Copper-catalyzed arylation of polycyclic aromatic hydrocarbons by the PO group

Article abstract of DOI:10.1039/d0cc06639g

The first example of a directed and regioselective arylation of polycyclic aromatic hydrocarbons (PAHs) by using a PO directing group is reported herein. The protocol uses a cheap copper catalyst, and results in a breakthrough meta-selective C-H functionalization of arylphosphine oxide compounds. Substrates with potential fluorescence properties, for example, pyrene and fluoranthene, were successfully arylated under the system, thus achieving an efficient modification of fluorescent molecules containing the PO functional group. This journal is

Full text of DOI:10.1039/d0cc06639g

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DOI: 10.1039/D0CC06639G
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Copper-Catalyzed Arylation of Polycyclic Aromatic Hydrocarbons
by P=O Group
Yuan Niu,a Zhichao Qi,a Qinxin Lou,a Pengbo Bai,a and Shangdong Yang*a b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The first example of a directed and regioselective arylation of the
polycyclic aromatic hydrocarbons (PAHs) by using a P=O directing
group is reported herein. The protocol uses cheap copper catalyst,
and results in a breakthrough meta-selective C–H functionalization
of arylphosphine oxides compounds. Substrates with potential
fluorescence properties, for example pyrene and fluoranthene,
were successfully arylated under the system, thus achieving an
efficient modification of fluorescent molecules containing P = O
functional group.
Transition-metal-catalyzed C–H functionalization has become
one of the most effective and convenient synthesis strategies at
present for the synthesis of organic molecules.[1] An approach that
has received widespread attention in this area is the use of
directing groups whose precise guidance opens up a new avenue
for the modification of original molecular framework in a defined
and predictable fashion. In recent years, great effort has been
devoted in the area of modification of aryl compounds by using
directing groups such as heterocycles,[2] anilides,[3] amides,[4]
carboxylic acid[5] and ketones[6] Most of these reports achieved
activation of the C–H bond ortho to the directing group via the
Scheme1. Strategies of functionalizations directed by aryl P = O group
formation of
a stable 5 or 6 membered cyclometalated
Since then, several methods for the direct functionalisation of
arylphosphine oxides have been reported.[12] It has been shown
that the transition metal can coordinate with the oxygen atom in
the arylphosphine oxides and this leads to the formation of five-
membered[13] or seven-membered cyclometalated intermediates,
[14],which deliver the corresponding products with high
regioselectivity (Scheme 1a and 1b). These developments have
made the modification of organophosphorus compounds more
readily attainable, including the modification of synthetically
relevant phosphorous containing ligands. Nevertheless, The
reactions still rely on precious metal catalyst such as Ru, Rh, Ir, Pd,
and only yielding functionalisation for specific C–H bonds. As a
consequence, it is imperative to find an alternative low-cost metal
catalyst as well as a new catalytic model for the C–H activation of
arylphosphine oxides. Furthermore, the modification of new
substrates beyond traditional phenyl or biphenyl phosphorus
sources is highly desirable considering the unique fluorescence
properties of both polycyclic aromatics as well as phosphine oxide
containing compound.[15] The installation of a phosphine oxide
intermediate. In 2009, the pioneering work of Gaunt and co-
workers reported the meta-arylation with acetanilide as the
directing group on the aryl ring, in a copper catalytic manifold.[7]
This reaction established a new activation mode in the field of C–H
bond activation.[8] Following this concept, we wanted to achieve
the meta-functionlisation of arylphosphine oxides. This goal would
be of significant interest to the synthetic community as it would
provide tools for the late stage functionalisation of phosphorus
containing ligands[9] and fluorescent molecules.[10] The work of
Shibata in 2012 confirmed that phosphine oxides could be used as
directing groups for ortho-C–H bond functionalization.[11]
a. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou
730000, P. R. China. E-mail: yangshd@lzu.edu.cn
b. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute
of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China. E-
mail: yangshd@lzu.edu.cn
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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directing group on polycyclic aromatics and the achieving (3ad). The reaction also showed high efficViieewncAyrticlewOhnleinne
subsequent modification by C–H bond functionalization would diaryliodonium triflate bearing electron-witDhOdrI:a1w0i.n10g3g9r/oDu0pCsCs0u6c6h39aGs
10b]
therefore be of great significance.[10a,
Previously, You and co- halogens, CF3, CO2Me and the corresponding products were obtain
workers reported the palladium catalysed C7–H arylation of in 56%-73% yield (3ah-3an). The structure of 3ai was
naphthamides.[16] Herein, by using a cheaper copper catalyst, we unambiguously confirmed by X-ray analysis. The diaryliodonium
are able to realize the C7–H arylation of naphthylphosphine oxides triflate salt contained 1-naphthyl could also be tolerated in this
with diaryliodonium triflate salts (Scheme 1c). This achievement not reaction and the product was delivered in 46% yield (3ao). In
only provides a new activation mode for arylphosphine oxide addition, asymmetric diaryliodonium triflate salts were also tested
substrates, but also yields an important access toward enhanced in the system. We were pleased to find that the reaction showed
scope of compounds with improved photophysical properties.
complete selectivity toward the mono-substituted aromatic
After detailed screening, the optimised reaction conditions component and the products were produced in 40%-70% yield (3ab,
were found to be; CuI (10 mol%) as catalyst in DCE, 1.0 equiv 1- 3ae, 3ag, 3af, 3ai, 3am) (Table 1, bottom). At the current stage of
P(O)(tBu)2
naphthalene
methylphenyl)iodonium triflate salt at 100 C under air (for details diaryliodonium triflate salts containing pyridine group (3ap).
see SI). In order to verify the generality of the reaction, the scope of Following this, we tested the scope of phosphorus component,
(1a)
and
1.5
equiv
di(p- development, the reaction couldn't proceed when asymmetric
o
diaryliodonium triflate salts was first explored. As shown in Table 1, using di(p-methylphenyl)iodonium triflate salt as the aryl source.
symmetric diaryliodonium salts bearing electron-donating groups The product could be obtained in high yields wherever naphthalene
were applied, and the desired C7–H arylation product were ring bearing an etlecron-donating group (Me or OMe) (Table 2, 3ba-
delivered in 61%-88% yield (3aa, 3ac, 3ae-3ag). Diphenyliodonium 3ca) or halogen and electron-withdrawing group (F, phenyl or
triflate salt (2b) could also be converted into corresponding product naphthyl) (3da-3ga). Further, different phosphorus environments,
in 86% yield (3ab). It should be noted that the reaction showed such as P(O)(tBu)2, could also be used as suitable directing groups
moderate sensitivity to the steric effect of the substrates, with di-o- and afforded the corresponding arylated products in moderate to
methylbenzene triflate salts (2d) giving a slightly lower yield of the high yields (3ha-3ka). Only trace amount of product was observed
corresponding product compared with the para and meta-variants
when using steric bulky 1-P(O)(tBu)2 unit as the directing group.
(3la).
Table 1. Substrate scope of the diaryliodonium saltsa
Table 2. Substrate scope of the fused rings bearing P(O)(tBu) directing groupa
O
O
P(tBu)2
P(tBu)2
Ar2IOTf
or
ArMesIOTf
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
Ar
+
O
O
C
P(tBu)2
R
P(tBu)2
R
OTf
I
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
+
C
1a
2
3
Scope of symmetrical diaryliodonium salts
1
2a
3
O
O
O
O
P(tBu)2
P(tBu)2
P(tBu)2
P(tBu)2
O
O
O
P(tBu)2
P(tBu)2
O
P(tBu)2
OMe
P(tBu)2
3aa, 88%
3ab, 86%
3ac, 82%
3ad, 61%
F
Ph
tBu
O
3da, 70%
MeO
F
O
O
3ba, 84%
3ca, 81%
3ea, 82%
P(tBu)2
P(tBu)2
P(tBu)2
O
P(tBu)2
O
P(tBu)2
O
O
P(tBu)2
P(tBu)2
O
P(tBu)2
3ae, 70%
3af, 82%
3ag, 75%
3ah, 73%
Cl
Cl
Br
O
O
P(tBu)2
O
P(tBu)2
P(tBu)2
3ha, 42%
3fa, 70%
3ga, 72%
3ia, 65%
O
O
P(tBu)2
P(tBu)2
3ai, 70%
3aj, 70%
3ak, 72%
O
P(tBu)2
F3C
MeO2C
Ph
O
O
O
O
P(tBu)2
P(tBu)2
P(tBu)2
P(tBu)2
3la, trace
3ja, 67%
3ka, 78%
3al, 56%
3am, 53%
3an, 56%
3ao, 45%
a
Reaction conditions: 1 (0.1 mmol, 1.0 equiv), 2a (0.15 mmol, 1.5 equiv), CuI
Scope of asymmetric diaryliodonium salts
tBu
O
(0.01 mmol, 10% mol) in DCE at 100 oC for 8 h under air.
MeO
O
O
P(tBu)2
P(tBu)2
P(tBu)2
O
P(tBu)2
To further explore the applicability of this reaction, more
compounds were subjected to the optimised reaction conditions.
We could obtain the desired product in moderate yields when using
isopropyl and cyclohexyl group based phosphorus oxides (3ma-
3na). However, the phenyl based variant failed to yield the product.
(Scheme 2a). Then the counter-ion of the diaryliodonium salts was
3ab, 70%b
3ae, 43%b
3ag, 70%b
3af, 55%b
Cl
MeO2C
O
O
O
P(tBu)2
P(tBu)2
P(tBu)2
N
3ai, 63%b
3am, 40%b
3ap, N.R.b
Reaction conditions: 1a (0.1 mmol, 1.0 equiv), 2 (0.15 mmol, 1.5 equiv), CuI examined. (Br-, BF4 , and PF6 ) were tested and the desired product
-
-
a
(0.01 mmol, 10% mol) in DCE at 100 oC for 8 h under air. Using ArMesIOTf
b
were produced in significantly lower yield (Scheme 2b). Following
this, substrate 1o bearing two phosphorus directing groups was
used in the reaction. With slight modifications to the reaction
instead of Ar2IOTf. Mes = mesitylene. N.R. = no reaction.
2 | J. Name., 2012, 00, 1-3
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conditions, a mixture of the mono and bis arylated compounds 3oa
and 3oa’ were obtained in 43% and 31% yields respectively
(Scheme 2c). In addition, we were pleased to find that the reaction
was amenable to increased scale with 3aa being isolated in 78%
yield on gram-scale (Scheme 2d).
View Article Online
Table 3. Photophysical properties of 1a, 1k, 3ka, 5 and 6
DOI: 10.1039/D0CC06639G
Compounds
λabsa (nm)
236, 291
246, 270, 281, 334, 351, 378
230, 248, 286, 341, 355, 382
246, 285, 346, 354
244, 279, 348
λemb (nm)
333
τFc (ns)
6.88
1a
1k
3ka
5
380
390
448
407
26.16
8.75
3.42
tBu
O
P
OTf
I
O
P
3ma, R=iPr
3na, R=Cy
R=Ph
yield=50%
yield=41%
no reaction
R2
R2
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
+
(a)
6
1.94
C
tBu
tBu
1m-1n
1.5 equiv
a Absorption maxima in DCM (1.0 × 10-5 M). b Emission maxima in DCM (1.0 × 10-5
M). c Photoluminescence lifetime in neat film
O
O
P
(tBu)2
P
(tBu)2
X
I
X=Br trace
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
+
X=BF4 yield=31%
X=PF6 yield=55%
(b)
C
1.5 equiv
1a
O
O
O
(tBu)2
P
(tBu)2
P
(tBu)2
P
OTf
I
CuI(20%), DCE(0.1 M)
Air, 8 h, 100 o
+
(c)
+
C
(tBu)2
P
3.0 equiv
(tBu)2
P
(tBu)2
P
O
1o
O
O
3oa, 43%
3oa', 31%
O
P
OTf
I
O
P
(tBu)2
(tBu)2
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
+
(d)
C
1a, 1.01 g
2a, 2.41 g
3aa, 78%
Scheme 2. Extension of reaction scope and gram scale experiment
Figure 1. (left) Absorption and (right) emission spectra of 1a, 1k, 3ka, 5 and 6 in
DCM (1.0 × 10-5 M).
Considering the fact that several arylphosphine oxides exhibit
fluorescence, especially when combined with the pyrene unit, we
To gain further insight into the mechanism of this reaction. We
ran the standard reaction with the addition of 1 equiv of 2,2,6,6-
tetramethylpiperidinooxy (TEMPO) as a radical scavenger. The
desired product was obtained in 50% which suggests that radical
species are not involved in this transformation (Scheme 4a).
Meanwhile, the intramolecular KIE experiment presents a small
KH/KD value (1.31) (Scheme 4b), which indicates that the activation
of C–H bond at the C7-position of naphthalene ring may not
involved in the rate-determining step. Based on these results and
previous reports on Cu catalyzed arylation, a tentative reaction
mechanism was proposed in the supporting information. (it's shown
in 7.3 of the table of content)
synthesized substrate 1j with
a pyrene functional group to
investigate its potential application in our system (Scheme 3a).
Taking advantage of the tolerance of the aryl bromides in our
system, compound 4 was delivered in 70% yield which can be
further modified by Suzuki coupling reaction, thus the extended
aromatic molecule 5. Meanwhile, compound
structure was also synthesized from same approach. (Scheme 3b).
6 with similar
Br
O
P
(tBu)2
O
O
P(tBu)2
P(tBu)2
1-Pyrenylboronic acid
Pd(PPh3
)
2Cl2
,
K2CO3
70%
(a)
OTf
I
Dioxane
:
H2O
=
3:1
Ar, Reflux,
6 h, 87%
Br
Br
4
5
1j
1.5 eq.
CuI(10%), DCE(0.2 M)
Air, h, 100 o
8
C
O
P(tBu)2
Br
O
P
(tBu)2
1-Pyrenylboronic acid
O
P(tBu)2
Pd(PPh3
)
2Cl2
,
K2CO3
68%
O
(b)
(tBu)2
P
CuI(10%), DCE(0.2 M)
Air, 8 h, 100 o
OTf
I
O
(tBu)2
P
Dioxane
:
H2O
=
3:1
Ar, Reflux,
6 h, 83%
C
1a
+
3ak
6
(a)
TEMPO (1.0 equiv)
Scheme 3. Further synthesis of potential fluorescent molecules on the basis of
1a
2a, 1.5 equiv
3aa, 50%
reaction
O
(tBu)2
P
OTf
I
O
CuI(10%), DCE(0.2 M)
(tBu)2
P
Air, 100 o
C
+
Subsequently, the photophysical properties of the compounds
(including the substrates and product) containing the pyrene unit
were investigated (Table 3 and Figure 1). The absorption band of
the substrate 1a ranges from 230 to 330 nm and only includes two
absorption peaks. Instead, compounds containing pyrene unit (1k,
3ka, 5, 6) exhibit more red-shifted absorptions (240−400 nm) due to
their extended π-conjugated skeleton. At the same time, when
compared with the substrate 1a, the compounds bearing a pyrene
unit emit violet to deep blue fluorescence and the emission
wavelength are generally red shifted by about 50-100 nm because
of the strong intramolecular charge-transfer effect. Fluorescence
lifetimes (τF) of compounds 1a, 1k, 3ka, 5 and 6 were also
determined and the results shown in Table 3. Interestingly, a
significant change of fluorescence lifetimes was observed between
the 1k and its arylated variants. We believe that the fluorescence
properties of these compounds would provide more choices for
chemists in screening fluorescent molecules.
H7/D7
15min - 30min
H6D6
(b)
kH /kD ~ 1.31
1a/[D7]-1a
3aa/[D6]-3aa
2a, 1.5 equiv
Scheme 4. Mechanism experiment
In conclusion, we have reported a new activation mode for
arylphosphine oxides, in which the C7–H bond of naphthalene ring
and other polycyclic aromatics which own potential fluorescence
properties were arylated by a cheap copper catalyst under simple
reaction conditions. This reaction provides a new method to
potentially modulate the photophysical properties of PAH’s and has
been shown to be tolerant of several relevant functional groups.
The reaction displays excellent regioselectivity and provides a new
pathway toward the modification of arylphosphine oxide
compounds.
We are grateful to the NSFC (No. 21532001) for financial
support.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0CC06639G
The copper-catalyzed regioselective arylation of the polycyclic aromatic hydrocarbons (PAHs)
with potential fluorescence properties by P=O group has been performed.