Palladium-catalyzed carbonylative negishi-type coupling of aryl iodides with benzyl chlorides

Article abstract of DOI:10.1002/asia.201100627

Do the competition: The synthesis of 1,2-diarylethanones has been accomplished using the palladium-catalyzed coupling of aryl iodides and CO/benzyl chlorides or benzoyl chlorides. These reactions proceed smoothly in the presence of zinc powder to afford the products in moderate to excellent yields.

Full text of DOI:10.1002/asia.201100627

COMMUNICATION
DOI: 10.1002/asia.201100627
Palladium-Catalyzed Carbonylative Negishi-type Coupling of Aryl Iodides
with Benzyl Chlorides
Xiao-Feng Wu, Johannes Schranck, Helfried Neumann, and Matthias Beller*[a]
Palladium-catalyzed coupling reactions have become pow-
erful and attractive methodologies in organic synthesis.[1,2]
Depending on the carbon nucleophile, important name reac-
tions such as Suzuki,[3] Kumada,[4] Hiyama,[5] Stille,[6] and
Negishi reactions[7] have been developed over the past four
decades. In general, in these reactions pre-formed organo-
metallic nucleophiles, for example, RZnX, RMgX, RSnX,
etc. are used, which sometimes limits the application of
these methodologies.[3–7] For example, organozinc reagents
are usually prepared by transmetalation of organomagnesi-
um reagents with zinc halides or by the direct insertion of
Rieke zinc into organic halides.[8] Obviously, the in situ gen-
eration of the active organometallic reagent, by combination
of commercially available zinc dust with organic halides and
a subsequent coupling reaction, avoids the handling of such
air- and moisture-sensitive compounds.[9] In this respect, the
recent reports by Lipshutz and co-workers are interesting.
They described the cross-coupling between benzyl halides
and aryl halides in the presence of zinc.[9] The advantages of
such procedures are obvious compared to previous reports,
because an additional synthetic step is omitted.[8]
In addition to the coupling of aryl halides with carbon nu-
cleophiles, the related catalytic carbonylation reactions have
also shown impressive development since the pioneering
work of R. Heck and co-workers.[10,11] We have a long-stand-
ing interest in such palladium-catalyzed carbonylation reac-
tions.[12] More recent developments from our group include
the aminocarbonylation of aryl halides to generate primary
amides using ammonia,[12b,c] the carbonylative Heck reac-
tions of aryl/vinyl triflates to afford chalcones,[12d] the car-
ful example applying aryl iodides and alkyl iodides in the
presence of stoichiometric amounts of zinc-copper is known,
from the work of Yoshida and co-workers. Using benzyl hal-
ides instead of alkyl halides, 1,2-diarylethanones should be
obtained easily in a straightforward manner. Notably, this
structural motif is used in organic synthesis for the prepara-
tion of potentially bio-active compounds as well as new ap-
plications for material science.[15] Unfortunately, using
benzyl chlorides as substrates, low temperatures (À788C to
À608C) were required and the substrate scope has been lim-
ited to only four examples so far.[14c]
Based on the synthetic utility of 1,2-diarylethanones and
our continuing interest in carbonylation reactions, herein,
we report a general and efficient palladium-catalyzed car-
bonylative coupling of aryl iodides with benzyl chlorides in
the presence of zinc.
Initially, the coupling of benzyl chloride and iodobenzene
using 1 equivalent of commercially available zinc was car-
ried out in 1,4-dioxane using 1 mol% of PdACTHNURGTNEUNG(OAc)2/DPPB
(1,4-bis(diphenylphosphino)butane). Under 10 bar of CO
after 16 hours at 1008C, 63% of the desired product was
formed with 70% conversion of iodobenzene (Table 1,
entry 1). When the reaction was carried out in toluene, no
ketone was formed. However, to our surprise, instead ben-
zylation of toluene occurred (Table 1, entry 2).[16] The use of
1,2-dimethoxyethane (DME) as a solvent led to low yield
(35% of 1,2-diphenylethanone) and moderate conversion
(54%) (Table 1, entry 5). Moderate yields were also ob-
served when the reaction was performed under 1 bar CO or
at 608C (Table 1, entries 6 and 7). Using an excess of benzyl
chloride and zinc (1.2 equiv) gave the highest yield of 1,2-di-
phenylethanone (78%; Table 1, entry 8).
Next, 15 different phosphines, including mono- and biden-
tate ligands, were tested (for a detailed list of ligands see
the Supporting Information). However, no significant influ-
ence of the ligand structure was observed in the model reac-
tion. From the work of Knochel and co-workers, it is known
that the addition LiCl to the respective organometallic com-
pound can improve the efficiency of the coupling process.[17]
Hence, this additive was also tested, but again no significant
difference in the product yield was observed. On the other
hand, higher conversion was achieved in the presence of
2 equivalents of benzyl chloride (70%; Table 1, entry 9). In
addition to the coupling with iodobenzene, the remaining
benzyl chloride was converted into 1,2-diphenylethane to-
gether with a very small amount of 1,3-diphenylpropanone.
À
bonylative coupling of aryl iodides with heteroarenes by C
H activation,[12e] and the reductive carbonylation of aryl bro-
mides to produce aldehydes, which is also applied on an in-
dustrial ton-scale.[12f] Whilst palladium-catalyzed carbonyla-
tive Suzuki coupling reactions have become a straightfor-
ward and generally accepted route for aromatic ketone syn-
thesis,[13] the analogous carbonylative Negishi couplings have
been only rarely reported.[14] For instance, only one success-
[a] X.-F. Wu, J. Schranck, Dr. H. Neumann, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse e.V. an der Universitꢁt Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
Fax : (+49)381-1281-5000
E-mail: matthias.beller@catalysis.de
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201100627.
40
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 40 – 44

Table 1. Palladium-catalyzed Negishi-type carbonylation: optimization of
the model reaction.[a]
Table 2. Palladium-catalyzed Negishi-type carbonylation of aryl iodides:
scope and limitations.[a]
Entry
Solvent
Conv. [%][b]
Yield [%][b]
Entry
1
Aryl iodide
Ketone
Yield [%][b]
1
2
3
4
1,4-dioxane
toluene
n-heptane
DMSO
70
0
0
63
0
0
78
75[c]
66[d]
0
0
5
DME
54
57
77
80
97
35
52
58
78
70
6[c]
7[d]
8[e]
9[f]
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
2
3
85
[a] PdACHTUNGTRENNUNG(OAc)2 (1 mol%), DPPB (1 mol%), solvent (2 mL), CO (10 bar),
iodobenzene (1 mmol), benzyl chloride (1 mmol), Zn (1 mmol), 1008C,
16 h. [b] Conversion and yield were determined by GC based on iodo-
benzene using hexadecane as internal standard. [c] 608C. [d] CO (1 bar).
[e] Benzyl chloride (1.2 mmol), Zn (1.2 mmol). [f] Benzyl chloride
(2 mmol), Zn (2 mmol). DMSO=dimethyl sulfoxide.
80
80[c]
4
5
6
7
71
80
84
With suitable conditions in hand, we then tested other
substrates (Tables 2 and 3); here, 24 different 1,2-diaryletha-
nones were synthesized in moderate to very good yield (42–
91%).
Ortho-, meta-, and para-methyl-substituted iodobenzenes
gave the corresponding ketones in good yields (71–85%;
Table 2, entries 2–4). Both electron-donating and electron-
withdrawing substituted iodoarenes were successfully trans-
formed into the desired ketones in good yields (60–88%;
Table 2, entries 7–15). Para-bromo- and para-chloro-substi-
tuted arenes also gave 88% and 81% yield of the corre-
sponding ketones, respectively (Table 2, entries 12 and 13).
3-Iodothiophene, as a representative example of a heteroar-
ene, resulted in 75% of the desired ketone (Table 2,
entry 16). Using bromobenzene instead of iodobenzene
under our typical reaction conditions gave 1,3-diphenylpro-
panone in 45% yield (not shown). Moreover, 4-bromoben-
zonitrile reacted with benzyl chloride to form the corre-
sponding product in 8% yield. However, the reaction of 4-
bromoanisole with benzyl chloride did not give any desired
product under the typical reaction conditions. This result
demonstrates the general scope for aryl bromides under our
reaction conditions. However, for practical use, further opti-
mization and the development of an improved catalyst sys-
tems is needed. On the other hand, various substituted
benzyl chlorides can also be used in this coupling process
with iodobenzene and moderate to excellent yield was at-
tained (42–91%; Table 3).
88
85[c]
8
9
85
68
63[c]
10
11
12
13
78
83
88
81
Finally, the established reaction conditions were tested for
the cross-coupling of benzoyl chlorides with benzyl chlorides
under CO-free conditions. Selected examples are listed in
Table 4. Again, various substitution patterns, both on the
benzoyl and benzyl moieties of the coupling partners, were
tolerated. Here, 1,2-diarylethanones were obtained in 70–
90% yield under an argon atmosphere.[18] It should be noted
Chem. Asian J. 2012, 7, 40 – 44
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41

M. Beller et al.
COMMUNICATION
Table 3. Palladium-catalyzed Negishi-type carbonylation of benzyl chlori-
des.[a]
Table 2. (Continued)
Entry
Aryl iodide
Ketone
Yield [%][b]
85
14
Entry
1
Benzyl Chloride
Ketone
Yield [%][b]
15
60
82
80[c]
75
16
70[c]
2
63
[a] PdACHTUNGTRENNUNG(OAc)2 (1 mol%), DPPB (1 mol%), 1,4-dioxane (2 mL), CO
(10 bar), aryl iodide (1 mmol), benzyl chloride (1.2 mmol), Zn
(1.2 mmol), 1008C, 16 h. [b] Yield was determinated by GC using hexade-
cane as internal standard based on aryl iodides. [c] Yield of isolated prod-
uct. [d] Iodobenzene (10 mmol), benzyl chloride (12 mmol), Zn
(12 mmol), 1,4-dioxane (15 mL); yield determined by GC analysis using
hexadecane as an internal standard based on iodobenzene.
3
4
5
6
7
87
42
90
91
that no desired product was detected when the reaction was
performed in the absence of palladium and ligand; instead,
decomposition of starting materials occurred.
Based on these results, the following reaction mechanism
is proposed in Scheme 1. In principle, the active palladi-
um(0) catalyst as well as the zinc species might undergo ad-
dition to the aryl iodide or the benzyl chloride. In a compe-
tition experiment on the insertion of zinc into iodobenzene
and benzyl chloride, the insertion of zinc into benzyl chlo-
ride was four times faster compared to the insertion of zinc
into iodobenzene. Hence, we conclude that the desired
product 1 is mainly produced via cycle I. After oxidative ad-
dition of palladium(0) to iodobenzene, insertion of carbon
monoxide takes place to give the acylpalladium complex.
Subsequent reaction with the in situ formed benzylic zinc
reagent provides 1,2-diphenylethanone after reductive elimi-
nation. Byproducts 2 and 3, which resulted primarily from
the oxidative addition of palladium(0) into benzyl chloride,
are formed from cycle II.
85
81[c]
8
76
[a] PdACTHUNTGRNE(NUG OAc)2 (1 mol%), DPPB (1 mol%), 1,4-dioxane (2 mL), CO
(10 bar), iodobenzene (1 mmol), benzyl chlorides (1.2 mmol), Zn
(1.2 mmol), 1008C, 16 h. [b] Yield was determined by GC using hexade-
cane as internal standard based on iodobenzene. [c] Yield of isolated
product.
In conclusion, an efficient and general procedure for the
preparation of 1,2-diarylethanones, which represent interest-
ing building blocks for organic synthesis, has been estab-
lished. Starting from readily available aryl iodides and
benzyl chlorides in the presence of commercially accessible
zinc powder, more than twenty 1,2-diarylethanone deriva-
tives have been produced in moderate to excellent yields.
Thus, this synthetic procedure allows for a straightforward
access to this class of compounds, which is complementary
to known methodologies. Furthermore, the optimized reac-
tion conditions can be successfully applied for the coupling
of benzoyl chlorides and benzyl chlorides under CO-free
conditions. This observation makes the latter methodology
valuable for laboratory scale synthesis without the need of
carbon monoxide equipment.
Scheme 1. Proposed reaction mechanism.
42
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ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 40 – 44

Carbonylative Coupling of Aryl Iodides with Benzyl Chlorides
Table 4. Palladium-catalyzed Negishi-Type coupling of benzoyl chlorides
with benzyl chlorides.[a]
an internal standard. After proper mixing of the reaction mixture, an ali-
quot of the solution was used for GC and GC-MS analysis. For purifica-
tion, the solution was extracted 3–5 times with 2–3 mL of ethyl acetate.
After evaporation of the organic solvent, the residue was adsorbed on
silica gel and the crude product was purified by column chromatography
using n-heptane/EtOAc (50:1) as the eluent.
General procedure for the cross-coupling of benzoyl chloride with benzyl
chloride
Entry
1
Ketone
Yield [%][b]
A 4 mL vial was charged with PdACHTNUTRGENNG(U OAc)2 (1 mol%), DPPB (1 mol%), Zn
(1.2 mmol: powder, CAS: 7440-66-6), and a stirring bar. Then, 2 mL 1,4-
dioxane (distilled), 1 mmol of benzoyl chloride, and 1.2 mmol of benzyl
chloride were injected by syringe. The vial (or several vials) was (were)
placed in an alloy plate, which was heated for 3 h at 1008C. After the re-
action hadfinished, the vial was cooled down to room temperature and
40 mg of hexadecane was added as an internal standard. After proper
mixing of the reaction mixture, an aliquot of solution was used for GC
and GC-MS analysis.
90
2
3
83
85
Acknowledgements
The authors thank the state of Mecklenburg-Vorpommern and the Bun-
desministerium fꢀr Bildung und Forschung (BMBF) for financial sup-
port.
4
5
6
7
8
89
81
80
83
70
Keywords: 1,2-diarylethanones
·
benzyl chlorides
·
carbonylation · Negishi coupling · palladium
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Received: July 18, 2011
Revised: August 21, 2011
Published online: October 11, 2011
44
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