Palladium-catalyzed carbonylative coupling of aryl iodides with an organocopper reagent: A straightforward procedure for the synthesis of aryl trifluoromethyl ketones

Article abstract of DOI:10.1039/c6ra12287f

A palladium-catalyzed carbonylative coupling of aryl iodides with a (trifluoromethyl)copper reagent has been developed. A wide range of substrates have been transformed into their corresponding trifluoromethyl ketones in good to excellent yields under mild conditions with high efficiency and excellent functional-group compatibility. Preliminary mechanistic investigations suggest that the transmetallation of an acylpalladium intermediate with the (trifluoromethyl)copper reagent seems to be involved in the catalytic cycle. Notably, this report represents one of the few studies on carbonylative coupling with organocopper reagents.

Full text of DOI:10.1039/c6ra12287f

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DOI: 10.1039/C6RA12287F
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Palladium-Catalyzed Carbonylative Coupling of Aryl Iodides with
Organocopper Reagent: A Straightforward Procedure for the
Synthesis of Aryl Trifluoromethyl Ketones
Received 00th January 20xx,
Accepted 00th January 20xx
Fengxiang Zhu,a,b Guangfu Yang,*a Shaolin Zhou*a and Xiao-Feng Wu*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
A palladium-catalyzed carbonylative coupling of aryl iodides with compounds are generally required and the regioselectivity is
(trifluoromethyl)copper reagent has been developed. A wide often limited to the para position.[10] Reactions between
range of substrates have been transformed into their organometallic reagents (Grignard and oranolithium reagents)
corresponding trifluoromethyl ketones in good to excellent yields and trifluoroacetic acids derivatives have been extensively
under mild conditions with high efficiency and excellent used for the synthesis of aryl trifluoromethyl ketones; however
functional-group
compatibility.
Preliminary
mechanistic the low functional group tolerance and formation of double-
investigations suggest that the transmetallation of an addition by-products represent major limitations.[11] While
acylpalladium intermediate with the (trifluoromethyl)copper other methods such as oxidation of secondary trifluoromethyl
reagent seems to be involved in the catalytic cycle. Notably, this carbinols,[12] nucleophilic trifluoromethylation of carboxylic
report represents one of the few studies on carbonylative acids derivatives[13] and Suzuki cross-coupling reactions[14]
coupling with organocopper reagents.
have been developed to make aryl trifluoromethyl ketones,
highly efficient and general protocol are still needed.
Owing to its high electronegativity and small size, the
introduction of fluorine atom into organic molecules greatly
alters the molecules’ physical, chemical and biological
The palladium-catalyzed multi-component cross-coupling
reaction of aryl halides, carbon monoxide and organometallic
reagents is
a valuable method for the synthesis of
unsymmetrical ketones.[15] This strategy enables the formation
of two carbon-carbon bonds in a single operation and provides
products that might be difficult to access otherwise. Over the
past decades, a variety of organometallic reagents including
properties,
such
as
lipophilicity,
bioavailability,
chemical/metabolic stability and binding selectivity.[1] For
these reasons, a great deal of efforts have been paid to
develop synthetic methods for preparing fluorinated organic
molecular.[2] Among these fluorinated organic molecular,
trifluoromethylketones (TFMKs) are a unique substructure in
medicinal chemistry, which have proven particularly useful as
probes in the study of hydrolytic enzymes[3] and as potent
enzyme inhibitors.[4] Moreover, trifluoromethylketones are of
important intermediates for the synthesis of CF3-substituted
heterocycles,[5] medicinal compounds,[6] and fluorinated
analogues of natural products.[7]
organoaluminium,[16]
organosilane,[17]
and
organotin
compounds[18] as well as arylboronic acids[19] have been used
for these carbonylative cross-coupling reactions. However, the
carbonylative coupling with organocopper reagents are still
rarely reported. From mechanism point of view, these
reactions proceed through a sequence of oxidative addition of
the aryl halide to Pd(0) providing Ar-Pd-X (I), migratory
insertion of CO giving acylpalladium intermediate (II),
transmetallation of organometallic reagents and finally
reductive elimination to generate the desired ketones and
reproduce Pd(0) species. We hypothesized that with a suitable
organocopper reagent would potentially trap the reactive
acylpalladium species II and subsequently reductive
elimination to afford the desired aryl ketones as well. In order
to confirm this hypnosis, we performed experiments and we
wish to describe here a successful example on palladium-
catalyzed carbonylative coupling of aryl iodides with
organocopper reagent. This procedure also represents a
convenient and straightforward methodology for the synthesis
of aryl trifluoromethyl ketones.
Despite a variety of procedures available for preparing
aliphatic trifluoromethyl ketones,[8,9] the related methods for
the synthesis of aryl trifluoromethyl ketones are still scarce.
Friedel-Crafts reaction is a commonly used method for the
synthesis of aromatic and heterocyclic trifluoromethyl
ketones; however, the highly nucleophilic aromatic
a.Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of
Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei
430079 (China), E-mail: gfyang@mail.ccnu.edu.cn, szhou@mail.ccnu.edu.cn
b.Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-
Strasse 29a, 18059 Rostock, Germany, E-mail: xiao-feng.wu@catalysis.de
Electronic Supplementary Information (ESI) available: [Experimental details and
NMR spectrum]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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[a] General reaction conditions: 2-iodonaphthalene (0.1 mmol), MCF3
View Article (O0n.1li2ne5
Initially, the reaction of 2-iodonaphthalene with different
commercially available (trifluoromethyl)copper reagents, such
mmol), solvent (2 mL), Pd catalyst (5 mol%), 70 oC, 24h. [b] Determined by 19F
DOI: 10.1039/C6RA12287F
NMR using trifluorotoluene as an internal standard. [c] 50 ℃. [d] 90 ℃. [e] 1.5
equiv. of (PPh3)3CuCF3. Phen: 1, 10-phenanthroline.
as
Hartwig’s
trifluoromethylator[20]
and
Grushin’s
(trifluoromethyl)copper reagents,[21] in the presence of 5 mol%
of PdCl2(PPh3)2 and 20 bar carbon monoxide was investigated
(Table 1, entries 1-3). To our delight, the desired product 1a
was obtained in moderate yields (46% and 41%) with Grushin’s
(trifluoromethyl)copper reagents (Table 1, entries 2 and 3).
Encouraged by these initial results, different palladium
catalysts were tested (Table 1, entries 4-8). As expected, the
reaction didn’t show any conversion in the absence of
palladium catalyst (Table 1, entry 4), while albeit slightly higher
yield was observed when using PdI2(PPh3)2 as the catalyst
(Table 1, entry 8). To further improve the reaction, we
evaluated the influence of critical reaction parameters such as
carbon monoxide pressure, temperature and solvent. Lower
yields were observed at 10 bar or 40 bar carbon monoxide
pressure (Table 1, entries 9-10). The reaction temperature is
To gain insight into the reaction mechanism, some
stoichiometric reactions using isolated palladium complexes
were performed (Scheme 1). When Ar-Pd-CF3 complex
treated with 20 bar CO at 70 C in xylene, the desired product
3 was
o
2b could not be observed (Scheme 1, a). However, treatment
of an acylpalladium complex
70 C in xylene allowed the formation of the desired product
4 with 1.5 equiv. (PPh3)3CuCF3 at
o
2b in 60% yield (Scheme 1, b). These results support the
reaction go through acylpalladium complex
intermediate.
4
as the key
PPh3
PhCOCF3
2b
(a)
Ph3P Pd CF3
CO (20 bar), xylene, 70 oC, 3h
Ph
3
o
crucial for the process. When the reaction performed at 50 C,
the yield decreased to 10% (Table 1, entry 11). Gratifyingly,
during the survey of reaction solvents excellent yield can be
achieved when using xylene as the solvent (Table 1, entry 16).
Remarkably, nearly quantitative yield was obtained with a
slightly excess amount of (PPh3)3CuCF3 (Table 1, entry 17). In
general, due to the coordination behavior of CO, increased
pressure might kill the palladium catalyst and lead to
lower yield. Temperature can affect CO insertion and
decarbonylation step and oxidative addition step, hence
yields changing can be observed in temperature variation.
No product
PPh3
1.5 equiv (PPh3)3CuCF3
xylene, 70 oC, 3h
PhCOCF3
(b)
Ph3P Pd
I
COPh
4
2b
60% yield
Scheme 1. Mechanistic studies.
Based on our mechanistic studies and previous
literature,[18c-e] a most plausible catalytic cycle is proposed in
Scheme 2. It is believed that this process started from
oxidation addition of the aryl iodide to Pd(0) providing Ar-Pd-I
(A), and subsequent migratory insertion of CO giving the
acylpalladium intermediate B, then transmetallation of
(PPh3)3CuCF3 generating intermediate C and finally reductive
elimination to yield the desired trifluoromethyl ketone and
reproduce Pd(0) species for next cycle.
Encouraged by these results, we studied the generality of
this catalyst system in more detail (Table 2). Various aryl
iodides were transformed smoothly into their corresponding
trifluoromethyl ketones with good to excellent yields. In most
cases, both electron-withdrawing and electron-donating
groups showed little impact on the reaction activities. This
process could also be easily scaled up; the same isolated yield
can be achieved on 5 mmol scale without problem (Table 2,
entry 5).
Table 1. Influences of different reaction parameters on the palladium-catalyzed
carbonylative trifluoromethylation of 2-iodonaphthalene.[a]
Yield[b]
Entry
Organocopper
[Pd]
Solvent
CO (bar)
(%)
1
2
[(phen)CuCF3]
[(Ph3P)3CuCF3]
[(p-Tol3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
[(Ph3P)3CuCF3]
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
/
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMF
20
20
20
20
20
20
20
20
10
40
20
20
20
20
20
20
20
0
46
41
0
3
4
5
Pd(dba)2
0
6
Pd(PPh3)4
Pd(dppf)Cl2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
PdI2(PPh3)2
8
7
0
8
50
45
31
10
50
0
9
10
11[c]
12[d]
13
14
15
16
17[e]
THF
10
62
89
99
benzene
xylene
xylene
2 | J. Name., 2012, 00, 1-3
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View Article Online
DOI: 10.1039/C6RA12287F
LnPd0
11
85 (77)
ArCOCF3
ArI
12
84
80
COAr
CF3
Ar
ll
ll
13
14
15
16
Ln-2Pd
LnPd
I
A
C
87 (75)
62
CO
CuI + PPh3
COAr
ll
Ln-2Pd
I
(PPh3)3CuCF3
B
99
L= PPh3
Scheme 2. Proposed reaction pathway.
17
18
19
88 (78)
98
Then the functional group tolerances of this catalyst
system were investigated. Dialkylamine, ester, nitrile, amide,
ketal, trifluoromethylsulfoxide as well as heteroaromatic
compound were well tolerated; however, substrates
containing aldehydes or ketones are not suitable, presumably
because of the nucleophilic addition of CF3 anion to form the
corresponding trifluoromethyl carbinols. To highlight the utility
of this protocol for the late-stage functionalize of bio-active
molecular, the carbonylative trifluoromethylation of estrone-
derived aryl iodide was attempted, which yielded the
corresponding trifluoromethyl ketone in 45% yield (Table 2,
entry 20).
99 (86)
20
(45)
[a] General reaction conditions: aryl iodides (0.2 mmol), (PPh3)3CuCF3 (0.3 mmol),
xylene (5 mL), CO (20 bar), Pd catalyst (5 mol%), 70 oC, 24h. [b] Yield determined
by 19F NMR using trifluorotoluene as an internal standard. The number within the
parentheses represents the isolated yield. [c] Isolated yield for 5 mmol scale.
Table 2. Palladium-catalyzed carbonylative trifluoromethylation of aryl iodides to form
aryl Trifluoromethyl Ketones.[a]
Conclusions
In summary, we have developed the first palladium-
catalyzed carbonylative coupling of aryl iodides with
organocopper reagent. The reaction allows the straightforward
and efficient preparation of
a
wide range of aryl
Entry
1
Product
Yield (%)[b]
99
trifluoromethyl ketones. The ready availability of starting
materials, broad substrates scope as well as excellent
functional group tolerance should make the new protocol
useful for drug discovery.
2
3
4
99
99
Notes and references
99 (80)
General reaction procedure: A 30 mL autoclave was charged
with Aryl iodides (0.2 mmol), (PPh3)3CuCF3 (0.3 mmol),
(PPh3)2PdI2 (0.01 mmol), xylene (5 mL) and a magnetic stirring
bar. Once sealed, the autoclave was purged 3 times with CO,
then pressurized to 20 bar and heated at 70 oC for 24 h. After
reaction, the autoclave was cooled to room temperature and
depressurized. The solvent was evaporated under reduced
pressure and the residue was purified by column
chromatography on silica gel to give the corresponding
compound.
85 (78)
75[c]
5
6
7
8
9
99 (96)
99
83
Acknowledgements: We appreciate the generous supports from
Professor Matthias Beller in LIKAT.
52
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