Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF5-substituted phenylboronic esters and iodobenzenes

Article abstract of DOI:10.3762/bjoc.11.162

Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl) phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.

Full text of DOI:10.3762/bjoc.11.162

Pyridine-promoted dediazoniation of aryldiazonium
tetrafluoroborates: Application to the synthesis of
SF5-substituted phenylboronic esters and iodobenzenes
George Iakobson1, Junyi Du2, Alexandra M. Z. Slawin2 and Petr Beier*1
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2015, 11, 1494–1502.
1Institute of Organic Chemistry and Biochemistry, Academy of
Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague
6, Czech Republic and 2EaStCHEM School of Chemistry, University
of St Andrews, St Andrews, KY16 9ST, United Kingdom
doi:10.3762/bjoc.11.162
Received: 25 March 2015
Accepted: 05 August 2015
Published: 26 August 2015
Email:
Petr Beier* - beier@uochb.cas.cz
Associate Editor: V. Gouverneur
* Corresponding author
© 2015 Iakobson et al; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
borylation; diazonium salts; iodination; pyridine; sulfur pentafluorides
Abstract
Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine,
or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (penta-
fluorosulfanyl)phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
Introduction
Pentafluorosulfanyl-containing compounds have been known mostly prepared by the derivatization of commercial nitro-
for more than half a century [1-4]; however, for a long time (pentafluorosulfanyl)benzenes [14,17-27] and approaches from
they remained a relatively underdeveloped class of compounds SF5-aliphatics have also been studied [28-30]. The unique
[5,6]. The main reason for the slow development of the chem- combination of properties the SF5 group imparts includes high
istry of SF5-containing compounds was the lack of availability chemical, thermal, and metabolic stability, strong electron-
of key building blocks. However, in recent years, the scientific acceptor property, and high lipophilicity. Furthermore, applica-
community has been witnessing a renewed interest in this func- tions of SF5 compounds in catalysis [31,32], life-science
tional group. Synthetic methods towards aliphatic SF5- [6,18,33-38], and material sciences [5,19,38,39] are emerging.
containing compounds are based on free radical addition of
SF5Cl or SF5Br to unsaturated compounds [7-9], whereas Arylboronic acids and arylboronates represent versatile building
aromatic derivatives are available either by the Umemoto’s two- blocks in organic synthesis [40]. They have found wide applica-
step synthesis from diaryl disulfides or benzenethiols [10-12], tions in transition metal-catalyzed cross-coupling reactions
or by the reaction of nitrophenyl disulfides with elemental fluo- [41,42]. These boron compounds are accessed mainly by the
rine [13-16]. Aromatic and heteroaromatic SF5 compounds are reactions of arylmagnesium or aryllithium species with trialkyl-
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boronates [43,44], Pd- or Cu-catalyzed borylations of aryl
halides using B2pin2, H-Bpin [45-50] or R2N-BH2 [51], direct
borylations via aromatic C–H bond activations [52-58], Lewis
acid catalyzed electrophilic borylations of electron-rich arenes
[59-62], and Sandmeyer-type borylation of arylamines or diazo-
nium salts with B2pin2 [63-67], B2(OH)4 [68] or R2N-BH2 [69].
Several attempts were made to synthesize the SF5-phenyl-
boronates. Patent literature describes the synthesis of 3- or
4-(pentafluorosulfanyl)phenylboronates or boronic acids from
SF5-bromobenzenes via lithiation or magnesiation. These
approaches suffer from low yields and other drawbacks [70,71].
For lithiation of the aryl bromide, t-BuLi had to be used and the
formation of Grignard reagents is inefficient. On the other hand,
Shibata and co-workers have recently reported the synthesis of
3,5-bis(pentafluorosulfanyl)phenylboronic acid from the corres-
ponding aryl bromide, trimethyl borate and iPrMgBr [32].
Table 1: Synthesis of boronates 2 from aniline derivatives 1a.
Entry
1
Additive
Temp. (°C)
2, Yield (%)b
1
2
3
1a, 3-SF5 BPO
1b, 4-SF5 BPO
rt
2a, 70
rt
2b, traces
2b, 55c
1b, 4-SF5
—
80
aReaction conditions: 1 (1 mmol), t-BuONO (1.5 mmol), B2pin2
(1.1 mmol), additive (2 mol %), MeCN (4 mL). bIsolated yield.
c82% purity.
Finally, Joliton and Carreira have recently shown efficient were obtained on 0.3–6 g scale (Table 2). Crystal structures of
Ir-catalyzed C–H borylation of several 1-substituted-3-(penta- 3a (CCDC 1009848) and 3b (CCDC 1009849) were deter-
fluorosulfanyl)benzenes and applied the products of borylation mined confirming the nature of the products. During the course
to the Pd-catalyzed Suzuki–Miyaura reaction with aryl bro- of our studies, Okazaki and co-workers reported the synthesis of
mides or iodides. However, the reaction is limited to boryla- 3b in 84% yield under similar conditions and have shown its re-
tions in position five of 1-substituted-3-(pentafluorosulfanyl)- activity in various cross-coupling reactions with varied degree
benzenes [72].
of success. The most efficient cross-coupling reactions were the
Heck reactions with alkenes, a biaryl homocoupling reaction, an
Straightforward access to SF5-phenylboronic acids or boronates azo coupling to electron-rich arenes, and a dediazoniation with
would be highly desirable since it would allow easy installation TMSN3 in an ionic liquid medium [74,75].
of the SF5-phenyl group by the subsequent Suzuki–Miyaura
reaction. Nitro-(pentafluorosulfanyl)benzenes are the primary An efficient borylation of aryldiazonium tetrafluoroborates with
industrial SF5-aromatics, therefore the easiest access to SF5- NHC-Pd catalysts was reported recently [63]. When applied to
phenylboronates appears to be starting from readily available 3a and 3b using Pd(OAc)2 and NHC ligand precursors L, the
SF5-substituted anilines or diazonium salts rather than SF5- borylated products 2a and 2b were isolated in only moderate
containing halobenzenes. Herein, we report a new protocol for yields (Table 2, entries 1 and 2). However, it was found that the
efficient borylation, iodination and hydrodediazoniation of SF5- Pd catalyst was not required for an efficient reaction. Alkali
phenyldiazonium tetrafluoroborates in the presence of pyridine. metal acetates are known to facilitate decomposition of aryldia-
The generality of the borylation and iodination reactions was zonium salts by the formation of diazoacetates and diazo anhy-
demonstrated on several examples.
drides, which decompose to aryl radicals [76]. These additives
were used in Meerwein arylation of isopropenyl acetate [77]. In
our case, two-fold excess of sodium acetate in acetonitrile
Results and Discussion
At the onset of our investigation, Sandmeyer-type borylation of afforded 2a and 2b in good and moderate yields, respectively
3- and 4-(pentafluorosulfanyl)anilines (1a and 1b, respectively) (Table 2 ,entries 3 and 4). The conditions reported by Yu and
to pinacolboronates 2a and 2b according to Wang and co-workers [66] (Table 2, entry 5) provided a mixture with
co-corkers was studied [64,65] (Table 1). The borylation of 1a starting 3b as the major component. While the diazonium salts
took place in a reasonable yield in the presence of catalytic 3a and 3b were found to be stable in acetonitrile, we observed
amounts of benzoyl peroxide (BPO, Table 1, entry 1), while for slow decomposition in methanol and in the presence of B2pin2
1b, heating without any additives was preferable; however, the under strictly Pd-free conditions (new Teflon stirring bar and
yield of 2b was only moderate (Table 1, entry 3).
glassware), the borylation took place with low conversion
(Table 2, entry 6) [78]. In pyridine, however, the decomposi-
For a detailed investigation of the borylation reaction, the diazo- tion of 3b was very fast and a vigorous evolution of nitrogen
nium tetrafluoroborates 3a and 3b were prepared and isolated was observed affording the borylated product in a moderate
according to Doyle conditions [73]. High yields (above 90%) of yield together with a mixture of SF5-pyridines in ca.
both isomers of the diazonium tetrafluoroborates 3a and 3b 10% GC–MS yield (Table 2, entry 7). Finally, the use of a
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Table 2: Synthesis of diazonium tetrafluoroborates 3a and boronates 2b.
Entry
3 (mmol)
3a (1)
Reagents (equiv), solvent Temp. (°C)
Time (h)
2, Yield (%)c
2a, 43
1
2
Pd(OAc)2 (0.01), L (0.02), rt
THF
18
18
3b (1)
Pd(OAc)2 (0.01), L (0.02), rt
2b, 57
THF
3
4
5
3a (1)
3b (1)
3b (1)
NaOAc (2), MeCN
NaOAc (2), MeCN
−50 to rt
−50 to rt
rt
3
2a, 73
2b, 49
2b, 23
3
CuBr (0.05), MeCN/H2O
(3:1)
330
6
3a (1)
3b (1)
3b (1)
3b (3)
3a (2)
—, MeOH
rt
24
2
2a, 32
2b, 55
2b, 77
2b, 77
2a, 80
7
—, pyridined
−30 to rt
−30 to rt
−30 to rt
−30 to rt
8
pyridine (4), MeCNd
pyridine (4), MeCNd
pyridine (4), MeCNd
2
9
2
10
2
aReaction conditions: 1 (1–28 mmol), BF3·OEt2 (2.1 equiv), t-BuONO (1 equiv), CH2Cl2 or Et2O (3 mL/1 mmol of 1), 30 min. bReaction conditions: 3
(1–3 mmol), B2pin2 (1 equiv), reagents, solvent (2 mL/1 mmol of 3) under N2. cIsolated yield. dThe reaction was conducted under air.
4-fold excess of pyridine in acetonitrile was found to be borylation with an equimolar amount of B2pin2 (Scheme 1);
optimal. Conducting the reaction on a gram scale proceeded however, ortho-substituted phenyldiazonium salts were found
without a notable loss of efficiency and the reaction can be to be either not efficient substrates (3f) or completely unreac-
performed in air (Table 2, entries 8–10).
tive (3g), presumably due to a large steric demand of B2pin2.
Pyridine is known to induce decomposition of aryldiazonium The mechanism of this borylation reaction remains to be eluci-
salts. Zollinger and Abramovitch studied the interaction of pyri- dated. Based on experimental results and literature precedent,
dine with aryldiazonium tetrafluoroborates and suggested the we propose the following free-radical mechanism (Scheme 2).
formation of diazopyridinium salts which homolytically decom- Aryldiazonium salt 3 reacts with pyridine to form aryldiazopyri-
pose to aryl radicals, nitrogen and a pyridinium tetrafluoro- dinium 4 which decomposes to an aryl radical, a pyridinium
borate radical [79,80]. Tanaka and co-workers have used the tetrafluoroborate radical and nitrogen. The aryl radical reacts
combination of PhN2+BF4− and pyridine for arylations of with B2pin2 to form the borylated product 2 and the Bpin
silylenol ethers [81]. They have observed the formation of large radical (likely to be stabilized by pyridine) [82]. The byprod-
amounts of phenylpyridines. In our case, we detected SF5- ucts pyridine·BF3 and F-Bpin are formed by the reaction of the
phenylpyridines in trace amounts only during borylation using pyridinium tetrafluoroborate radical and the Bpin radical.
pyridine as a solvent. The major products in the borylation reac-
tion apart from 2a and 2b were found to be F-Bpin and pyri- Subjecting the diazonium salt 3i to the borylation conditions
dine·BF3 complexes. Both compounds are easily hydrolyzable gave further indirect evidence for the formation of aryl radicals
but they were observed by NMR of the crude reaction mixture (Scheme 3). Full conversion of 3i was observed affording a
and compared to the synthetized authentic samples. On the mixture of products 2i, 2i’, 5i (two isomers of unknown con-
other hand, we were not able to observe a pyridine·B2pin2 com- figuration) and 6i in 16:31:28:25 GC–MS ratio. The presence of
plex by 11B NMR in CD3CN or CDCl3. The borylation was these products can be explained only by the formation of the
extended to several other aryldiazonium tetrafluoroborates substituted SF5-phenyl radical which undergoes borylation to
showing that both electron-donor and electron-acceptor substi- 2i, hydrogen atom transfer followed by borylation to 2i’,
tuted phenyldiazonium tetrafluoroborates undergo efficient intramolecular cyclization to 5i or hydrogen abstraction to 6i.
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Scheme 1: Borylation of aryldiazonium tetrafluoroborates 3. Reaction conditions: 3 (1 mmol), B2pin2 (1 mmol), pyridine (4 mmol), MeCN (2 mL), 2 h.
Table 3: One pot diazotization-borylation of 1ba.
Entry
Acid (equiv)
Time (h)
2b, Yield (%)b
1c
2
p-TsOH·H2O (1) 15
51
81
78
Scheme 2: Proposed reaction mechanism.
aq HBF4 (1.7)
aq HCl (1.7)
1
1
3
aReaction conditions: 1b (1 mmol), acid, t-BuONO (1 mmol), MeCN
(3 mL), B2pin2 (1.0–1.1 mmol), pyridine (4 mmol). bIsolated yield.
cReaction temperature for steps 1 and 2 was rt.
Starting from aniline derivative 1b, a one pot diazotiza-
tion–borylation sequence using different acids afforded the
corresponding borylated product 2b in good yields (Table 3).
Suzuki–Miyaura cross-coupling reactions of boronates 2a and Transformation to SF5-phenylboronic acid 8b and potassium
2b with aryl iodides using a simple system without any optimi- trifluoroborates 9 was straightforward under standard condi-
zation proceeded in satisfactory yields considering the electron- tions (Scheme 5). Similar potassium SF5-phenyltrifluoro-
deficient character of the boronates and consequently less effi- borates were found to be highly reactive with a variety of aryl
cient transmetallation step (Scheme 4).
bromides and iodides in the presence of catalytic amounts of
Scheme 3: Reaction of diazonium salt 3i under borylation conditions.
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Beilstein J. Org. Chem. 2015, 11, 1494–1502.
Scheme 4: Suzuki–Miyaura reaction of boronates 2a and 2b with aryl iodides. Reaction conditions: 2 (1 mmol), ArI (1.1 mmol), Pd(PPh3)4 (5 mol %),
LiOH·H2O (4 mmol), 1,4-dioxane (2 mL), water (1 mL), 3.5 h.
To extend the synthetic utility of the pyridine-mediated derivati-
zation of aryldiazonium tetrafluoroborates we investigated the
reaction with iodobenzene and iodine as efficient scavengers of
aryl radicals [83,84]. A competitive experiment starting from 3a
and equimolar amounts of B2pin2 and iodobenzene in the pres-
ence of pyridine (4 equiv) in MeCN afforded a mixture of 2a
(72% yield) and 1-iodo-3-(pentafluorosulfanyl)benzene (10a,
23% yield). Additionally, a reaction of 3b with PhI (4 equiv) in
Scheme 5: Syntesis of boronic acid 8b and trifluoroborates 9. Reac-
tion conditions for the synthesis of 8b: 2 (2 mmol), NaIO4 (8 mmol),
the absence of B2pin2 gave 1-iodo-4-(pentafluorosulfanyl)-
benzene (10b) in 35% yield. Both experiments point to the for-
mation of aryl radicals during the reaction and suggest a possi-
bility to conduct practical aromatic iodination. Indeed, the iodi-
nation reaction with I2 proved to be more efficient than with PhI
THF (8 mL), H2O (2 mL), rt, 1 h. Reaction conditions for the synthesis
of 9: 2 (2 mmol), KHF2 (10 mmol), MeOH (8 mL), H2O (3.6 mL), rt,
20 min.
PdCl2(dppf)·CH2Cl2 or Pd(OAc)2 [72]. The recently published (Scheme 6). In contrast to borylation, iodination with I2 shows a
synthesis of arylboronic acids from anilines or aryldiazonium higher sensitivity to electronic properties of substituents on the
tetrafluoroborates using B2(OH)4 [68] applied to 3b provided aromatic ring. Electron-acceptor substituted aryldiazonium
8b in only 25% 19F NMR yield.
compounds are excellent substrates while those with electron-
Scheme 6: Iodination of aryldiazonium tetrafluoroborates 3. Reaction conditions: 3 (1 mmol), I2 (1.1 mmol), pyridine (4 mmol), MeCN (3 mL), 2 h.
aYields in the presence of collidine instead of pyridine.
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donor groups react much less efficiently. The substitution of
pyridine with collidine (2,4,6-trimethylpyridine) gave similar
yields. Unlike borylations, the iodination reactions were not
sensitive to ortho substitutions. In the case of 3i, compound 10i
was the sole product; no product of hydrogen atom transfer or
cyclization was observed, demonstrating that the reaction with
I2 is much faster than with B2pin2. Importantly, the yields of
SF5-phenyl iodides 10a and 10b using our two-step diazotiza-
tion–iodination method significantly exceed those obtained by
classical Sandmeyer reaction (ca. 80% yield over two steps
compared to 63% for 10a and 50% for 10b by one-pot Sand-
meyer procedure requiring 10 fold excess of KI) [14]. The side-
product in the iodination of 3 was bis(pyridine)iodonium tetra-
fluoroborate, which can be easily isolated from the reaction
mixture by precipitation upon addition of diethyl ether. This
iodonium salt was first synthetized by Barluenga [85] and later
used for mild iodination of alkenes, alkynes and aromatics [85-
87]. Its formation can be explained by the reaction of the pyri-
dinium tetrafluoroborate radical (Scheme 2), pyridine and I2 or
iodine radical. Bromination of 3b with Br2 was attempted under
conditions similar to iodination but the reaction was slow and
inefficient resulting in a mixture of products with expected
Table 4: Hydrodediazoniation of 3a and 3b with THFa.
Entry 3 (mmol) D source D enrichmentb 6, Yield (%)c
1
2
3
3a (0.5)
3b (0.5)
3b (0.5)
—
—
n/a
6, 75
n/a
6, 70
THF-d8
77–82
6-D, 48
(0.5 mL)
4
5
3b (0.25) C5D5N
0
0
6, 70
6, 67
(4 mmol)
3b (0.25) CD3CN
(0.75 mL)
aReaction conditions: 3 (0.25–0.5 mmol), pyridine (4 equiv), THF
(1 mL/1 mmol of 3), MeCN (3–4 mL/1 mmol of 3), 2 h. bBased on
GC–MS. cBased on 19F NMR using 1-nitro-4-(pentafluorosulfanyl)-
benzene as an internal standard.
1-bromo-4-(pentafluorosulfanyl)benzene as a minor product. furan (11) and pyridinium tetrafluoroborate were identified as
With equimolar NBS instead of bromine, the reaction is much byproducts of the dediazoniation reactions. Similarly to the
cleaner but slow; after overnight at ambient temperature the previous processes, we presume the formation of aryldiazopyri-
bromo product was isolated in 35% yield.
dinium 4 and its decomposition to an aryl radical and the pyri-
dinium tetrafluoroborate radical. The aryl radical abstracts a
Finally, hydrodediazoniation using tributyltin hydride or THF hydrogen atom from THF forming 6 and a THF radical. The
was tested and THF proved to be a more efficient hydrogen THF radical then transfers the hydrogen atom to the pyridinium
atom donor. The addition of excess pyridine to MeCN/THF tetrafluoroborate radical giving dihydrofuran (11) and pyri-
solution of diazonium tetrafluoroborates 3a or 3b led to an effi- dinium salt.
cient hydrodediazoniation and the formation of (pentafluoro-
sulfanyl)benzene (6). Deuteration experiments established that Conclusion
the hydrogen atom in the product comes exclusively from THF In conclusion, a novel dediazoniation–borylation methodology
and not from pyridine or MeCN (Table 4). The observed was developed based on the reaction of aryldiazonium tetra-
deuterium enrichment using THF-d8 was around 80%. Thermal fluoroborates with pyridine and B2pin2 to give arylpinacol-
decomposition of aryldiazonium salts prepared from immobi- borates. Particular emphasis was on the synthesis of SF5-
lized triazene precursors and the formation of deuterated phenylboronates where our methodology represents a consider-
aromatics using THF-d8 was reported [88]. We explain the able improvement in reaction efficiency compared to previ-
reduced yield of 6-D (48% yield) and the formation of tar prod- ously published syntheses. Furthermore, no transition metals are
ucts by hydrogen atom abstraction from 3 or 6 and subsequent needed and mild reaction conditions are used. The borylation is
polymerization. No significant amounts of double deuterated applicable to a variety of aryldiazonium tetrafluoroborates with
products were detected. The kinetic isotope effect was deter- electron-donor or acceptor groups while ortho-substituted
mined from intermolecular competition experiment using 3b substrates are less reactive. A mechanism involving aryl radi-
and a 1:1 mixture of THF and THF-d8 giving KIE = 5.5 (6:6-D cals is suggested. The Suzuki–Miyaura reaction of SF5-phenyl-
ratio determined by GC–MS) and combined yield of 62%. This boronates with aryl iodides provided the cross-coupling biaryl
means that the hydrogen abstraction is much faster than the products. In analogy to the borylation reaction, iodination of
deuterium abstraction and suggests the C-H(D) bond formation aryldiazonium tetrafluoroborates with pyridine and iodine
as the rate-limiting step. For unambiguous identification of the resulted in aryl iodides. An efficient reaction was observed with
rate-limiting step, individual rate constants kH and kD in two electron-acceptor substituted aromatic compounds even with
parallel reactions would have to be determined [89]. Dihydro- ortho-substituted derivatives. In the case of SF5-substituted
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Acknowledgement
Financial support from the Academy of Sciences of the Czech
Republic (Research Plan RVO: 61388963) and the Grant
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