Palladium and visible-light mediated carbonylative Suzuki-Miyaura coupling of unactivated alkyl halides and aryl boronic acids

Article abstract of DOI:10.1039/c7cc02763j

Herein, a simple and efficient method for the palladium-catalyzed carbonylation of aryl boronic acids with unactivated alkyl iodides and bromides under visible-light irradiation, ambient temperature and low CO-pressure is presented. Notably, the procedure uses readily available equipment and an inexpensive palladium catalyst to generate the key alkyl radical intermediate. These mild conditions enabled the synthesis of a range of functionalized aryl alkyl ketones including the antipsychotic drug, melperone.

Full text of DOI:10.1039/c7cc02763j

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C7CC02763J
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Palladium and Visible-Light Mediated Carbonylative Suzuki-
Miyaura Coupling of Unactivated Alkyl Halides and Aryl Boronic
Acids†
Received 00th January 20xx,
Accepted 00th January 20xx
Sara Roslina and Luke R. Odella
DOI: 10.1039/x0xx00000x
www.rsc.org/
Herein, a simple and efficient method for the palladium-catalyzed
carbonylation of aryl boronic acids with unactivated alkyl iodides
and bromides under visible-light irradiation, ambient temperature
and low CO-pressure is presented. Notably, the procedure uses
readily available equipment and an inexpensive palladium catalyst
to generate the key alkyl radical intermediate. These mild
conditions enabled the synthesis of a range of functionalized aryl
alkyl ketones including the antiphyscotic drug, melperone.
and versatile platform for accessing radical chemistry.
Importantly, these methods require only inexpensive
equipment and allow radical generation under exceedingly
mild and catalytic conditions. This approach has been elegantly
applied to the functionalization of unactivated alkyl halides
using
cross-coupling6,
hydrodehalongenation7
and
aminocarbonylation8 reactions. Herein we present the
development of a visible-light mediated and palladium-
catalyzed carbonylative Suzuki-Miyaura coupling for the
preparation of unsymmetrical ketones from alkyl halides and
aryl boronic acids. Importantly, the reaction is not burdened
by the need for high-energy light irradiation, elevated
temperatures or high CO-pressures, thereby overcoming the
drawbacks associated with existing radical carbonylation
procedures (Figure 1).
The carbonylation reaction is one of the most versatile
synthetic manifolds in modern organometallic chemistry and
has found extensive application in the synthesis of numerous
carbonyl containing compounds.1 Despite the tremendous
recent progress in this area, the electrophilic coupling partner
substrate has largely been restricted to aryl, vinyl and benzyl
(pseudo)-halides whereas engaging alkyl halides has been
difficult. The slow oxidative addition to the metal center, made
even more challenging by the π-acidic character of carbon
monoxide, and the risk of β-elimination from the alkyl-metal
oxidative addition complex has undoubtedly hampered the use
of this valuable substrate class.1,2
Over the past decade, radical-mediated reactions have
emerged as a powerful alternative approach to engage alkyl
halides. These methods utilize an orthogonal mechanistic
manifold, based on a single-electron transfer (SET) event,
generating an alkyl radical, to circumvent the problems
associated with the oxidative addition pathway. Generally
these methods employ either intense UV/light irradiation3
together with high pressures of CO4 or elevated temperatures5
to generate and functionalize the key radical intermediate,
representing significant practical drawbacks.
work
Previous
O
B
R1
(HO)2
CO
R1
I
[Pd],
R3
Xe lamp
atm)
(45
R3
R2
R2
Use of CO
-
-
-
-
at
pressures
(g) high
lamp
Ref 4f
xenon
500 W
Limited to alkyl iodides
Highly specialized equipment
work
This
O
B
(HO)2
R1
X
[Pd], Mo(CO)6
LED
R1
R3
R3
R2
R2
=
X
Br
I,
-
ex
Ambient
atm)
of
CO
generated
situ
pressure
(2-3
-
-
-
two-champer reaction set-up
Simple
2 W blue/white LEDs
and
Unactivated alkyl iodides
alkyl bromides
Figure 1. Palladium/light-mediated synthesis of aryl alkyl ketones.
Recently, visible-light photocatalysis has attracted
considerable interest in the synthetic community as a simple
The investigation began using a dual Ir/Pd catalytic system
comprising of palladium(II)bis(triphenylphosphine) dichloride
a. Organic Pharmaceutical Chemistry, Department of Medicinal Chemistry, Uppsala
Biomedical Center, Uppsala University, P. O. Box 574, SE-751 23 Uppsala, Sweden.
E-mail: luke.odell@orgfarm.uu.se; Fax: +46-18-471447; Phone: +46-18-4714297
(Pd(PPh3)2Cl2) and fac-Ir(ppy)3 (
1) with cyclohexyl iodide (2)
and phenylboronic acid ( ) as model substrates. To avoid the
3
use of gaseous CO, molybdenum hexacarbonyl [Mo(CO)6] was
used as a solid CO-source together with a double-chamber
reaction set-up.9 Initially, irradiation with LEDs resulted in
†Electronic Supplementary Information (ESI) available. For ESI 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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and a NMR yield Notably, the protected piperidine derivative 8 was isolated in
modest conversion to the desired product
of 17% was obtained (Table 1, entry 1).10 Changing the Pd 60% yield and is readily amenable for further modifications.
4
View Article Online
DOI: 10.1039/C7CC02763J
catalyst to Pd(PPh3)4 gave a slight improvement in yield (24%,
entry 2) as did heating the CO-releasing chamber (31% yield,
entry 3).
Scheme 1. Alkyl halide scope and limitations
:
Chamberrxn
K CO
2
3
,
Pd(PPh3)4
benzene/water 2:1
rt, 24 h
OH
B
O
blue/white LEDs,
OH
R
R
X
:
ChamberCO
, DBU
Mo(CO)6
70o MeCN
Table 1. Optimization of reaction conditions
C,
=
X
Br
4-19
3
I,
:
Chamberrxn catalyst, HE
K2CO3 benzene/water 2:1
OH
B
O
4
,
Alkyl iodides
I
O
rt, 24 h
blue/white LEDs,
O
OH
O
:
C6
H13
ChamberCO
Mo(CO)6
DBU, MeCN
2
3
O
5
6 64%
62%
4
47%a
7
64%
65%,
entry
catalyst
temperature CCO
NMR yielda
O
O
O
O
1
2
Pd(PPh3)2Cl2, 1
Pd(PPh3)4, 1
Pd(PPh3)4, 1
Pd(PPh3)4, 1b
Pd(PPh3)4
rt
17%
24%
C8H17
C7
H15
TsN
rt
11
50%
9 55%
10 71%
8 60%
3
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
70 °C
50 °Cf
31%
O
4
5c
6c
7c
8c,d
9c,e
10c
46%
O
49%
Cl
3
O
Pd(PPh3)4
64%
14
61%
13 71%
12
67%
Pd(PPh3)4
71% (65 %)
70%
Alkyl bromides
Pd(PPh3)4
O
O
O
C8H17
C7H15
Pd(PPh3)4
(23 %)
71%
O
Pd(PPh3)4
41%,
48%c
9
40%c
b
12
10 42%
30%,
4
35%, 39%
O
O
O
Conditions: Chamberrxn 0.25 mmol 2 (entries 1-6), 0.3 mmol 2 (entries 7-10), 1.5
eq 3, 5 mol% Pd-catalyst, 1 mol% 1, 1 eq K2CO3, 2 eq Hantszch ester (HE), 2 mL
solvent (entries 1-5) 4 mL solvent (entries 6-10) ChamberCO 2.5 eq Mo(CO)6 5 eq
DBU 2 mL MeCN (entries 1-5) 4 mL (entries 6-10). aDetermined by 1H NMR using
an internal standard. Number in brackets represents isolated yield. b2 mol% 1.
cNo HE. dToluene instead of benzene. eAnisole instead of benzene. Crxn and CCO
were heated to 50 °C.
O
Cl
3
3
19 26%
18
13 61%
14
32%
34%
O
f
Alkyl iodides
Alkyl bromides
Limitations
O
O
O
HO
Increasing the amount of
reducing the amount of Hantzsch ester (HE) to 0.5 equivalents
increased the yield to 46% (entry 4). Surprisingly, a control
experiment omitting the photocatalyst
investigating its role in the reaction, returned an increased
yield of 49% (entry 5). When continuing without the expensive
1 to 2 mol%, in combination with
d
17
reaction
Traces
reaction
17 No
15 No
16
Traces
Conditions from entry 7, Table 1. a1 mmol scale. Crxn and CCO heated to 50 °C.
b
1 with the intent of
cReaction time 55 h. dReaction time 72 h.
Primary iodides performed equally well as substrates,
giving products 9-13, in yields ranging from 50%-71%. Excellent
photocatalyst
1 and increasing the solvent volume to 4 mL to
minimize the gas-phase volume,11 the yield was further
improved (64%, entry 6). Furthermore, increasing the amount
chemoselectivity for the iodide center was observed in the
synthesis of 13, with no detection of side-products arising from
substitution of the chlorine atom (GC/MS). Finally, the tertiary
iodide 1-iodoadamantane returned the desired product 14 in
61% yield. Unfortunately, tert-butyl iodide furnished only trace
amounts of 17, even after prolonged reaction time (72 h)
presumably due to high radical stability and slow carbonylation
rate.15
of
2 to 0.3 mmol gave a yield of 71% (isolated yield 65%, entry
7). Screening of aromatic solvents that have been previously
used in Suzuki-Miyaura couplings, revealed that toluene was
equally efficient (70%, entry 8) whereas anisole gave
4 in 23%
isolated yield (entry 9) due to a cumbersome purification.12,13
To avoid the risk of side-reactions resulting from C-H
functionalization of toluene,14 we continued our studies using
benzene. A final experiment, where both Crxn and CCO were
heated to 50 °C, gave a yield of 71% (entry 10). However, for
ease of handling the conditions in entry 7 were chosen for
further evaluation.
To further extend the scope of this carbonylative process,
we set about exploring even more challenging alkyl bromide
substrates. Gratifyingly, a range of unsymmetrical aryl alkyl
ketone products (4, 9-10, 12-14 and 18-19) were isolated in up
to 61% yield from the respective alkyl bromide (Scheme 1).
Not surprisingly, the alkyl bromides were found to be less
reactive than their iodide counterparts and, in some instances,
the reactions did not go to completion after 24h. Heating both
chambers to 50 °C led to a slight improvement in yield (e.g.
whereas when irradiating the reaction for 55h, the yields of
With the optimized conditions in hand, the scope of the
reaction with respect to the alkyl halide component was
explored (Scheme 1). A range of unactivated secondary alkyl
iodides, including acyclic and cyclic derivatives, were efficiently
4)
9
transformed into the desired products
4
-
8
in good yields.
2 | J. Name., 2012, 00, 1-3
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and 12 increased from 30% and 41% to 40% and 48%, experiments were performed using cyclohexyl- iodide (
View Article2O)nlioner
respectively. The reactivity trend was the same as for the alkyl bromide.10 In both cases, removal of the catalyst was
DOI: 10.1039/C7CC02763J
iodides, with primary and secondary alkyl bromides deleterious for conversion and conducting the reaction in the
performing equally well. The chlorinated derivative 13 was absence of light, or under ambient light conditions, resulted in
also isolated in 61% yield, another demonstration of high only traces of the ketone product. Furthermore, the addition
reaction selectivity and, in 19, no competing reaction with the of TEMPO completely abolished product formation and the
pendent olefin was noted.7,16 Here, the ring-size of the cyclohexyl-TEMPO adduct could be detected by LC/MS
putative cyclized product probably disfavored the analysis. Based on these results,
a tentative reaction
intramolecular reaction.
mechanism is depicted in Scheme 3. A SET between Pd(0) and
the alkyl halide, here an alkyl iodide, initiates the reaction by
forming alkyl radical 36 and Ln(CO)nPd(I)I 37. The exact role of
the visible light in this process is yet to be elucidated and the
Pd-catalyst may act either as a photosensitizer, to promote
radical formation19, or as a photocatalyst through a SET from
an excited state species.18a,b The need for irradiation supports
a radical mechanism, as does the formation of a TEMPO-
adduct. The alkyl radical can then react via two different
pathways (path A or B).
Scheme 2. Boronic acid scope and limitations
:
Chamberrxn
Pd(PPh3)
4
K2CO3 benzene/water 2:1
blue/white LEDs,
,
OH
B
O
rt, 24 h
R
I
Ar
OH
:
ChamberCO
, DBU
Mo(CO)6
70°C, MeCN
R
Ar
20-34
O
O
O
O
C7H15
22 79%
21 59%
20 43%
CF3
23 64%
R
I
R
I
O
O
O
O
Pd(0)
Cl
Path A
Path B
Visible
C7H15
H15
C7
C7H15
Visible
light
O
F
Cl
F
light
36
R
27 83%
26 68%
R
Ph
24 56%
25 71%
43
37
nLn
R
Pd(I)I(CO)
CO
R
O
O
O
S
36
O
O
S
nLn 37
Pd(I)I(CO)
CO
36 R
C7H15
C7H15
29 80%, 27%a
H15
C7
R
Pd PhLn
(II)
O
38
O
42
O
CO
28 26%
Limitations
41
nLn
31 53%
30 62%
Pd(II)I(CO)
R
IB(OH)2
or CO
O
O
O
R
I
Pd(II)I(CO)n-1Ln
R
I
PhB(OH)2
C7H15
C7
H15
R
37
36
O
40
Br
NO2
N
R
Pd Ln
(II)I
32 Traceb
reaction
reaction
33 No
34 No
O
39
Melperone synthesis
Scheme 3. Plausible reaction mechanism.
O
O
KI, NaHCO3
N
Cl
NH
toluene, 100°C
22 h
In path A, the alkyl radical traps CO to form acyl radical 38
which after addition to 37 gives acyl-palladium complex 39
,
.
F
F
35
26
55%
Melperone
Radical 38 can also propagate the alkyl radical formation by
iodine transfer, whereby acyl iodide 40 is formed which can
enter the catalytic cycle after addition to a palladium species.
This pathway is favored for carbonylation of alkyl iodides
performed under high CO-pressures (> 45 bar)4b,c,e,f,20 and the
maximum CO-pressure here was measured to 2.5 bar.10 In
path B, 36 and 37 form a caged radical pair which can collapse
to a Pd(II)-complex 41 in which the alkyl group can migrate to
Pd-coordinated CO. Alternatively 36, formed either through
path A or after escaping the radical cage,21 can add directly to
a bound CO on 37. Both pathways converge on 39, which can
undergo transmetallation with the aryl boronic acid to give
complex 42. A reductive cleavage regenerates Pd(0) and
liberates the ketone product 43. Path B has been proposed to
operate in conditions with low CO-pressures, where increasing
the CO-pressure had a detrimental effect on the yield.3a,5b,22
The lower yield obtained for 29 using formic acid as CO-source
may be partly attributed to this phenomenon as a higher CO-
pressure is reached (3.5 bar).8 As for the pathway under
operation here, two lines of evidence support a reaction via
path A namely, the addition of TEMPO completely abolishes
product formation and the removal of CO results only in
Conditions from entry 7, Table 1. aHCO2H/H2SO4 used instead of Mo(CO)6.
bReaction time 48 h.
Next, the scope of boronic acid component was explored
and the reaction was found to be compatible with a range of
electronically diverse coupling partners affording products 20-
31 in moderate to very good yields (Scheme 2). Notably, bulky
or potentially coordinating ortho-substituents were well
tolerated (e.g. 20
heterocycle (30). Halogenated boronic acids were also suitable
substrates (24 27), however the bromosubstituted analog 32
, 24 and 31) as was an electron rich
-
was formed in trace amounts, even after prolonged irradiation
time (55 h). Product 29 was also synthesized using formic acid
as a CO-source albeit in an unoptimized yield of 27%. Product
26 is a precursor in the synthesis of the atypical antipsychotic
drug melperone, and has been previously synthesized in two
steps using sequential palladium and gold catalysis.17 Further
elaboration via
a
nucleophilic substitution with 4-
methylpiperidine (35) gave melperone in 55% yield (Scheme 2)
in an overall step-efficient process.
To delineate whether the reaction presented herein
proceeds via SN2 or SET pathways18, a set of control
This journal is © The Royal Society of Chemistry 20xx
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unreacted starting material. This suggests the intermediacy of
a discreet radical intermediate rather than a caged radical
pair5b and that acyl radical 38 may be required for efficient
radical propagation. However, further studies are needed to
fully elucidate the reaction mechanism.
In summary, a carbonylative Suzuki-Miyaura coupling of
unactivated alkyl halides with aryl boronic acids has been
presented. By using visible-light irradiation, alkyl halides were
coupled with aryl boronic acids under ambient temperature
and low CO-pressure in moderate to very good yields. In
general, the isolated yields were in the same range as
previously reported using elevated CO-pressures and high
energy irradiation. Notably, a SET or photosensitization event
between Pd(PPh3)4 and the alkyl halide substrate circumvents
the need for an expensive photocatalyst. Furthermore, the
application of challenging alkyl bromides as substrates has
been realized for the first time. Additional improvements to
related methods are the use of a solid CO-source instead of 10
gaseous CO and use of cheap and readily available LED lights 11
that together with the double-chamber system constitutes a
convenient reaction set-up. Moreover, the discovery that the 12
combination of a simple palladium catalyst and visible-light
irradiation can promote efficient radical generation from 13
challenging alkyl halide substrates opens up an exciting new
dimension in both palladium and photocatalysis chemistry.
Further studies to explore the scope of this process are
currently underway in our laboratory and will be reported in
due course.
Chem. Soc. 2016, 138, 7520–7523; c) D. R. Pye, L-J. Cheng,
N. P. Mankad, Chem. Sci. 2017, DOI: 10.1039/c7sc01170a.
View Article Online
DOI: 10.1039/C7CC02763J
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