Pd-catalyzed carbonylation for the construction of tertiary and quaternary carbon centers with sp3 carbon partners

Article abstract of DOI:10.1039/c4ob00568f

The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp³ carbon partners are presented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structurally unique carbonyl compounds. By

Full text of DOI:10.1039/c4ob00568f

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Pd-catalyzed carbonylation for the construction of
tertiary and quaternary carbon centers with sp3
carbon partners†
Cite this: Org. Biomol. Chem., 2014,
12, 5243
Wei Lu,a Yang Li,a Chao Wang,a Dong Xue,*a Jian-Gang Chena and Jianliang Xiao*a,b
The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp3 carbon partners are pre-
sented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structu-
rally unique carbonyl compounds. By employing 2-substituted 1,3-diesters, synthetically-challenging
quaternary carbon centres were accessed. In total, 42 examples of aryl carbonyl compounds were pre-
pared in moderate to good yields. The catalytic system features the use of a bidentated phosphine ligand
and a relatively low CO pressure (5 atm), providing an easy, alternative method for the preparation of
triketones.
Received 15th March 2014,
Accepted 29th April 2014
DOI: 10.1039/c4ob00568f
www.rsc.org/obc
ketones and ketone esters as nucleophiles reported by the
groups of Skrydstrup and Beller.17
Introduction
Palladium-catalyzed coupling reactions have become powerful
Aryl boronic acid derivatives are air and moisture stable,
tools for the building of chemical bonds.1 They are of signifi- and are compatible with a broad range of common functional
cant value in a wide range of applications, in particular groups.18 The carbonylation of aryl boronic acids and deriva-
medical chemicals2 and agrochemicals,3 as well as functional tives with various coupling partners, including alcohols,
materials.4 Among the various palladium-catalyzed coupling alkenes and alkynes, has also been successfully developed
reactions, carbonylation has been extensively studied.5 So far, (Scheme 1).19–21 However, to the best of our knowledge, no
the carbonylation of aryl halides,5a,b,6 triflates,7 and tosylates8 examples of the carbonylation of aryl boronic acid with sp3
have all been realized. Examples of carbonylation via C–H carbon partners have been reported yet. Herein, we would like
activation are also emerging.9 The most common nucleo-
philic coupling partners in these reactions are water,5l,10
alcohols,5k,11 and amines,5n,10d,12 which allow for the synthesis
of aryl carboxylic acids, esters or amides. The use of carbon-
based coupling partners has also been reported. For example,
the carbonylative Suzuki reaction couples aryl halides, CO and
aryl boronic acids to form aromatic ketones.5d,13 Alkenes and
alkynes are also viable nucleophiles, as seen in the carbonyla-
tive Heck14 and Sonogashira15 reactions. All of these carbon
nucleophiles contain sp2 and sp carbon centers. Carbonylation
reactions that can accommodate a sp3 carbon coupling
partner, however, are scarce. Although the carbonylation of
aryl halides in the presence of malonates was seen early in
1986,16 only recently was the carbonylation of aryl halides with
aKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education
School of Chemistry and Chemical Engineering Shaanxi Normal University, Xi’an,
710062, P. R. China. E-mail: xuedong_welcome@snnu.edu.cn;
Fax: +86-29-81530727; Tel: +86-29-81530840
bDepartment of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK.
E-mail: j.xiao@liv.ac.uk
†Electronic supplementary information (ESI) available. See DOI:
Scheme 1 The palladium-catalyzed carbonylation of aryl boronic acids
10.1039/c4ob00568f
with oxygen and carbon nucleophiles.
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to report the first case of an oxidative carbonylation of aryl product biphenyl was formed in a significant amount. It is
boronic acids with sp3 carbon-based nucleophiles, i.e. malo- also worth noting that when a weaker base, such as Et3N, was
nates and diketones. The resulting products, triketones, are used instead of the t-BuOLi, no product could be isolated
useful intermediates in organic synthesis, especially for the (Table 1, entry 16).
preparation of biologically active molecules such as phloro-
glucinols and 5-deazaaminopterin.22
To explore the scope of the carbonylation reaction, various
aryl boronic acids were then examined for coupling with malo-
nates under CO (5 bar), using Pd(OTFA)2/BINAP as a catalyst
and t-BuOLi as a base. The results are summarized in Table 2.
para-Substituted phenyl boronic acids reacted well with diethyl
malonate to afford good yields (Table 2, 2b–2i). No correlation
between the electronic properties of the substituents and the
reactivity was apparent under the conditions employed.
However, lower yields were generally observed for meta-substi-
tuted substrates, although yields were still acceptable (Table 2,
2j–2l). As might be expected, ortho-substituted boronic acids
failed to undergo carbonylation, most likely due to their
increased steric demand, which hampers the attack of the
nucleophile (see below). Naphthalen-2-ylboronic acid and
dimethyl malonate were also viable substrates, albeit ones
which showed lower yields (Table 2, 2n, 2o).
Results and discussion
We set out to examine the Pd-catalyzed carbonylation of
phenyl boronic acid with diethyl malonate as the coupling
partner (Table 1). The desired product 2a was obtained in a
yield of 16% when catalyzed by Pd(OAc)2 and DPPP in the pres-
ence of AgOAc and t-BuOLi in MeCN at 80 °C for 12 h (Table 1,
entry 1). Control experiments revealed that the metal, ligand,
and oxidant were all indispensable for the reaction (Table 1,
entries 2–4). Screening of the ligand, solvent and oxidant
brought about a better system (Table 1, entries 5–12). Thus,
with BINAP as a ligand, Ag2O as an oxidant and toluene as a
solvent, the yield of 2a was increased to 55% (Table 1, entry
12). Monodentate ligands were inferior. For instance, when
using PPh3 instead of BINAP, the yield dropped to 21%.
Further experiments revealed that the catalyst precursors sig-
nificantly affected the reaction (Table 1, entries 12–14), and it
was pleasing that when Pd(OTFA)2 (OTFA: trifluoroacetate) was
used as the catalyst, a good yield of 68% was obtained
(Table 1, entry 14); this increased to 87% when the concen-
tration of boronic acid was lowered (Table 1, entry 15).
Without lowering the concentration, the homo-coupling
Table 2 The carbonylation of aryl boronic acids with diestersa,b
Table 1 Optimization of the reaction conditionsa
Entry
Catalyst
Ligand
Oxidant
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
Pd(OAc)2
NO
DPPP
DPPP
NO
AgOAc
AgOAc
AgOAc
NO
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
MnO2
Cu(OAc)2
Ag2O
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
THF
MePh
Dioxane
MePh
MePh
MePh
MePh
MePh
MePh
MePh
16
0
0
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
DPPP
BINAP
DPPE
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
0
20
Trace
16
49
10
32
25
55
38
68
87c
0d
9
10
11
12
13
14
15
16
Ag2O
Ag2O
Ag2O
Ag2O
Pd(OTFA)2
Pd(OTFA)2
Pd(OTFA)2
a Reaction conditions: aryl boronic acid (0.50 mmol), carbon
nucleophile (2 equiv.), CO (5 atm), Pd (5 mol%), ligand (5 mol%), a Reaction conditions: aryl boronic acid (0.25 mmol), carbon
t-BuOLi (0.5 mmol), oxidant (2 equiv.), solvent (3 mL), 80 °C, 12 h. nucleophile (0.5 mmol), CO (5 atm), Pd(OTFA)2 (5 mol%), BINAP
b Isolated yield. c 0.25 mmol of aryl boronic acid. d Et3N was used as a (5 mol%), Ag2O (0.5 mmol), t-BuOLi (0.5 mmol), toluene (3 mL), 80 °C,
base.
12 h. b Isolated yield given below each product.
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Apart from the malonates, 1,3-diketones turned out to be reported by Skrydstrup and co-workers in the carbonylation of
good carbonylation coupling partners with boronic acids. aryl bromides.17c
Good to excellent yields were obtained for a range of aryl
The more challenging carbonylation with 2-substituted 1,3-
boronic acids coupled with cyclohexane-1,3-dione (Table 3, dicarbonyl compounds, which leads to quaternary carbon
3a–3m). Compared with the malonates, slightly higher yields centers, was also examined. Using Pd(OTFA)2/BINAP as a cata-
were observed for 1,3-diketones in general, presumably reflect- lyst, the carbonylation was slower than those shown in Table 2,
ing their reduced steric demand. Notably, an excellent yield of affording unsatisfactory yields in general (Table 4). Consider-
87% was obtained for the very electron deficient para-CF3- ing the possible reaction mechanism (see below), a ligand with
phenyl boronic acid (Table 3, 3h). Interestingly, excellent yields a smaller steric bulkiness, 2,2′-bis(diphenylphosphino)-1,1′-
were also obtained for some meta-substituted aryl boronic biphenyl (BIPHEP), was tested and found to give better yields,
acids (Table 3, 3i, 3k). A 75% yield was recorded for thiophen- although they were still inferior to those given above. As is
3-yl boronic acid, showcasing the utility of this method for seen in Table 4, substituents with varying steric hindrances,
functionalizing heterocycles (Table 3, 3n). With cyclopentane- including methyl, ethyl, propyl and benzyl groups, could all be
1,3-dione as the nucleophile, a remarkable yield of 95% was tolerated. Interestingly, the increase in chain length of the sub-
produced (Table 3, 3o). The noncyclic compound, pentane-2,4- stituents on the manolates even increased the yields of pro-
dione, also reacted; however, the yield was lower (Table 3, 3p). ducts in some cases (Table 4, 4a, 4d, 4h). Notably, a good yield
These examples lend support to the suggested steric effect. of 72% was obtained for the reaction of para-methylphenyl
The yields obtained appear to be comparable with those boronic acid with n-propyl substituted diethyl manolate
(Table 4, 4i). These reactions represent the first examples of
Table 3 Carbonylation of aryl boronic acids with cyclic diketonesa,b
Table 4 The carbonylation of aryl boronic acids with 2-substituted
1,3-diestersa,b
a Reaction conditions: aryl boronic acid (0.25 mmol), carbon
a Reaction conditions: aryl boronic acid (0.25 mmol), carbon nucleophile (0.5 mmol), CO (5 atm), Pd(OTFA)2 (10 mol%), BIPHEP
nucleophile (0.5 mmol), CO (5 atm), Pd(OTFA)2 (5 mol%), BINAP (10 mol%), Ag2O (0.5 mmol), t-BuOLi (0.5 mmol), toluene (3 mL),
(5 mol%), Ag2O (0.5 mmol), t-BuOLi (0.5 mmol), toluene (3 mL), 80 °C, 80 °C, 12 h. b Isolated yield given below each product; the number in
12 h. b Isolated yield given below each product.
brackets refers to the yield obtained with BINAP.
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carbonylative coupling of boronic acids which form quaternary
carbon centers.
To further demonstrate the power of this new synthetic
method, the synthesis of an indazole,23 5, was carried out.
Using our method as a key step, an 81% yield of 5 was
obtained over two steps, starting from simple phenyl boronic
acid (Scheme 2). Indazoles are compounds with various bio-
activities and 5 is in fact a key intermediate for the synthesis
of an antitumour agent.24
ð1Þ
Fig. 2 Variation of the yield with the amount of base in the carbonyla-
tion of phenyl boronic acid. Conditions (B/A, molar ratio of base :
boronic acid): phenyl boronic acid (0.25 mmol), 1,3-diketone
(0.5 mmol), Pd(OTFA)2 (5 mol%), BINAP (5 mol%), CO (1 or 5 bar),
t-BuOLi, Ag2O (0.5 mmol), 80 °C, 10 h, in toluene (3 mL).
To gain insight into the reaction mechanism, the kinetic
profiles and the effect of the concentration of the base, as well
as the CO pressure, were studied, using the carbonylation of
phenyl boronic acid with cyclohexane-1,3-dione as a model
reaction under the conditions shown in eqn (1). A steady
increase in the yield with time was observed, showing that the
carbonylation rate varies with the concentration of the sub-
strate (Fig. 1). The effect of the amount of base was also inves-
tigated (Fig. 2). Interestingly, at 1 bar of CO pressure, the
reaction rate was not significantly affected by the base concen-
tration; whilst at 5 bar of CO pressure, an increase in the
amount of base led to faster reaction rates. Since the concen-
tration of the nucleophile, i.e. the enolate derived from the di-
ketone, is directly proportional to that of the base, the
observed effect of the base concentration seems to suggest that
at a high CO pressure, the reaction rate is determined by the
step that involves the enolate; whilst at a low CO pressure, the
CO concentration affects the reaction rate. This hypothesis is
further supported by the effect of the CO pressure observed
(Fig. 3).
A volcano-shaped curve was obtained for the variation of
yields with the pressure of CO (Fig. 3). The highest yield was
obtained at 5 bar of CO. At pressures lower than 5 bar, the
reaction rate increased with an increase in CO pressure, indi-
cating that the diffusion of CO gas into the solution may limit
the reaction rate. The decrease in the rate at higher than 5 bar
CO pressure may stem from the faster reduction of Pd(II) to
Pd(0) by CO, which would slow down the transmetalation of
boronic acid to Pd(II).25 Alternatively, catalytically inactive pal-
ladium carbonyl species may be formed under a high CO
pressure.26 Without CO, however, homo-coupled biphenyl and
phenol were obtained as the major products, indicating that
the transmetalation process easily occurs. This result, together
with the fact that homo-coupling and deboronation products
Scheme 2 The carbonylation-enabled synthesis of an indazole.
Fig. 1 Variation of the yield with time in the carbonylation of phenyl
boronic acid. Conditions: phenyl boronic acid (0.25 mmol), 1,3-diketone
(0.5 mmol), Pd(OTFA)2 (5 mol%), BINAP (5 mol%), CO (5 bar), t-BuOLi
(0.5 mmol), Ag2O (0.5 mmol), 80 °C, in toluene (3 mL).
Fig. 3 Variation of the yield with CO pressure in the carbonylation of
phenyl boronic acid. Conditions: phenyl boronic acid (0.25 mmol), 1,3-
diketone (0.5 mmol), Pd(OTFA)2 (5 mol%), BINAP (5 mol%), CO, t-BuOLi
(0.5 mmol), Ag2O (0.5 mmol), 80 °C, 10 h, in toluene (3 mL).
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reported in ppm, using TMS as an internal standard. Data are
presented as follows: chemical shift (ppm), multiplicity (s =
singlet, d = doublet, t = triplet, q = quartet, m = multiplet).
Toluene was dried over sodium for 4 h, and distilled under N2
atmosphere.
Procedure for preparation of diethyl 2-benzoylmalonate
The reaction was carried out in an autoclave containing a
10 mL Teflon reaction tube. t-BuOLi (0.5 mmol) and carbon
nucleophiles (0.5 mmol) were placed in a 10 mL Teflon reac-
tion tube and then solvent (1 mL) was added. The reaction
mixture was stirred at room temperature for 1 h. Next, a Pd
catalyst (0.025 mmol), a ligand (0.025 mmol), aryl boronic acid
(0.25 mmol) and an oxidant (0.5 mmol) were added to the
tube, to which was added 2 mL solvent with a syringe. The
tube was placed in the autoclave. Once sealed, the autoclave
was purged several times with CO, and then pressurized to
5 atm with CO at room temperature and heated in an oil bath
at 80 °C for 12 h. The autoclave was then cooled to room temp-
erature and vented, to discharge the excess CO in the fume
hood. Water (10 mL) was added, and the product was extracted
with ethyl acetate (3 × 15 mL). The organic layers were washed
with brine, dried over Na2SO4, and evaporated. The crude
product was purified by column chromatography on silica gel
using a mixture of ethyl acetate and petroleum ether as an
eluent, to give the carbonylation product.
Scheme 3 A proposed mechanism for the carbonylation of boronic
acid featuring a sp3 carbon nucleophile.
were not observed in the presence of CO, suggests that CO
insertion is also a relatively fast process.
A suggested mechanism is presented in Scheme 3.27 The
transmetalation of aryl boronic acid with a Pd(II) complex, A,
produces the intermediate B, which undergoes CO insertion to
afford the Pd-acyl complex C. The enolate then coordinates
to the Pd center to form the intermediate D, which isomerizes
to E. E could also be formed via a palladium-enolate species
without going through D.28 Product G is released through
reductive elimination, generating the Pd(0) species F, the oxi-
dation of which regenerates the active catalyst A. Alternatively,
a direct nucleophilic attack by the enolate at the Pd-acyl may
take place, affording G and F. The results above do not allow
these two pathways to be discerned, however.
Acknowledgements
This work was supported by the Program for Chang Jiang
Scholars, 111 project and Innovative Research Team in Univer-
sity (IRT 1070), the National Nature Science Foundation of
China (21372148), the Cheung Kong Scholar Programme, and
the Shaanxi Innovative Team of Key Science and Technology
(2013KCT-17).
Conclusions
Notes and references
In conclusion, we have developed the first carbonylation of
aryl boronic acids with sp3 carbon coupling partners. The cata-
lytic system demonstrates a broad substrate scope, allowing for
the carbonylation of various aryl boronic acids with malonates
or 1,3-diketones to afford tertiary and, more remarkably, qua-
ternary carbon centers. Whilst preliminary studies indicate
that the carbonylation turnover is limited by the nucleophilic
attack or reductive elimination steps, details of the reaction
mechanism remain to be delineated.
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