dd, J ¼ 17.7/1.3 Hz, 3H), 6.63 (dd, J ¼ 11/
17.7 Hz, 3H), 7.23 (d, J ¼ 7.8 Hz, 6HAr), 7.66 (d, J ¼ 7.8 Hz, 6HAr); 13C
NMR (THF-d8, 50 MHz): d 110.9 (3C), 124.8 (6CAr), 135.3 (3C), 139.3
(3CAr), 139.6 (6CAr), 160.1 (3CAr).
1
Tri(m-vinylphenyl)indium(III) (In-2). H NMR (THF-d8, 200 MHz): d 5.00
(dd, J ¼ 11/1.7 Hz, 3H), 5.60 (dd, J ¼ 17.6/1.5 Hz, 3H), 6.64 (dd, J ¼ 11/
17.6 Hz, 3H), 7.09 (m, 6H), 7.59 (d, J ¼ 6.4 Hz, 3H), 7.77 (bs, 3H); 13C
NMR (CDCl3, 50 MHz): d 111.2 (3C), 123.8 (3CAr), 126.9 (3CAr), 135.8
(3CAr), 137.8 (3C), 139.1 (3CAr), 139.4 (3CAr), 159.0 (3CAr).
1
Tri(o-vinylphenyl)indium(III) (In-3). H NMR (THF-d8, 200 MHz): d 4.76
(dd, J ¼ 11/1.7 Hz, 3H), 5.41 (dd, J ¼ 17.3/1.7 Hz, 3H), 6.91–7.13
(m, 6HAr þ 3H), 7.45 (d, J ¼ 8.6 Hz, 3HAr), 7.76 (d, J ¼ 6.7 Hz, 3HAr); 13C
NMR (CDCl3, 50 MHz): d 110.4 (3C), 123.4 (3CAr), 126.1 (3CAr), 126.3
(3CAr), 140.7 (3C), 145.0 (3CAr), 146.3 (3CAr), 161.5 (3CAr).
General Procedure for the Preparation of Ketones
Approximately 0.1 M triarylindium in THF (16 mL, 1.6 mmol) was added to a
solution of benzoyl chloride (4.8 mmol) in dry THF (18 mL) and Pd(PPh3)4

3266
C. Croix et al.
(56 mg, 0.05 mmol, 1 mol%) in an argon atmosphere. The reaction mixture
was stirred at 658C for 3 h. The reaction was quenched by the addition of
ethanol (10 mL). The solvent was removed under reduced pressure, and the
residue was diluted with Et2O. The organic layer was washed successively
with 5% aqueous HCl (20 mL), saturated aqueous NaHCO3 (25 mL), and
brine (20 mL). The organic layer was dried (MgSO4) and the solvents
removed in vacuo to give the crude product, which was purified by column
chromatography (silica gel) using light petroleum ether (40–608C)–Et2O
(90/10). Unknown compounds or compounds for which incomplete
1
physical data were reported in the literature were characterized by FTIR, H
and 13C NMR, and MS spectral data.
Selected Data
Phenyl( p-vinylphenyl)ketone (1). Oil; IR (neat) n ¼ 3052, 1646, 1602,
1
1448 cm21; H NMR (CDCl3, 200 MHz): d 5.38 (dd, J ¼ 11/0.7 Hz, 1H),
5.96 (dd, J ¼ 17.6/0.7 Hz, 1H), 6.81 (dd, J ¼ 11/17.6 Hz, 1H), 7.46–7.82
(m, 9HAr); 13C NMR (CDCl3, 50 MHz): d 116.6, 126.7 (2CAr), 128.9
(2CAr), 130.4 (2CAr), 131.0 (2CAr), 132.8 (CAr), 137.0, 137.7 (CAr), 138.7
(CAr), 142.2 (CAr), 195.3; MS (EI, 70 eV): m/z (%) ¼ 208 (Mþ, 69), 131
(100), 105 (33), 103 (23), 77 (51), 51 (14).
p-Bromophenyl( p-vinylphenyl)ketone (2). Solid; mp: 129–1318C; IR
(KBr) n ¼ 3088, 3060, 1660, 1597, 1478 cm21
;
1H NMR (CDCl3,
200 MHz): d 5.36 (d, J ¼ 11 Hz, 1H), 5.95 (d, J ¼ 17.7 Hz, 1H), 6.82 (dd,
J ¼ 11/17.7 Hz, 1H), 7.58–7.78 (m, 8HAr); 13C NMR (CDCl3, 50 MHz): d
116.7, 126.8 (2CAr), 127.5 (CAr), 130.9 (2CAr), 132.2 (2CAr), 132.3 (2CAr),
136.9, 137.2 (CAr), 137.9 (CAr), 142.5 (CAr), 194.3; MS (EI, 70 eV): m/z
(%) ¼ 288 (Mþ, 28), 286 (Mþ, 29), 207 (13), 185 (15), 183 (15), 157 (11),
155 (11), 131 (100), 103 (27), 77 (39).
Phenyl(m-vinylphenyl)ketone (3). Oil; IR (neat) n ¼ 3089, 3065, 1645, 1602,
1479 cm21; 1H NMR (CDCl3, 200 MHz): d 5.30 (dd, J ¼ 11/0.8 Hz, 1H), 5.85
(dd, J ¼ 17.6/0.8 Hz, 1H), 6.74 (dd, J ¼ 11/17.6 Hz, 1H), 7.45–7.68
(m, 6HAr), 7.78–7.85 (m, 3HAr); 13C NMR (CDCl3, 50 MHz): d 115.3, 128.4
(CAr), 129.1 (2CAr), 129.3 (CAr), 130.0 (CAr), 130.4 (CAr), 130.7 (2CAr), 133.1
(CAr), 137.2, 138.7, 138.9, 139.2 (3CAr), 195.9; MS (EI, 70 eV): m/z
(%) ¼ 208 (Mþ, 100), 131 (55), 105 (43), 103 (20), 77 (74), 51 (33).
p-Bromophenyl(m-vinylphenyl)ketone (4). Solid; mp: 85–868C; IR (KBr)
1
n ¼ 3092, 3062, 1650, 1584, 1480 cm21; H NMR (CDCl3, 200 MHz): d
5.30 (dd, J ¼ 11/0.5 Hz, 1H), 5.88 (dd, J ¼ 17.6/0.6 Hz, 1H), 6.78 (dd,
J ¼ 11/17.6 Hz, 1H), 7.46 (t, J ¼ 7.6 Hz, 1HAr), 7.62–7.83 (m, 7HAr); 13C
NMR (CDCl3, 50 MHz): d 115.5, 127.9 (CAr), 128.4 (CAr), 129.4 (CAr),

Synthesis of Ketones from Acyl Chlorides and Triorganoindium
3267
130.0 (CAr), 130.7 (CAr), 132.5 (4CAr), 137.1, 137.6 (CAr), 138.8, 139.0
(2CAr), 195.0; MS (EI, 70 eV): m/z (%) ¼ 288 (Mþ, 68), 286 (Mþ, 68),
207 (49), 185 (62), 183 (62), 157 (25), 155 (25), 131 (100), 103 (34), 77
(42), 51 (17).
Phenyl(o-vinylphenyl)ketone (5). Oil; IR (neat) n ¼ 3062, 3026, 1663, 1596,
1
1478 cm21; H NMR (CDCl3, 200 MHz): d 5.17 (dd, J ¼ 11/1.2 Hz, 1H),
5.73 (dd, J ¼ 17.4/1.2 Hz, 1H), 6.76 (dd, J ¼ 11/17.4 Hz, 1H), 7.33–7.58
(m, 6HAr), 7.73–7.79 (m, 3HAr); 13C NMR (CDCl3, 50 MHz): d 116.4,
126.5 (CAr), 128.0 (CAr), 129.3 (2CAr), 129.6 (CAr); 130.9 (2CAr), 131.0
(CAr), 133.9 (CAr), 135.3, 137.4 (CAr), 138.8, 139.3 (2CAr), 197.6; MS (EI,
70 eV): m/z (%) ¼ 208 (Mþ, 100), 207 (52), 179 (24), 178 (20), 103 (16),
77 (54), 51 (25).
p-Bromophenyl(o-vinylphenyl)ketone (6). Oil; IR (neat) n ¼ 3088, 3063,
1
1666, 1584, 1478 cm21; H NMR (CDCl3, 200 MHz): d 5.19 (dd, J ¼ 11/
1.1 Hz, 1H), 5.72 (dd, J ¼ 17.4/1.1 Hz, 1H), 6.77 (dd, J ¼ 11/17.4 Hz,
1H), 7.34–7.36 (m, 2HAr), 7.45–7.52 (m, 1HAr), 7.66 (bs, 4HAr), 7.74
(d, J ¼ 7.7 Hz, 1HAr); 13C NMR (CDCl3, 50 MHz): d 116.8, 126.7 (CAr),
128.1, 128.9 (2CAr), 129.3 (CAr), 132.0 (CAr), 132.5 (2CAr), 132.6 (2CAr),
135.2, 137.5 (CAr), 137.7, 138.7 (2CAr), 196.6; MS (EI, 70 eV): m/z
(%) ¼ 288 (Mþ, 71), 287 (33), 286 (Mþ, 72), 285 (22), 208 (16), 207 (100),
206 (13), 179 (50), 178 (77), 157 (18), 155 (18), 131 (16), 103 (33), 77
(47), 76 (39), 75 (26), 51 (26), 50 (28).
Napht-2-yl(p-vinylphenyl)ketone (7). Solid; mp: 80–818C; IR (KBr)
1
n ¼ 3054, 1648, 1603, 1506, 1463 cm21; H NMR (CDCl3, 200 MHz): d
5.39 (dd, J ¼ 11/0.8 Hz, 1H), 5.97 (dd, J ¼ 17.6/0.8 Hz, 1H), 6.85 (dd,
J ¼ 11/17.6 Hz, 1H), 7.55–7.65 (m, 4HAr), 7.83–7.97 (m, 6HAr), 8.31 (bs,
1HAr); 13C NMR (CDCl3, 50 MHz): d 116.6, 126.9 (CAr), 127.0 (2CAr),
127.6 (CAr), 129.0 (CAr), 129.3 (CAr), 130.2, 131.2 (2CAr), 132.2 (1C),
133.5, 136.1, 136.3, 137.2 (4CAr), 138.0, 138.2 (CAr), 142.3 (CAr), 195.5;
MS (EI, 70 eV): m/z (%) ¼ 258 (Mþ, 100), 155 (61), 131 (60), 127 (57),
103 (27), 77 (44).
6-Bromohexyl( p-vinylphenyl)ketone (8). Solid; mp: 40–418C; IR (KBr)
1
n ¼ 3093, 3069, 2935, 1682, 1672, 1602, 1460 cm21; H NMR (CDCl3,
200 MHz): d 1.46–1.57 (m, 2H), 1.65–1.76 (m, 2H3), 1.81–1.88
(m, 2H5), 2.98 (t, J ¼ 7 Hz, 2H), 3.45 (t, J ¼ 7 Hz, 2H), 5.34 (dd,
J ¼ 11/0.7 Hz, 1H), 5.90 (dd, J ¼ 17.6/0.8 Hz, 1H), 6.78 (dd, J ¼ 11/
17.6 Hz, 1H), 7.51 (d, J ¼ 6.7 Hz, 2HAr), 7.94 (d, J ¼ 6.6 Hz, 2HAr); 13C
NMR (CDCl3, 50 MHz): d 24.1, 28.8, 33.8, 34.3, 38.7, 116.5, 127.0
(2CAr), 129.2 (2CAr), 137.1, 137.5 (CAr), 142.6 (CAr), 198.6; MS (EI,
70 eV): m/z (%) ¼ 282 (Mþ, 2), 280 (Mþ, 2), 146 (70), 131 (100), 103
(29), 77 (24).

3268
C. Croix et al.
General Procedure for the Preparation of Ketones (Table 1, entries
9 and 10)
Approximately 0.1 M triarylindium in THF (32 mL, 3.2 mmol) was added to
a solution of 4-bromo-benzoyl chloride (4.8 mmol) in dry THF (18 mL) and
Pd(PPh3)4 (56 mg, 0.05 mmol, 1 mol%) in an argon atmosphere. The
reaction mixture was stirred at 658C for 3 h. The reaction was quenched
by addition of ethanol (10 mL). The solvent was removed under reduced
pressure and the residue was diluted with Et2O. The organic layer was
washed successively with 5% aqueous HCl (20 mL), saturated aqueous
NaHCO3 (25 mL), and brine (20 mL). The organic layer was dried
(MgSO4) and the solvents removed in vacuo to give the crude product,
which was purified by column chromatography (silica gel) using light
petroleum ether (40–608C)–Et2O (90/10). Unknown compounds or
compounds for which incomplete physical data were reported in the
1
literature were characterized by FTIR, H and 13C NMR, and MS spectral
data.
Selected Data
p-[( p-Vinylphenyl)phenyl](p-vinylphenyl)ketone (9). Solid; mp: 169–
1
1718C (decomposition); IR (KBr) n ¼ 3085, 3026, 1700, 1604 cm21; H
NMR (CDCl3, 200 MHz): d 5.26 (dd, J ¼ 11/1 Hz, 1H), 5.38 (dd, J ¼ 11/
1 Hz, 1H), 5.86 (dd, J ¼ 17.6/1 Hz, 1H), 5.96 (dd, J ¼ 17.6/0.9 Hz, 1H),
6.71–6.92 (m, 2H), 7.53–7.90 (m, 12HAr); 13C NMR (CDCl3, 50 MHz): d
114.5, 116.6, 126.9 (2CAr), 127.4 (2CAr), 127.5 (2CAr), 127.7 (2CAr), 131.1
(2CAr), 131.3 (2CAr), 137.2, 137.4 (2C), 137.6, 138.1, 138.6 (3CAr), 140.2
(CAr), 142.4 (CAr), 145.2 (CAr), 195.0; MS (EI, 70 eV): m/z (%) ¼ 310
(Mþ, 100), 207 (62), 131 (43), 103 (25), 77 (26).
p-(m-Vinylphenyl)phenyl(m-vinylphenyl)ketone (10). Oil; IR (neat)
;
1H NMR (CDCl3, 200 MHz):
n ¼ 3087, 3059, 1657, 1602, 1480 cm21
d 5.31 (dd, J ¼ 11/2.3 Hz, 2H), 5.88 (d, J ¼ 17.6 Hz, 1H), 5.91 (dd,
J ¼ 17.6/0.8 Hz, 1H), 6.77–6.98 (m, 2H), 7.44–7.94 (m, 12HAr); 13C
NMR (CDCl3, 50 MHz): d 114.7, 115.4, 126.1 (2CAr), 127.0 (CAr), 127.5
(CAr), 127.7 (2CAr), 128.4 (CAr), 129.3 (CAr), 130.0 (CAr), 130.4 (CAr),
131.4 (2CAr), 137.2, 137.5 (1CAr), 137.7 (1C), 138.8, 139.3, 139.4 (3CAr),
141.2 (CAr), 145.7 (CAr), 195.5; MS (EI, 70 eV): m/z (%) ¼ 310 (Mþ, 94),
207 (100), 178 (48), 131 (24), 103 (22), 77 (21).
ACKNOWLEDGMENTS
We thank CEA Le Ripault for providing financial support and characterization.

Synthesis of Ketones from Acyl Chlorides and Triorganoindium
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