Iron-catalysed borylation of arenediazonium salts to give access to arylboron derivatives via aryl(amino)boranes at room temperature

Article abstract of DOI:10.1002/adsc.201200942

Complementary to previously described Miyaura borylation methods, a new access to boron derivatives via aryl(amino)boranes is described. Direct coupling between aryldiazonium salts and diisopropylaminoborane is catalysed by 0.1% ferrocene leading to the formation of a carbon-boron bond. The obtained aryl(amino)boranes could eventually then be transformed into boronic acids, boronates or borates. Copyright

Full text of DOI:10.1002/adsc.201200942

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DOI: 10.1002/adsc.201200942
Iron-Catalysed Borylation of Arenediazonium Salts to Give
Access to Arylboron Derivatives via Aryl(amino)boranes at
G
Room Temperature
Ludovic D. Marciasini,a Nicolas Richy,b Michel Vaultier,a and Mathieu Pucheaulta,*
a
Institut des Sciences Molꢀculaires, UMR5255, Universitꢀ de Bordeaux 1, IPB, CNRS, 351 Cours de la libꢀration, 33405
Talence cedex, France
Fax : (+33)-540-006-632; phone: (+33)-540-006-733; e-mail: m.pucheault@ism.u-bordeaux1.fr
Chimie et Photonique Molꢀculaire UMR 6510 CNRS Universitꢀ de Rennes 1, 263 avenue du gꢀnꢀral Leclerc, campus de
b
Beaulieu, 350420 Rennes cedex, France
Received: October 24, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200942.
Abstract: Complementary to previously described
Miyaura borylation methods, a new access to boron
derivatives via arylACTHNUTRGNEU(GN amino)boranes is described.
Direct coupling between aryldiazonium salts and
diisopropylaminoborane is catalysed by 0.1% ferro-
cene leading to the formation of a carbon-boron
bond. The obtained arylACTHNUTRGNE(UNG amino)boranes could even-
tually then be transformed into boronic acids, boro-
nates or borates.
tions have been optimised using iron complexes as
catalyst for the formation of carbon-carbon,[3] carbon-
oxygen,[4] carbon-nitrogen,[5] carbon-sulphur,[6] or
carbon-silicon[7] bonds. To the best of our knowledge,
no general borylation process has been reported so
far using iron-based catalysts, and only one paper on
borylation of furans and thiophenes has been recently
published.[8]
The main borylation methods have been developed
using palladium activation of carbon-halide bonds
(Miyaura borylation)[9] or Ar H activation using iridi-
À
Keywords: aminoboranes; borylation; homogene-
ous catalysis; iron; metallocenes
um catalysts (Hartwig borylation).[10] Both are very
efficient and traditionally use pinacolborane 1a or pi-
nacolatodiboron 1b as boron source (Scheme 1).
Aminoboranes[11] such as (i-Pr)2N-BH2 1d have
been used since 2003 as borylation agent in palladi-
Iron catalysis has rapidly emerged as an alternative to um-catalysed transformations of aryl bromides, io-
palladium complexes in advanced scaffold synthesis.[1] dides and triflates.[12] We recently extended the use of
Despite its discovery 40 years ago,[2] the use of iron such aminoboranes for the direct synthesis of biaryl
has recently exploded due to numerous advantages compounds,[13] which was part of our ongoing research
over commonly used transition metal complexes in- project on designing a better access to and use of
cluding an affordable price, a lower toxicity and a rela- boron derivatives. Herein, we describe an iron-cata-
tive environmental innocuousness. To date many reac- lysed borylation of arenediazonium salts which pro-
Scheme 1. Catalytic borylation methods and reagents
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Table 1. Iron-catalysed borylation of 4-MeOC6H4N2BF4.
to the poor solubility of the diazonium salts. Amino-
borane 1d is fairly unstable in polar protic solvents
and those solvents unsurprisingly led to no expected
boronates. However, in aprotic polar solvents such as
dioxane
(Table 1,
entry 3),
dimethylacetamide
(Table 1, entry 4) or N-methylpyrrolidine (Table 1,
entry 5), reaction proceeded faster with less competi-
tive reduction into the corresponding arene.
Our best result was obtained with acetonitrile for
which 87% of the expected boronate was isolated
with >99% purity. The boronate is isolated after in
situ methanolysis and transesterification of the result-
ing dimethylboronate with pinacol. As witnessed by
11B NMR, a complete conversion of the diazonium
salt into the corresponding arylaminoborane is ob-
tained in less than 1 h. Despite the large variety of
commercially available ferrocene derivatives, the
parent molecule turned out to be the most efficient.
Acetylferrocene (Table 1, entry 7) and n-butylferro-
cene (Table 1, entry 8) led to 72% and 77% yields, re-
spectively, whereas bromoferrocene (Table 1, entry 9),
tert-butylferrocene (Table 1, entry 10), vinylferrocene
(Table 1, entry 11) did not afford the product in more
than 65% yield. Although the reaction proceeded effi-
ciently with 1% ferrocene, we found that increasing
the loading was detrimental to the reaction (Table 1,
entry 12). Intrigued by this phenomenon, we investi-
gated the possibility of having the addition of an aryl
radical 6 onto the aminoborane 1d as a key step in-
Entry
Catalyst
Solvent
5a [%]
4a[a]
1
2
3
4
5
6
7
8
Cp2Fe
Cp2Fe
Cp2Fe
Cp2Fe
Cp2Fe
Cp2Fe
AcCpFeCp
n-BuCpFeCp
BrCpFeCp
t-BuCpFeCp
vinylCpFeCp
Cp2Fe[b]
THF
22
0
38
–
36
<1
<1
4
1
3
1
1
toluene
dioxane
DMAc
NMP
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
24
81
71
87
72
77
51
65
65
61
9
10
11
12
1
1
[a]
Reduction was measured using GC/MS with mesitylene
as an internal standard.
5% of catalyst was used.
[b]
ceeds at room temperature with high catalytic activi- stead of a classical ionic mechanism (Scheme 2).[20]
ties. In our quest for active catalysts, we were in- The resulting intermediate 8 would react with the
trigued by an interesting recent report by Manners starting diazonium 2 to afford the arylACTHNUTRGNE(NUG amino)borane
et al. who described the iron-catalysed dehydrogena- 3 and regenerate the aryl radical [Scheme 2, Eq. (3)].
tion of borane·amine complexes in the presence of The aryl radical 6 would originate from the known re-
light sources.[14] Traditionally those reactions were action between ferrocene and the arenediazonium
performed using thermal treatment or a catalytic salt [Scheme 2, Eq. (1)]. The generated ferricinium
amount of late transition metal complexes[11,15]
tetrafluoroborate 7 could be reduced directly by 8 re-
In that case, we thought about using this unusual generating the starting ferrocene and affording the
reactivity in combination with the known reactivity of aryl(amino)borane 3. Alternatively direct reduction
AHCTUNGTRENNUNG
ferrocene with arenediazonium salts leading to aryl- of the ferricinium 7 by the aminoborane 1d would
ferricinium intermediates before further rearrange- lead to the formation of ferrocene and subsequent in-
ment.[16] If some reactions have been described using crease in reaction rate, which is observed at the low
areneadiazonium salts for borylation with bis(pinaco- concentration of radical initiator.
lato)diboron[17] 1b even very recently,[18] one might
Albeit unprecedented, this radical approach is cor-
expect a completely different reactivity in the pres- roborated by the light activation of CpFe(CO)2Bcat
ence of such a reducing agent as an aminoborane.[19] in benzene leading to the stoichiometric formation of
Side reactions may include reduction of the diazoni- the
corresponding
arylcatecholboronate
and
um salt into the arene or the aniline, and (or) reduc- [CpFe(CO)2]2 indicating a homolytic cleavage of the
[21]
À
tion of the catalyst.
Fe B bond.
Additionally, amine-borane dehydro-
Fortunately, this reduction of the diazonium salt is genation can be catalysed by [CpFe(CO)2]2 upon UV
not predominant, and we found that in the presence irradiation, showing the high propensity of aminobor-
of 1% of ferrocene, borylation of the 4- ane to undergo radical reactions.[14] In our case, at-
MeOC6H4N2BF4 occurred using (i-Pr)2N-BH2 1d as tempts to initiate the radical propagation differently,
boron source. A modest but encouraging 22% yield using UV light activation (54%), AIBN (48%) or
was obtained after 16 h at room temperature in THF. BEt3/O2 (63%) led to product formation but in de-
The reaction is unsuccessful in apolar solvents such as creasing yields as compared to ferrocene. The radical
toluene (Table 1, entry 2) or heptane, most likely due nature of the mechanism was also confirmed by the
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Iron-Catalysed Borylation of Arenediazonium Salts to Give Access to Arylboron Derivatives
Scheme 2. Radical addition on aminoborane.
transformation of 2-allyloxyphenyldiazonium tetra- afford accurate and reproducible gas evolution meas-
fluoroborate, which under previously described condi- urements. Initial constant kinetics were found to be of
tions, showed no boron incorporation but a mixture a zero order with respect to reagents up to 40% con-
of 5-exo and 6-endo cyclisation products (Scheme 3).
version which is consistent with a rate determining
Most likely, the (2)+(3) propagation alone is not propagation (see the Supporting Information). Initial
viable as in the absence of ferricinium 7, the competi- rate constants were determined and found to be pro-
tive disproportionation of 6 into the product 3 and portional to the root square of ferrocene concentra-
the amine arylborane complex 8 is terminating the tion (see the Supporting Information) which suggests
cycle (5). Combining the formation of aryl radical two propagations can be considered with the same
with ferrocene with a fast addition on the aminobor- contribution, one independent of iron concentration
ane and the reduction of the ferricinium by 6 is the (2)+(3); one dependent of ferrocene concentration
key to success. A radical process is consistent with the (1)+(2)+(4).
yield decrease observed with higher initiator (ferro-
The mechanism is thought to involve a radical addi-
cene) input (Table 1, entry 12), leading to an in- tion to aminoborane. The success of the reaction
creased concentration of reactive intermediate, there- relies in combining the ferrocene-catalysed generation
fore recombining more easily while terminating the of aryl radical and the fast propagation cycle with the
cycle.
Consequently, using the nitrogen release from the mechanistic studies are currently under investigation.
diazonium salt was found to be an accurate measure- We then tackled the application of this new reac-
ment of the aryl(amino)borane formation. Compara- tion to a large variety of arenediazonium salts. Over-
formation of the carbon-boron bond. More detailed
ACHTUNGTRENNUNG
tive studies showed a significant effect of catalyst con- all, most tested diazonium salts led to a yield com-
centration on reaction rates and unsurprisingly higher prised in the 65-90% yield range. No real trend could
catalyst concentrations led to faster reaction (see the be determined between electron-donating or elec-
Supporting Information). Despite our attempts, 5% tronn-withdrawing groups. Methyl and methoxy
ferrocene led to a reaction which was too fast to groups led to 47 to 87% isolated yields (Table 2, en-
tries 1–5), whereas reaction on diazonium salts bear-
ing electron-withdrawing groups afforded the corre-
sponding boronates in 55–91% yield (Table 2, en-
tries 6–10). Fluorine- and chlorine-substituted boro-
nates were obtained in 61–71% yield (Table 2, en-
tries 12–19). In the case of 2-chlorophenyldiazonium
tetrafluoroborate (Table 2, entry 15), the correspond-
ing boronate was isolated in a modest 49% yield, due
to the lower stability of the diazonium salt. One big
advantage of this methodology is the compatibility
Scheme 3. Cyclisation of 2-allyloxyphenyldiazonium tetra-
fluoroborate .
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Table 2. Ferrocene-catalysed borylation of diazonium salts.
Entry
1
Product
Yield [%][a]
80
Entry
14
Product
Yield [%][a]
61
2
3
4
69
57
87
15
16
17
49
70
71
5
47
18
66
6
7
8
71
63
55
19
20
21
68
74
72
9
65
22
65
10
11
91
62
23
24
70
74
[b]
12
61
70
25
26
–
13
56
[a]
Isolated yield.
Benzophenone was obtained in 60% yield.
[b]
with bromides and iodides. Few methods are allowing nediazonium salts. In that case, the only isolated com-
the synthesis with complete selectivity of bromine- or pound is the corresponding benzophenone resulting
iodine-substituted boron derivatives.[10]
from the competitive direct reduction of the C N
À
À
In our case, the selectivity is complete as no reac- into a C H bond (Table 2, entry 21). Bis boronates
tion is observed when iodobenzene or bromobenzene were also synthesized in good yield considering that
are put under the same reaction conditions. Hence, the resulting product arose from 6 consecutive reac-
bromo- and iodo-susbtitued pinacol benzeneboro- tions with an average of 91% yield per transformation
nates were isolated in 65–74% yield (Table 2, en- (Table 2 entry 26).
tries 20–24). One limitation we found to this reaction
is related to the reaction on 4-benzoyl-substituted are- ward method for arylAHCNUTGTRENNUNG
Overall we have managed to develop a straightfor-
(amino)borane synthesis by
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Iron-Catalysed Borylation of Arenediazonium Salts to Give Access to Arylboron Derivatives
Overall, this new method allows an easy access to
various boron derivatives using simple ferrocene as
mediator.
Experimental Section
General Procedure for Pinacol Boronate Synthesis
In a dried tubular reactor under argon, were dissolved the
diazonium salt (1 mmol) and ferrocene (10 mmol, 1.8 mg) in
2 mL of anhydrous CH3CN. Diisopropylaminoborane
(2 mmol 226 mg) was then added to the solution and stirred
for 2 h 30 min at room temperature. The reaction mixture
was quenched by the slow addition of anhydrous MeOH at
08C (2 mL) and stirred for an additional hour at room tem-
perature. After removal of all the volatiles, 1.3 equiv. of pi-
nacol were added in Et2O (2 mL), the mixture was stirred
4 h at room temperature. The crude mixture was washed
with a 50 gL À1CuCl2 solution (2ꢂ5 mL). The organic layer
was separated, dried over Na2SO4, filtered and concentrated
to dryness. The resultant oil was dissolved with CH2Cl2 and
filtered of a pad of silica gel, eluting with CH2Cl2 to afford
the corresponding boronate.
Scheme 4. Versatility of the aminoborane chemistry.
using ferrocene as a simple catalyst. Although the
atom economy of the overall process is far from ideal,
the accessibility of aniline derivatives make the meth-
ods complementary to previously described reactions
À
based on C H activation or halides. Furthermore, be-
cause they mostly use bispinacolatodiboron, those
methods afford pinacol boronates which are quite
stable but display a lower reactivity in cross-coupling
reactions. Our sequence is allowing for a direct prepa-
ration of various boron derivatives. Depending on re-
action work-up, the borylated product can be isolated
as a pinacol boronate, a boronic acid, a trifluoroborate
salt or a diaminonaphthylborane (Scheme 4).
Acknowledgements
L.M. thankings the Aquitaine Region for a fellowship. This
work was supported by the Aquitaine Region.
Concerned by safety issues associated with handling
diazonium salts, we performed the reaction in a con-
tinuous flow system (Figure 1). The reaction condi-
tions were briefly optimised and we found that pre-
mixing the diazonium salt and ferrocene in a T mixer
allowing for 5 min of reaction before adding the ami-
noborane (T2) was the best set of conditions. 408C
was optimal; lower temperatures were detrimental to
yield, and higher temperature decreased the product
purity. The compound was isolated with 80% yield,
on a 10-mmol scale, with safe generation of nitrogen
throughout the process.
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Iron-Catalysed Borylation of Arenediazonium Salts to Give
7
Access to Arylboron Derivatives via ArylACHTNUTRGNEUNG(amino)boranes at
Room Temperature
Adv. Synth. Catal. 2013, 355, 1 – 7
Ludovic D. Marciasini, Nicolas Richy, Michel Vaultier,
Mathieu Pucheault*
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