Reconnaissance of reactivity of an Ag(II)SO4 one-electron oxidizer towards naphthalene derivatives

Article abstract of DOI:10.1039/c7nj02299a

We test divalent silver sulphate, Ag(ii)SO₄ as a novel reagent for oxidative coupling of aromatic hydrocarbons under ambient temperature conditions. The applicability of the C(sp²)-C(sp²) coupling protocol is illustrated for naphthalene and its 1-substituted derivatives containing either electron donating (e.g. Me, MeO, or Ph) or electron-withdrawing groups (X = F?I), leading to 4,4′-disubstituted-1,1′-binaphthyls. Coupling of 2-bromo-naphthalene yields a mixture of 2,2′-, 2,7′-, and 7,7′-dibromo-1,1′-binaphthyls together with their trimeric and tetrameric analogues. The coupling of strongly electron-withdrawing 1-CF₃-naphthalene provides the 5,5′-disubstituted-1,1′-binaphthyl derivative. The new method does not require the presence of halogen substituents, in contrast to most of the known C-C coupling methods, and it preserves them, if present. Ag(ii)SO₄ may be easily electrochemically regenerated from the Ag(i)HSO₄ byproduct. However, the C-C coupling method currently suffers from low yields, up to 17%, and it requires further optimization.

Full text of DOI:10.1039/c7nj02299a

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Reconnaissance of reactivity of an Ag(II)SO4
one-electron oxidizer towards naphthalene
Cite this:DOI: 10.1039/c7nj02299a
derivatives†
Adam K. Budniak,ab Michał Masny,c Kristina Prezelj,a Mikołaj Grzeszkiewicz,d
Jakub Gawraczynski,ab Łukasz Dobrzycki,e Michał K. Cyranski,e Wiktor Kozminski,b
´
´
´
´
Zoran Mazej,f Karol J. Fijałkowski,a Wojciech Grochala *a and
Piotr J. Leszczynski*a
´
We test divalent silver sulphate, Ag(II)SO4 as a novel reagent for oxidative coupling of aromatic
hydrocarbons under ambient temperature conditions. The applicability of the C(sp2)–C(sp2) coupling
protocol is illustrated for naphthalene and its 1-substituted derivatives containing either electron
donating (e.g. Me, MeO, or Ph) or electron-withdrawing groups (X = Fꢀ ꢀ ꢀI), leading to 4,40-disubstituted-
1,10-binaphthyls. Coupling of 2-bromo-naphthalene yields a mixture of 2,20-, 2,70-, and 7,70-dibromo-
1,10-binaphthyls together with their trimeric and tetrameric analogues. The coupling of strongly
electron-withdrawing 1-CF3-naphthalene provides the 5,50-disubstituted-1,10-binaphthyl derivative. The
new method does not require the presence of halogen substituents, in contrast to most of the known
C–C coupling methods, and it preserves them, if present. Ag(II)SO4 may be easily electrochemically
regenerated from the Ag(I)HSO4 byproduct. However, the C–C coupling method currently suffers from
low yields, up to 17%, and it requires further optimization.
Received 27th June 2017,
Accepted 15th August 2017
DOI: 10.1039/c7nj02299a
rsc.li/njc
of the organic substrate; also, it is not uncommon to find
demanding substrates that are incompatible with the published
Introduction
The transition metal catalyzed aromatic coupling reactions procedures.10
preceded by oxidative C–H bond activation constitute an extremely
The Cu-based reactions are inexpensive and thus attractive
valuable synthetic tool in modern chemistry.1,2 Most prevalent are for large industrial-scale reactions.11 An interesting example of
the Pd-, Cu-, and FeCl3-catalyzed reactions which have been a recently reported copper-based aromatic coupling protocol
successfully used to synthesize a number of fascinating and useful without prior functionalization of substrates is the Hirano–
compounds.3 Along with routinely used reagents, new oxidizers Miura reaction;12 this method has been successfully applied for
have been introduced, such as e.g. MoCl5,4 CoF3,5 TiCl4,6 various substrates,13 but it proceeds at elevated temperature,
iodonium(III) salts,7 (H3C)ReO3,8 the environmentally friendly T 4 180 1C, as typical for Cu-based methods. Silver, a heavier
H2O2/peroxidase-catalyst system,9 and highly toxic Hg(II), Tl(III) or analogue of copper, has been traditionally used for the coupling
Pb(IV) reagents. These methods usually require prefunctionalization reactions involving only the acetylide C(sp) fragment, since Ag(I)
readily forms acetylide complexes. Also, the 2-electron Ag(III)/
a
Ag(I) redox pair has recently been applied for cross-coupling
reactions.14 However, the potential of the 1-electron Ag(II)/Ag(I)
redox pair has not yet been properly explored in organic
chemistry15 and that is mainly due to the very high oxidizing
power of Ag(II), which is not compatible with an aqueous
environment (E0 E +2 V vs. normal hydrogen electrode).16 Thus,
Ag(II) has only been used as a short-lived redox-intermediate in
combination with peroxodisulphate oxidizers, the respective
reactions leading to oxidation rather than C–C coupling of
reagent molecules.17 On the other hand, reactions involving
AgF2 and other fluoro Ag(II) species lead to partial or exhaustive
fluorination of organic compounds.18
˙
Center of New Technologies, University of Warsaw, Zwirki i Wigury 93,
02089 Warsaw, Poland. E-mail: piotr.leszczynski@cent.uw.edu.pl,
w.grochala@cent.uw.edu.pl
b Faculty of Chemistry, University of Warsaw, Pasteur 1, 02093 Warsaw, Poland
c Faculty of Physics, University of Warsaw, Pasteur 5, 02093 Warsaw, Poland
d Department of Materials Engineering, Warsaw University of Technology,
Wołoska 141, 02507 Warsaw, Poland
e The Czochralski Laboratory of Advanced Crystal Engineering, Faculty of
˙
Chemistry, University of Warsaw, Zwirki i Wigury 101, 02089 Warsaw, Poland
f
ˇ
Department of Inorganic Chemistry and Technology, Jozef Stefan Institute,
Jamova cesta 39, 1000 Ljubljana, Slovenia
† Electronic supplementary information (ESI) available. CCDC 1476385–1476390,
1476392–1476397, 1528855 and 1528856. For ESI and crystallographic data in CIF
or other electronic format see DOI: 10.1039/c7nj02299a
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Cl, Br, I, MeO, Me, and Ph gives the corresponding 4,40-
disubstituted-1,10-binaphthyls (1–8) with rather small yields
(B10%) (Scheme 1 and Table S3 in the ESI†) albeit under
milder temperature conditions as compared to the relevant
Cu(II)-based Hirano–Miura reaction.12 The 1,10-binaphthyls
formed from pristine naphthalene (X = H), as well as for
X = F, Cl, Br, I, Me, OMe, and Ph, trace amounts of ternaphthyl
derivatives (unknown isomers, 11, 12) have also been detected
in the post-reaction mixture using the GC/MS technique for
X = H and F, respectively, thus showing that the formation of
oligomeric species using this method is in principle possible.
The identity of the products was confirmed using X-ray diffraction
on single crystals. In the case of H, MeO, Me and Br substituents,
we have confirmed the previously published structures.24 However,
for 2, 3, and 5 with electron-withdrawing substituents and for 8,
their crystal structures were determined here for the first time
(Table 1).
+
The organic products, formed from (R–H)ꢂ , Rꢂ in the course
of reactions, remain in the solution, and they may be easily
separated using extraction and preparative thin-layer chromato-
1
graphy, their chemical identity being confirmed using H, 13C,
19F and 1H vs. 13C HSQC NMR spectra, and IR spectrometry
(ESI†), as well as single crystal X-ray crystallography – see Table 1.
The complete structural and spectroscopic characteristics of all
products will be described in a separate contribution.
Cross-coupling compatible with the presence of halogens in
the aromatic ring has previously been revealed by Kita and
co-workers.7 We have also attempted several cross-coupling reactions
using mixtures of two different 1-halogenonaphthalenes (9–10);
GC/MS analysis clearly shows the presence of the cross-coupled
products in addition to the homo-di-halogenated ones (ESI†);
however, the separation of the products is troublesome due to
their similar retention times, and all products co-crystallize
while forming mixed crystals (ESI†).
In the case of 1-trifluoromethylnaphthalene, an aromatic
system with a very strongly electron withdrawing substituent,
C–C coupling proceeds, as expected, with very low yield (B1.5%),
but it leads to 5,50- (13) rather than the 4,40-disubstituted-1,10-
binaphthyl derivative (Fig. 1). This turns out to be the first
structurally characterized 5,50-disubstituted-1,10-binaphthyl, since
the multi-step method published so far leads to the 4,40-substituted
derivative as a side product (26% yield) of Grignard synthesis on the
Br-preactivated substrate.25 The ring-deactivating influence of the
CF3 substituent clearly shifts reactivity to the adjacent aromatic ring
in the Br-free molecule, as seen in the Ag(II)SO4-based synthetic
Scheme 1 Ag(II)SO4-based C–C coupling reactions involving naphtha-
lene and its derivatives.
Here we attempt to expand the family of inorganic substrates
used for aromatic coupling reactions by applying a powerful
Ag(II)SO4 oxidizer as a substrate; Ag(II)SO4 is a unique example of
a divalent silver compound containing a fluorine-free anion.19
For reconnaissance of the Ag(II)SO4 C–H activation capability and
to illustrate the most fundamental features of the method we
have initially chosen naphthalene and a set of its 1-substituted
derivatives, which contain selected electron donating (MeO, Me,
Ph) or withdrawing groups (F, Cl, Br, I, CF3, CN, NO2) (Scheme 1).
The targeted products – homochiral 1,10-binaphthyl derivatives –
have been utilized in the past as chiral auxiliaries and/or inducers
for highly stereoselective reactions because of their axial asymmetry
and molecular flexibility.20,21
Results and discussion
Due to the lack of solubility of Ag(II)SO4 in common organic protocol. It turns out that the reaction yield may be increased to
solvents the reactions proceed initially at the solid–liquid 17% by using nitromethane as a reaction medium. Despite the
interphase. Selection of an appropriate liquid medium is not still unsatisfactory yield, formation of 13 constitutes an improve-
trivial due to the high reactivity of the inorganic substrate. ment over the previously used methods since 1-trifluoromethyl-
During a preliminary screening of reaction conditions we have naphthalene could not so far be activated to form a C–C coupled
found out that selectivity of reactions as well as their speed and product. In the case of a 1-cyano substituted substrate, the yield of
yield increase when lower aliphatic or alicyclic hydrocarbons are the C–C coupling was even lower than for the CF3 one (regardless
substituted by hexafluoroisopropyl alcohol, HFIPA (F6-i-PrOH). of the solvent), as evidenced by GC/MS, and the corresponding
This polar solvent is known to stabilize organic radical cations,22 binaphthyl product (14) could not be isolated. Finally, for R = NO2
and also facilitates the 1eꢁ and proton-transfer heterophasic the reaction did not proceed to any detectable extent, which
reactions.23 The herein reported procedure applied to R = H, F, shows that even stronger oxidizers may be needed to prepare 15.
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previously for the naphthalene derivatives (e.g., orange-brown in
nitromethane, purple in (CF3)3COH, etc.; for the –CRCH derivative
we have observed a faint green colour of the solution but no product
could be isolated).
Given the electron-transfer character of the first step of
reaction (eqn (1)), one might try to influence its fate by using
solvents of large dielectric constants; HFIPA (e = 17.8) and NM
(e = 35.9) certainly count as such and the yields in these solvents
were much higher than those in nonpolar cyclohexane (e = 2.0).
Further improvement would require the use of N-methylacetamide
(e = 170) or N-methylformamide (e = 182.4) but, regretfully, these
solvents are readily oxidized by Ag(II)SO4.
Analysis of the white solid residue using powder X-ray
diffraction and IR spectroscopy has showed that Ag(I)HSO4 is
the solid by-product of the reaction; this suggests that a
subsequent proton transfer reaction must take place, eqn (2):
Fig. 1 Thermal ellipsoid plot drawn at the 50% probability level for crystal
structure of 13. CF3 groups are labelled for clarity.
+
ꢁ
(R–H)ꢂ + Ag(I)SO4 - Rꢂ + Ag(I)HSO4
(2)
Interestingly, 2-halogenoaphthalenes react under the same
conditions with the formation of a mixture of 2,20-, 2,70-, and
7,70-dihalogeno-1,10-binaphthyls (16–24) together with trace
amounts of their trimeric (25–27) and even tetrameric analogues
(28), as evidenced from ESI-TOF spectra (ESI†). The crystal
structures of 22 and 23 were determined for the first time and
will be focused on elsewhere.
Indeed, we have observed that if reactions are conducted in
(CF3)3COH (which is more (Brønsted) acidic than (CF3)2C(H)OH,
by 4 orders of magnitude in pKa values) the reaction yields are
usually even smaller than for (CF3)2C(H)OH solvent. On the
other hand, some improvement of the reaction yield may be
achieved in selected cases when using nitromethane (NM) as a
solvent; note that NM is 2 orders of magnitude less acidic than
(CF3)2C(H)OH. Taken together this suggests that proton transfer
is an important step in the overall reaction cycle. Consequently,
we have attempted to influence the equilibrium of this reaction
stage by adding Lewis bases (such as amines or fluorinated
amines) to the reaction mixture; regretfully, most Lewis bases
are not capable of withstanding the presence of Ag(II)SO4 and
the reaction yields could not be improved.
Tentative reaction mechanism and attempts of yield improvement
Given the low yields, we have attempted to gain preliminary
insight into the reaction mechanism, so that the reaction
conditions could be further judiciously optimized.
It turns out that the first steps of reaction, connected with
the formation of deeply-coloured organic radical-cations, and
discoloration of black Ag(II)SO4, proceeds immediately at room
temperature and even at ꢁ35 1C in most cases, which suggests
the presence of an intrinsically low barrier for the electron-
transfer reaction, eqn (1):
Given the chemical nature of the main reaction products, the
simplified overall reaction of the oxidative dehydrodimerization
may be written as:
+
ꢁ
R–H + Ag(II)SO4 - (R–H)ꢂ + Ag(I)SO4
(1)
2R–H + 2Ag(II)SO4 - R–R + 2Ag(I)HSO4
(3)
Importantly, Ag(II)SO4 may be easily regenerated from
The small barrier for electron transfer reaction described by
eqn (1) is consistent with the large electron affinity of the surface
of Ag(II)SO4 crystallites. Our preliminary screening of organic
reagents with diverse ionization potentials (not shown) has
indicated that the electron affinity of Ag(II)SO4 is at least 9.3 eV,
which is quite large as compared to that of common organic
electron acceptors, such as TCNQ (4.8 eV), TCNE (2.9–3.2 eV), or
F4-TCNQ (5.2 eV). This means that the giant electron affinity of
the naked Ag(2+) cation in the gas phase (21.5 eV) is reduced to
about 43% of its value due to ligation by SO42ꢁ Lewis bases. Still,
what remains suffices for electron transfer reactions with
aromatics. It is quite likely that given the large difference of
ionization potential of organic molecules studied (e.g. naphthalene
8.14 eV, 1-F-naphthalene 8.15 eV, 2-F-naphthalene 8.23 eV, etc.)
and electron affinity of AgSO4 (49.2 eV) the reaction (eqn (1))
proceeds via the outer sphere mechanism when an organic
Ag(I)HSO4 via electrolysis with B70% current yield:26,27
2Ag(I)HSO4 - H2 + 2Ag(II)SO4
(4)
Eqn (1) might suggest that Ag(II) is a substrate of the
reaction; however, since it may be regenerated (eqn (3)) it
rather becomes a redox mediator, and the overall reaction cycle
((3) + (4)) corresponds jointly to:
2R–H - R–R + H–H
(5)
The process described by eqn (5) is thermodynamically uphill
for naphthalene (DH1 E +280 kJ molꢁ1, DG1 E + 240 kJ molꢁ1),
and its derivatives, but reactions (1)–(3) are jointly downhill in
free energy, while only eqn (4) requires energy input.
Synthetic procedures
molecule approaches the surface of AgSO4. In any case, the AgSO4 was obtained as described in the literature.19,27
A
+
radical-cations formed, (R–H)ꢂ , are deeply coloured, as observed typical synthetic procedure is as follows: 2 mmol of Ag(II)SO4
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(2-fold excess) was added to 1 mmol of naphthalene dissolved (10-1 in C2/c), (10-2 in C2) and (10-2 in C2/c), 13, 22, and 23,
in 10 ml of HFIPA at room temperature. After 72 h the resulting respectively.
dark mixture was evaporated using a rotary evaporator. The
residue was washed with hexane (2 ꢃ 5 ml) and methylene
Conclusions
chloride (2 ꢃ 5 ml) and evaporated again. The crude product
was then dissolved in 2 ml of methylene chloride and purified
In conclusion, we have described the application of a divalent
on a preparative silica gel TLC plate using hexane as the eluent.
silver compound, Ag(II)SO4, for CH activation and oxidative
The products were obtained by collecting the appropriate
coupling of naphthalene derivatives. A novel regioselective
phases and subsequent removal of the solvent under reduced
single-pot protocol leads to the formation of 1,10-coupled
pressure. The purity and physicochemical properties of the
binaphthyls when corresponding substrates contain the electron
product were investigated using the tandem GC/MS technique,
donating groups or mildly electron withdrawing groups;
oligomerization and cross-coupling have also been observed.
and 1H, 13C, 19F and 1H vs. 13C HSQC NMR & IR spectra (ESI†).
The crystal structures of the products were determined using
For very strongly electron withdrawing and ring-deactivating
single-crystal XRD, with the help of the software and procedures
substituents 5,50-coupled products are formed. Ag(II)SO4 turns
described in ref. 28.
out to be the only oxidizer currently known which enables direct
Four investigated crystals obtained after cross-coupling
oxidative aromatic coupling of electron-poor CF3-substituted
reactions involving F/Cl and F/Br substituted naphthalene
naphthalene, albeit with low yield up to 17%. Despite their
derivatives are disordered and contain non-integer numbers
rather low yields, the syntheses on the 2 mmol scale followed by
of halogen atoms. This is due to the co-crystallization of F/Cl
preparative thin layer chromatography allowed us to prepare
and F/Br reaction products in a non-stoichiometric ratio to
about a dozen novel binaphthyl derivatives.
form mixed crystals. During the structural refinement of the
The Ag(II)-based protocol does not require any prefunctio-
mixed crystals the position and anisotropic temperature factors
nalization of the organic substrate (similarly to the Hirano–
for all non-H atoms were refined. The occupancy ratio of F/Cl or
Miura method12 and to the cross-dehydrogenative coupling of
F/Br atoms was free to refine. To check if this ratio was
the C(sp3)–H bonds, which has been recently reviewed29), and it
preserved in the solid phase we measured two different crystals
even preserves the halogen substituent, if present. The reactions
for both cross-coupling reactions. Crystals (9) and (10) correspond
proceed without the formation of substituted naphthoquinones
or phthalic acids, as would be typical for Ag(II)-mediated reactions
to F/Cl and F/Br samples respectively. In the case of F/Br mixed
crystals we observed possible lowering of the space group
using peroxodisulphate reagents in the aqueous environment; on
symmetry from C2/c to chiral C2. For a better comparison we
the other hand, this method does not tolerate functional groups,
which may easily be oxidized (NH2, OH, CHO, etc.). The inorganic
present both refinements for each crystal of (10) [(10-1 in C2),
(10-1 in C2/c), (10-2 in C2) and (10-2 in C2/c)]. When applying the
chiral C2 symmetry the crystals appeared to be twinned by
inversion. The twin component ratios were refined to be
0.53(3) and 0.47(3) and 0.80(3) and 0.20(3) for (10-1 in C2) and
(10-2 in C2) crystals respectively. Indeed, better structural refine-
ment parameters in the chiral space group comparable to the
centrosymmetric C2/c choice and the statistically significant
Ag(I) intermediate (Ag(I)HSO4) may easily be separated from
organic products, and recycled back to Ag(II)SO4;30 minor Ag(I)-
containing impurities are considered to be biocompatible, unlike
many other transition metal traces. The low yields, currently up
to 17% at room temperature, are difficult to be improved by the
judicious choice of the reaction medium due to constraints
imposed by the very potent one-electron oxidizer, Ag(II)SO4.
component ratio definitely far from 0.5 for (10-2 in C2) suggests
In forthcoming contributions we will describe the applicability of
the lowering of the symmetry in mixed F/Br crystals. All the
Ag(II)SO4 and other Ag(II) salts in the formation of C(sp2)–C(sp3) and
mixed crystals can be considered as isostructural with (2), (3),
C(sp3)–C(sp3) coupled products including phenyl derivatives,23 novel
and (4) with molecules located on a 2-fold axis. In the F/Br
crystals refined in the C2 space group the asymmetric part of the
unit cell contains, however, two halves of the organic molecule.
reactivity patterns, more detailed mechanistic studies of the reaction
mechanism and further attempts of reaction optimization.31
The presence of the binaphthyl derivative on the special symmetry
suggests that the reaction products are homo-halogens. One should Conflicts of interest
have in mind, however, that mixed coupling products in the
There are no conflicts of interest to declare.
solid state may imitate higher symmetry using substitutional
disorder. Larger and elongated thermal ellipsoids of C atoms in
mixed crystals compared to their single-component analogues
suggest that whole molecules in (9) and (10) exhibit positional
Acknowledgements
disorder.
PJL thanks the National Science Centre of the Republic of
Further details of the crystal structures may be obtained Poland (NCN) for the OPUS grant (UMO-2012/07/B/ST5/01872).
from Cambridge Crystallographic Data Centre on quoting the ZM acknowledges the Slovenian Research Agency (ARRS) for
CCDC 1476385, 1476386, 1476387, 1476388, 1476389, 1476392, financial support of the Research Program P1-0045. AKB thanks
1476393, 1476394, 1476395, 1476396, 1476397, 1476390, the Warsaw Consortium of Academic Chemistry for the KNOW
1528855 and 1528856 for 2, 3, 4, 5, 8, (9-1), (9-2), (10-1 in C2), scholarship. The authors thank Mr Maciej Sojka from IChO PAN
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´
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