Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible light oxidative C–C and C–P bond formation

Article abstract of DOI:10.1016/j.tet.2019.04.071

A highly efficient visible light mediated C–C and C–P coupling reactions of sp³ C–H bonds adjacent to the nitrogen atom in tetrahydroisoquinoline derivatives with pronucleophiles such as nitroalkanes, malononitrile, dimethyl malonate and H-phos

Full text of DOI:10.1016/j.tet.2019.04.071

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient
heterogeneous catalyst for visible light oxidative CeC and CeP bond
formation
a
,
b
,
*
, Guan-Wu Wang a , Xianjin Zhu , Lei Wang
,
**
b
b
Pinhua Li
a
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, PR China
b
a r t i c l e i n f o
a b s t r a c t
A highly efficient visible light mediated CeC and CeP coupling reactions of sp3 CeH bonds adjacent to
the nitrogen atom in tetrahydroisoquinoline derivatives with pronucleophiles such as nitroalkanes,
malononitrile, dimethyl malonate and H-phosphonate diesters were achieved by using a magnetic
nanoparticle-supported eosin Y bis-benzyltriethylammonium salt (MNPs-Eosin Y) as catalyst and air as
the sole oxidant, affording the corresponding products in good to excellent yields under mild reaction
conditions. Notably, the supported eosin Y catalyst can easily be separated from the reaction mixture by
an external permanent magnet and can be recycled at least eight times without a significant loss of
activity.
Article history:
Received 9 March 2019
Received in revised form
24 April 2019
Accepted 28 April 2019
Available online xxx
Keywords:
Cross-dehydrogenative-coupling
Supported eosin Y catalyst
N-aryl tetrahydroisoquinoline
Visible light
©
2019 Published by Elsevier Ltd.
Recycle
1
. Introduction
others [11] shown that this type reaction can be photocatalyzed
with iridium complex, Ru(bpy) Cl or photosensitive dyes using
3
2
3
Direct functionalization of the Csp -H bond has emerged as
powerful synthetic approaches for the CeC and C-Heteroatom bond
formation in organic chemistry [1]. Of particular note is the cross-
dehydrogenative-coupling (CDC) reaction [2], which is the ideal
process for building a CeC(X) linkage directly via the cleavage of
dual Csp eH bonds or one Csp -H bond and one heteroatomꢀH
bond using molecular oxygen as the terminal oxidant, has been
successfully developed into the most atom-economic, clean, and
efficient strategy in synthetic organic chemistry. Though func-
various nucleophiles. However, the homogeneous photocatalysts
are generally considered of low efficiency due to the high catalyst
loading and the difficulty in separation from the products.
Furthermore, their potential toxicity could lead to detrimental
effects on the environment. Accordingly, the development of
recyclable heterogeneous photocatalytic systems based on these
homogeneous photocatalysts would be highly desirable.
3
3
In the past few years, conjugated microporous polymers (CMPs)
have been serve as an ideal platform for incorporating photosen-
sitive monomers into highly stable, recyclable, and reusable het-
erogeneous photocatalyst systems. For example, Lin and Liras
reported the porous cross-linked polymers with phosphorescent
3
tionalization of benzylic C(sp )ꢀH bonds in N-aryl tetrahy-
droisoquinolines including Mannich [3], aza-Henry [4], cyanation
[
5] and phosphorylation [6] have been intensively investigated,
2þ
þ
most of these reactions have been reported with transition metals
as catalysts and peroxo-compounds as terminal oxidants. Recently,
the groups of Stephenson [7], K o€ nig [8], Rueping [9], Wu [10] and
[Ru(bpy)
3
]
2
and [Ir(ppy) (bpy)] building blocks for efficient
photocatalysis [12]. Cooper et al. reported a conjugated micropo-
rous polymers with Rose Bengal dye for the heterogeneous pho-
tocatalytic aza-Henry reactions [13]. Very recently, Chen and Han
et al. reported the efficient heterogeneous photocatalytic aza-
Henry reactions catalyzed by conjugated microporous poly-
carbazole containing tris(2-phenylpyridine) iridium(III) complexes
and Eosin Y dye-based porous organic polymers, respectively [14].
In 2014, Kobayashi developed a polymer-immobilized iridium-
*
Corresponding author. Department of Chemistry, University of Science and
Technology of China, Hefei, Anhui 230026, PR China.
*
* Corresponding author.
E-mail addresses: pinhuali@mail.ustc.edu.cn (P. Li), gwang@ustc.edu.cn
(
G.-W. Wang).
https://doi.org/10.1016/j.tet.2019.04.071
040-4020/© 2019 Published by Elsevier Ltd.
0
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

2
P. Li et al. / Tetrahedron xxx (xxxx) xxx
based photocatalyst and demonstrated its effectiveness as a visible
light photocatalyst for the aerobic CDC reaction [15]. However,
most of the photosensitive monomers used in the above-
mentioned examples either require tedious experimental proced-
ures to prepare or expensive, that limit the usability of preparation
of the polymers on a large scale. Within the past few years, mag-
netic nanoparticles (MNPs) emerged as a new class of semi-
heterogeneous supports for catalysts, and the intrinsic magnetic
properties of the support allow for operationally convenient sep-
aration via magnetic decantation [16]. In continuation of our efforts
to develop economical and eco-friendly synthetic pathways for
organic transformations from the viewpoint of green chemistry
[
17], herein we will report a very convenient method for immobi-
lization of eosin Y on the quaternary ammonium salt functionalized
magnetic nanoparticles by overall ion-exchange process. The re-
sults indicated that the MNPs supported eosin Y catalyst exhibits
high photocatalytic activity for the CeC and CeP coupling reactions
Scheme 2. Preparation of the magnetic nanoparticles supported eosin Y catalyst.
3
of sp CeH bonds adjacent to the nitrogen atom in N-aryl tetra-
hydroisoquinoline derivatives with pronucleophiles such as nitro-
alkanes, malononitrile, dimethyl malonate and H-phosphonate
diesters (Scheme 1). More importantly, the grafted catalyst could be
recovered and reused well at least 8 times without significant loss
of catalytic activity.
2
. Results and discussion
The magnetic nanoparticles supported eosin Y catalyst was
prepared according to the procedure in Scheme 2. Silica-coated
Fe (SiO @Fe ) was prepared according to the literature [18].
Commercially available Fe nanoparticles, with an average
diameter of 15 nm after sonication (Fig. 1a), were coated with a thin
layer of silica using a solegel process to give silica-coated Fe
TEM images of the SiO @Fe indicated the coreeshell structure
3
O
4
2
3 4
O
3 4
O
3 4
O .
2
3 4
O
of the particles and the silica coating, which has a uniform thick-
ness of 5 nm (Fig. 1b). The benzyl chloride was anchored easily onto
the surface of SiO @Fe O by using (4-chloromethylphenyl)ethyl-
2 3 4
3 4 3 4
Fig. 1. TEM images of the catalysts: (a) Fe O nanoparticles; (b) silica-coated Fe O
(SiO
2 3
@Fe O
4
); (c) MNPs-eosin Y catalyst; (d) recycled MNPs-eosin Y catalyst.
trimethoxysilane at refluxing temperature in toluene, with a
loading of 0.32 mmol of benzyl chloride per gram, which was
quantified via CHN microanalysis based on carbon content deter-
mination. Immobilization of the benzyltriethylammonium chloride
was carried out by the reaction of triethylamine with the benzyl
chloride functionalized magnetic coreeshell nanoparticles in
anhydrous acetonitrile. The supported eosin Y catalyst was ob-
tained by simply dissolving eosin Y in the mixture of acetone and
water (3:1, V/V), and treating it with the above quaternary
ammonium salt-functionalized SiO
2 3 4
@Fe O , with a loading of
0
.10 mmol of eosin Y per gram determined via spectrophotometric
method. TEM image confirmed the nanometre dimensions of the
supported catalyst as well as the existence of silica coating (Fig. 1c).
XRD measurements of the supported eosin.
Fig. 2. XRD determination of the supported eosin Y catalyst.
Y catalyst shown in Fig. 2 exhibited diffraction peaks corre-
sponding to the typical spinel maghemite structure and the
diffraction peak of the layered amorphous silica was not obvious.
Furthermore, TEM images showed that after eight reuses the sup-
ported eosin Y catalyst still maintained nanospheric dimensions as
well as the silica coating but with slight aggregation (Fig. 1d).
In order to evaluate the catalytic activity of the magnetic
nanoparticle-supported eosin Y, the cross-dehydrogenative
coupling of N-phenyl-1,2,3,4-tetrahydroisoquinoline (1a) with
nitromethane (2a) was chosen as model reaction to optimize the
Scheme 1. Magnetic nanoparticles supported eosin Y catalyzed visible light oxidative
CeC and CeP bond formation.
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

P. Li et al. / Tetrahedron xxx (xxxx) xxx
3
Table 1
give 3a in 87% yield (Table 1, entry 8). In the absence of magnetic
nanoparticle-supported eosin Y catalyst or visible-light irradiation,
no desired product was observed, even the reaction was performed
a
Optimization of reaction conditions.
ꢁ
in a 60 C oil bath (Table 1, entries 9 and 10). A comparable yield of
3a was achieved when an oxygen atmosphere was used instead of
an air atmosphere (Table 1, entry 11). However, no product 3a was
obtained when the reaction was performed under a nitrogen at-
mosphere (Table 1, entry 12). The loading of the supported pho-
tocatalyst, the ratio of 1a to 2a, as well as the reaction time were
optimized, which are also summarized in Table 1 (entries 13e15). In
addition, under the optimized conditions, other pronucleophiles,
such as malononitrile, dimethyl malonate and diethyl phosphate
were also examined under the optimized conditions, and the
desired products were obtained in good to excellent yields (71%,
Entry
Catalyst
Solvent
Light source
Yield (%)b
1
2
3
4
5
6
7
8
9
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
none
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
MNPs-Eosin Y
none
DMSO
Green LED
Green LED
Green LED
Green LED
Green LED
Green LED
Green LED
Sunlight
72c
92
68
62
47
32
21
CH
CH
3
CN
CH
3
2
OH
DMF
1,4-dioxane
toluene
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
86% and 96%, respectively) and found that for efficient conversion
87
n.r., n.r.d
both light and catalyst are required, as shown in Scheme 3.
With the optimized reaction conditions in hand, the generality
of the cross-dehydrogenative coupling reaction of N-aryl tetra-
hydroisoquinoline derivatives with nitromethane was investi-
gated. As shown in Scheme 4, a series of N-aryl tetrahy-
droisoquinolines with both electron-donating (Me, OMe) and
electron-withdrawing (Cl, Br) groups on the aromatic rings were
able to undergo the CDC reaction with nitromethane efficiently,
thus resulting in the corresponding products 3aꢀ3g in good to
excellent yields (81e92%). It is worth noting that the use of nitro-
ethane as a nucleophile also gave the desired compounds 3h and 3i
in good yields (the ratios of the two diastereoisomers are 2:1).
Subsequently, the present photocatalytic CDC method was
further extended to the coupling of N-aryl tetrahydroisoquinolines
and malononitrile, and the results were shown in Scheme 5. The N-
phenyl tetrahydroisoquinoline derivatives 1 were treated smoothly
Green LED
In dark
d
1
1
1
1
1
1
0
1
2
3
4
5
n.r., n.r.
e
Green LED
Green LED
Green LED
Green LED
Green LED
91
n.r.
66 , 92
76 , 91
f
g
h
i
j
k
l
DMSO
80 , 90
a
3 2
Reaction conditions: 1a (0.25 mmol), CH NO (1.25 mmol), MNPs-Eosin Y
catalyst (50 mg, 2.0 mol %), solvent (2 mL), under 3 W green LED (530e535 nm)
irradiation for 12 h at room temperature in air.
b
Isolated yield, n. r. ¼ no reaction.
c
CH
3
NO
2
(2 mL) was added.
d
e
f
ꢁ
At 60 C.
Oxygen balloon.
nitrogen atmosphere.
MNPs-Eosin Y catalyst (25 mg, 1.0 mol %).
MNPs-Eosin Y catalyst (75 mg, 3.0 mol %).
g
h
i
CH
CH
3
NO
NO
2
(0.75 mmol) was added.
(2.0 mmol) was added.
j
3
2
k
l
with malononitrile in air under standard conditions, and a-amino
8
1
h.
6 h.
nitriles (5aꢀ5f) were obtained in good yields. It seems that the
electronic effect of the substitute group was not obvious, both
electron-withdrawing group and electron-donating group located
at the phenyl ring of the substrates gave the comparable results.
Similarly, the photocatalytic aerobic CDC reaction was also
applicable to the oxidative Mannich reaction between N-aryl tet-
rahydroisoquinolines 1 and dimethyl malonate, and the results
were shown in Scheme 6. Under visible-light irradiation, the N-
phenyl tetrahydroisoquinoline derivatives 1 reacted with dimethyl
malonate under an air atmosphere to afford the desired products 7
in high yields.
The success of CeC bond formation by using the magnetic
nanoparticle-supported eosin Y encouraged us to investigate CeP
bond coupling reactions. In general, various N-aryl tetrahy-
droisoquinolines could react with diethyl phosphate and dibenzyl
phosphate smoothly in the presence of the supported eosin Y
catalyst to give the desired products in excellent yields under
irradiation with 530e535 nm green LED for 12 h. Both electron-
donating and electron-withdrawing groups on the aromatic rings
were compatible in the oxidative CeP coupling reaction, and the
Table 2
Recycling MNPs-eosin Y catalyst for the cross-dehydrogenative coupling reaction of
N-phenyl tetrahydroisoquinoline with nitromethane.
a
Run
Yieldb (%)
Run
Yieldb (%)
1
2
3
4
92
90
91
88
5
6
7
8
87
90
88
89
a
3 2
Reaction conditions: 1a (0.25 mmol), CH NO (1.25 mmol), reused MNPs-Eosin
Y catalyst (50 mg, 2.0 mol %), DMSO (2 mL), under 3 W green LED (530e535 nm)
irradiation for 12 h at room temperature in air.
b
Isolated yield.
reaction conditions, and the results were shown in Table 1. To our
delight, the model reaction proceeded well in the presence of
magnetic nanoparticle-supported eosin Y, and the desired product
was obtained in 72% isolated yield under irradiation with a
5
30e535 nm green LED light in neat reaction conditions for 12 h
(Table 1, entry 1). Subsequently, various solvents were evaluated in
this transformation. Among the solvents screened, DMSO exhibited
the highest reactivity (Table 1, entry 2). Other solvents exhibited
less reactivity towards the reaction in the following order:
Scheme 3. Oxidative coupling reaction of N-aryl tetrahydroisoquinolines with other
pronucleophiles under the optimized reaction conditions. 1 (0.25 mmol), 2 (0.5 mmol),
MNPs-eosin Y (50 mg, 2.0 mol %), DMSO (2 mL), under 3 W green LED (530e535 nm)
irradiation in air for 12 h; Isolated yields of the products are based on compound 1a.
CH
e7). When the reaction was exposed to sunlight irradiation, the
cross-dehydrogenative-coupling could also undergo smoothly to
3 3 2
CN > CH CH OH > DMF >1,4-dioxane > toluene (Table 1, entries
3
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

4
P. Li et al. / Tetrahedron xxx (xxxx) xxx
Scheme 4. Oxidative coupling reaction of N-aryl tetrahydroisoquinolines with nitro-
alkane using MNPs-eosin Y as photocatalyst. Reaction conditions: 1 (0.25 mmol), 2
(
(
1.25 mmol), MNPs-eosin Y (50 mg, 2.0 mol %), DMSO (2 mL), under 3 W green LED
530e535 nm) irradiation in air for 12 h; isolated yields of the products are based on
compound 1.
Scheme 7. Oxidative coupling reaction of N-aryl tetrahydroisoquinolines with dialkyl
phosphate using MNPs-eosin Y as photocatalyst. Reaction conditions: 1 (0.25 mmol), 8
(
(
0.5 mmol), MNPs-eosin Y (50 mg, 2.0 mol %), DMSO (2 mL), under 3 W green LED
530e535 nm) irradiation in air for 12 h; Isolated yields of the products are based on
compound 1.
the O ꢂ
into the reaction mixture under green LED irradiation. Meanwhile,
ꢀ
adduct with DMPO was detected when DMPO was added
2
1
no signal of the
2
O adduct with TEMP was observed when the
reaction solution was irradiated with a green LED (See Supporting
Information for detail). On the basis of the above investigation and
literature [8], a plausible mechanism was proposed in Scheme 8.
The reaction begins with the photoexcitation of eosin Y by visible
light to generate its excited state (eosin Y *). Then a single electron
transfer from 1a to the excited state of eosin Ygave an aminyl cation
radical (I) along with the generation of eosin Yꢂ , which is subse-
quently oxidized by the molecular oxygen to regenerate eosin Y,
ꢀ
Scheme 5. Oxidative synthesis of
a-amino nitriles using MNPs-eosin Y as photo-
catalyst. Reaction conditions: 1 (0.25 mmol), 4 (0.5 mmol), MNPs-eosin Y (50 mg,
.0 mol %), DMSO (2 mL), under 3 W green LED (530e535 nm) irradiation in air for
2 h; Isolated yields of the products are based on compound 1.
ꢂ
ꢀ
2
).
along with the generation of superoxide radical anion (O
Subsequently, I lost a hydrogen atom by the superoxide radical
2
1
ꢂ
ꢀ
anion (O
2
) to generate iminium ion (II), which reacted with
pronucleophiles resulted in the desired product. Apparent quan-
tum efficiency (AQE) is an important factor to reflect the photon
utilization in the photocatalytic process, and the AQE of the
representative reaction at 530 nm was measured and calculated as
4
.55%.
Finally, the viability of recovering and reusing the magnetic
nanoparticle-supported eosin catalyst for the cross-
Y
dehydrogenative coupling reaction of N-phenyl tetrahydroiso-
quinoline (1a) with nitromethane was examined. It was found
that the catalyst could be reused at least eight times without a
noticeable loss of catalytic activity with minimal levels of eosin Y
leaching, and the characteristic absorption of eosin Y could not be
detected in the separated reaction crude by spectrometric method.
The supported catalyst could be collected and reused by using an
external permanent magnet and the separated catalyst was washed
with ethyl acetate and diethyl ether, respectively. After being dried
in air, it can be reused directly without any further treatment.
Scheme 6. Oxidative coupling reaction of N-aryl tetrahydroisoquinolines with
dimethyl malonate using MNPs-eosin Y as photocatalyst. Reaction conditions:
0.25 mmol), 6 (0.5 mmol), MNPs-eosin Y (50 mg, 2.0 mol %), DMSO (2 mL), under 3 W
green LED (530e535 nm) irradiation in air for 12 h; Isolated yields of the products are
based on compound 1.
1
(
desired
a
-amino phosphonates (9aꢀ9k) were obtained in excellent
yields (86e97%), as shown in Scheme 7.
3
. Conclusions
In order to determine the active species of oxygen for this
transformation, 2,2,6,6-tetramethylpiperidine (TEMP) and 5,5-
dimethyl-pyrroline-N-oxide (DMPO) were employed to capture
In summary, we have developed a simple and highly efficient
magnetic nanoparticle-supported eosin Y catalyst and demon-
strated its effectiveness as a recyclable visible light photocatalyst
for the oxidative CeC and CeP bond formation. The cross-coupling
1
ꢂ
ꢀ
O
2
and O
2
, respectively. The resulting electron-spin resonance
(
ESR) spectra shown that there was a strong characteristic signal of
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

P. Li et al. / Tetrahedron xxx (xxxx) xxx
5
5. Characterization data for all products
5.1. Nitromethyl-2-phenyl-1,2,3,4-tetrahydroisoquinoline (3a) [8a]
1
Pale yellow oil (61.7 mg, 92% yield); H NMR (400 MHz, CDCl
3
)
d
:
7
.33e7.15 (m, 6H), 7.02e7.00 (m, 2H), 6.88 (t, J ¼ 7.2 Hz, 1H), 5.58 (t,
J ¼ 7.2 Hz, 1H), 4.92e4.87 (m, 1H), 4.61e4.56 (m, 1H), 3.73e3.61 (m,
13
2H), 3.15e3.08 (m, 1H), 2.85e2.79 (m, 1H); C NMR (100 MHz,
CDCl : 148.4, 135.2, 132.9, 129.5, 129.2, 128.1, 127.0, 126.7, 119.4,
3
) d
115.1, 78.8, 58.1, 42.1, 26.4.
5.2. 2-(4-Methoxyphenyl)-1-(nitromethyl)-1,2,3,4-tetrahydroiso-
quinoline (3b) [8a]
Yellow oil (60.4 mg, 81% yield); 1H NMR (400 MHz, CDCl
3
) d:
Scheme 8. The proposed mechanism.
7
5
3
.25e7.12 (m, 4H), 6.91 (d, J ¼ 8.8 Hz, 2H), 6.81 (d, J ¼ 8.8 Hz, 2H),
.38 (t, J ¼ 7.2 Hz, 1H), 4.84e4.79 (m, 1H), 4.57e4.53 (m, 1H), 3.74 (s,
1
3
H), 3.57e3.54 (m, 2H), 3.05e2.96 (m, 1H), 2.70e2.66 (m, 1H);
C
reactions of N-aryl tetrahydroisoquinolines with pronucleophiles
such as nitroalkanes, malononitrile, dimethyl malonate and H-
phosphonate diesters generate the corresponding coupling prod-
ucts in good to excellent yields at the present reaction conditions.
Furthermore, the catalyst is readily prepared, easily recoverable,
and reusable for at least eight cycles without significant loss of its
activity.
3
NMR (100 MHz, CDCl ) d
1
: 153.9, 143.0, 135.4, 132.8, 129.4, 127.8,
26.9, 126.6, 118.8, 114.6, 78.9, 58.9, 55.5, 43.1, 25.7.
5
.3. 2-(4-Methyl)-1-nitromethyl-1,2,3,4-tetrahydroisoquinoline
(3c)
1
Pale yellow oil (60.9 mg, 86% yield); H NMR (400 MHz, CDCl ) d:
3
7
4
3
.25e7.05 (m, 6H), 6.87 (d, J ¼ 8.4 Hz, 2H), 5.48 (t, J ¼ 7.2 Hz, 1H),
.86e4.81 (m, 1H), 4.56e4.52 (m, 1H), 3.66e3.53 (m, 2H),
4
. Experimental section
13
.09e3.01 (m, 1H), 2.77e2.70 (m, 1H), 2.25 (s, 3H); C NMR
(
1
3
100 MHz, CDCl ) d: 146.4, 135.3, 133.0, 129.9, 129.2, 129.1, 128.0,
26.9, 126.6, 115.9, 78.8, 58.4, 42.3, 26.2, 20.3.
4.1. General considerations
The H NMR and 13C NMR spectra were recorded on a 400 MHz
1
5
.4. 2-(4-Chlorophenyl)-1-(nitromethyl)-1,2,3,4-tetrahydroiso-
Bruker FT-NMR spectrometer (400 MHz and 100 MHz, respec-
tively). All chemical shifts are given as value (ppm) with reference
quinoline (3d) [10a]
d
to tetramethylsilane (TMS) as an internal standard. The peak pat-
terns are indicated as follows: s, singlet; d, doublet; t, triplet; m,
multiplet; q, quartet. The coupling constants, J, are reported in
Hertz (Hz). CHN analysis was performed using a Vario EL III ele-
mentar. Transmission electron micrographs (TEM) were obtained
Yellow oil (64.1 mg, 85% yield); 1H NMR (400 MHz, CDCl
3
) d:
7
4
(
1
.28e7.12 (m, 6H), 6.89 (d, J ¼ 8.8 Hz, 2H), 5.48 (t, J ¼ 7.2 Hz, 1H),
.87e4.82 (m,1H), 4.59e4.54 (m,1H), 3.66e3.56 (m, 2H), 3.10e3.02
13
3
m, 1H), 2.81e2.74 (m, 1H); C NMR (100 MHz, CDCl ) d: 147.1,
35.0, 132.5, 129.3 (double), 128.2, 126.9, 126.8, 124.4, 116.5, 78.6,
8.2, 42.2, 26.1.
using
a JEOL-2010 transmission electron microscope. X-ray
5
diffraction (XRD) measurements were carried out at room tem-
perature using a Bruker D8 Advance X-ray powder diffractometer.
All the solvents and commercially available reagents were pur-
chased from commercial suppliers. Products were purified by flash
5
.5. 2-(4-Bromophenyl)-1-(nitromethyl)-1,2,3,4-tetrahydroiso-
quinoline (3e) [8a]
chromatography on 200e300 mesh silica gels, SiO
2
.
1
Yellow oil (72.1 mg, 83% yield); H NMR (400 MHz, CDCl
3
) d: 7.33
(
d, J ¼ 8.4 Hz, 2H), 7.27e7.23 (m, 3H), 7.17e7.11 (m, 1H), 6.83 (d,
J ¼ 8.8 Hz, 2H), 5.48 (t, J ¼ 7.2 Hz, 1H), 4.85e4.80 (m, 1H), 4.58e4.53
4.2. Typical procedure for oxidative coupling reaction of N-phenyl-
(m, 1H), 3.64e3.58 (m, 2H), 3.09e3.02 (m, 1H), 2.80e2.75 (m, 1H);
1
3
1,2,3,4-tetrahydroisoquinoline with nitromethane using the
3
C NMR (100 MHz, CDCl ) d: 147.5, 135.0, 132.4, 132.2, 129.2, 128.2,
supported eosin Y
126.9, 126.8, 116.7, 111.5, 78.6, 58.1, 42.0, 26.1.
N-phenyl-1,2,3,4-tetrahydroisoquinoline
(1a,
0.25 mmol),
5.6. 1-(Nitromethyl)-2-(m-tolyl)-1,2,3,4-tetrahydroisoquinoline
nitromethane (1.25 mmol, 5.0 equiv), the prepared MNPs-eosin Y
50 mg, 2.0 mol %) and DMSO (2 mL) were added to an oven-dried
reaction vessel equipped with magnetic stirring bar, and the reac-
(3f) [13]
(
1
Pale yellow oil (59.1 mg, 84% yield); H NMR (400 MHz, CDCl
3
)
d
:
tion vessel was irradiated with 3 W green LED (530e535 nm) for
7.22e7.11 (m, 5H), 6.78 (d, J ¼ 5.2 Hz, 2H), 6.66 (s, 1H), 5.53e5.52
12 h under air atmosphere at room temperature. After the reaction
(m, 1H), 4.87e4.81 (m, 1H), 4.56e4.52 (m, 1H), 3.62e3.61 (m, 2H),
13
was completed (monitored by TLC), the mixture was transferred to
the separating funnel, diluted with ethyl acetate and washed with
water. The aqueous phase was extracted three times with ethyl
acetate. The combined organic layers were dried over anhydrous
3.07e3.06 (m, 1H), 2.79e2.74 (m, 1H), 2.32 (s, 3H); C NMR
(100 MHz, CDCl : 148.4, 139.2, 135.3, 133.0, 129.3, 129.1, 128.0,
3
) d
127.0, 126.6, 120.3, 115.9, 112.2, 78.7, 58.1, 42.1, 26.5, 21.8.
MgSO
4
, filtered and concentrated in vacuum. Purification of the
5.7. 1-(Nitromethyl)-2-(o-tolyl)-1,2,3,4-tetrahydroisoquinoline (3g)
crude product was achieved by flash chromatography (silica gel,
petroleum ether/ethyl acetate ¼ 30:1) to give the desired product
[9c]
1
2
a in 92% yield as a pale oil.
Pale yellow oil (57.2 mg, 81% yield); H NMR (400 MHz, CDCl
3
)
d
:
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

6
P. Li et al. / Tetrahedron xxx (xxxx) xxx
7
.27e7.24 (m, 2H), 7.20e7.16 (m, 3H), 7.00e6.98 (m, 2H), 6.73e6.71
CDCl
3
)
d
: 7.32e7.23 (m, 6H), 7.01 (d, J ¼ 8.4 Hz, 2H), 5.45 (s, 1H),
(
m, 1H), 5.15e5.11 (m, 1H), 4.83e4.78 (m, 1H), 4.61e4.57 (m, 1H),
3.71e3.70 (m, 1H), 3.49e3.42 (m, 1H), 3.19e3.10 (m, 1H), 2.99e2.95
(m, 1H); C NMR (100 MHz, CDCl ) d: 146.9, 134.3, 129.5, 129.3,
3
129.2, 128.9, 127.0, 126.9 (double), 118.8, 117.4, 53.1, 44.3, 28.4.
13
3
(
.53e3.46 (m, 1H), 3.23e3.18 (m,1H), 2.88e2.79 (m,1H), 2.56e2.52
: 149.0, 136.3,
m, 1H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl
)
d
3
134.2,133.2,131.2,129.8,127.6,126.6,126.5,126.3,124.4,122.8, 79.4,
5
9.6, 43.3, 24.5, 17.7.
5.14. 2-(4-Bromophenyl)-1,2,3,4-tetrahydroisoquinoline-1-
carbonitrile (5e) [8a]
5
.8. 1-(1-Nitroethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (3h)
[
8a]
Pale yellow solid (58.7 mg, 75% yield); 1H NMR (400 MHz,
CDCl
3
)
d
: 7.45 (d, J ¼ 8.4 Hz, 2H), 7.32e7.23 (m, 4H), 6.94 (d,
1
Pale yellow oil (57.9 mg, 82% yield); H NMR (400 MHz, CDCl
.28e7.19 (m, 3H), 7.18e7.07 (m, 3H), 7.00e6.96 (m, 2H), 6.81e6.78
m, 1H), 5.25e5.21 (m, 1H), 5.06e4.99 and 4.90e4.83 (m, 1H),
3
) d:
J ¼ 8.8 Hz, 2H), 5.45 (s, 1H), 3.72e3.70 (m, 1H), 3.49e3.42 (m, 1H),
13
7
(
3
3.18e3.10 (m, 1H), 3.00e2.95 (m, 1H); C NMR (100 MHz, CDCl ) d:
147.3,134.4,132.4,129.3,129.2,128.9,127.0,126.9,119.0,117.4,114.3,
52.8, 44.2, 28.4.
3
(
.84e3.77 and 3.59e3.52 (m, 2H), 3.06e2.99 (m, 1H), 2.92e2.83
13
m, 1H), 1.67 and 1.51 (d, J ¼ 6.4 Hz, 3H); C NMR (100 MHz, CDCl
3
)
d
: 149.1, 148.8, 135.5, 134.7, 133.7, 131.9, 129.4, 129.2, 129.0, 128.6,
5.15. 2-(m-tolyl)-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile (5f)
128.3, 128.1, 127.2, 126.5, 126.0, 119.2, 118.7, 115.3, 114.4, 88.9, 85.4,
[11j]
6
2.7, 61.1, 43.4, 42.6, 26.7, 26.3, 17.3, 16.3.
1
Pale yellow solid (45.3 mg, 73% yield); H NMR (400 MHz, CDCl
3
)
5.9. 1-(1-Nitroethyl)-2-(p-tolyl)-1,2,3,4-tetrahydroisoquinoline (3i)
d: 7.30e7.22 (m, 5H), 6.90e6.82 (m, 3H), 5.50 (s, 1H), 3.77e3.74 (m,
[
13]
1H), 3.49e3.42 (m, 1H), 3.18e3.10 (m, 1H), 2.97e2.93 (m, 1H), 2.36
13
3
(s, 3H); C NMR (100 MHz, CDCl ) d: 148.4, 139.3, 134.6, 129.6,
1
Pale yellow oil (59.3 mg, 80% yield); H NMR (400 MHz, CDCl
.24e7.21 (m, 1H), 7.18e7.13 (m, 2H), 7.09e6.99 (m, 3H), 6.88 (d,
3
)
d:
129.3 (double),128.7,127.0,126.8,122.7,118.3,117.7,114.7, 53.3, 44.1,
28.5, 21.7.
7
J ¼ 8.4 Hz, 2H), 5.18e5.14 (m,1H), 5.05e4.98 and 4.90e4.83 (m,1H),
3
.83e3.76 and 3.56e3.51 (m, 2H), 3.05e2.98 (m,1H), 2.89e2.79 (m,
5.16. Dimethyl-2-(2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)
malonate (7a) [8a]
1
3
1
H), 2.25 and 2.23 (s, 3H), 1.68 and 1.52 (d, J ¼ 6.8 Hz, 3H); C NMR
: 147.2, 146.8, 135.8, 134.9, 133.8, 132.1, 129.9,
29.8,129.2,128.9,128.8,128.4,128.1,127.3,126.5,126.1,116.1,115.2,
(
3
100 MHz, CDCl ) d
1
1
8
Colourless oil (72.9 mg, 86% yield); H NMR (400 MHz, CDCl
3
)
d
:
9.0, 85.5, 62.9, 61.5, 43.9, 43.1, 26.6, 26.3, 20.4, 20.3, 17.4, 16.4.
7.22e7.18 (m, 3H), 7.16e7.14 (m, 1H), 7.11e7.09 (m, 2H), 6.99e6.97
m, 2H), 6.76e6.73 (m, 1H), 5.71 (d, J ¼ 9.2 Hz, 1H), 3.95 (d,
J ¼ 9.2 Hz, 1H), 3.72e3.66 (m, 1H), 3.63 (s, 3H), 3.61e3.58 (m, 1H),
(
5.10. 2-Phenyl-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile (5a)
13
[
8a]
3.53 (s, 3H), 3.09e3.01 (m, 1H), 2.88e2.82 (m, 1H); C NMR
100 MHz, CDCl : 168.1, 167.2, 148.6, 135.5, 134.6, 129.0, 128.8,
(
3
) d
1
Pale yellow solid (41.5 mg, 71% yield); H NMR (400 MHz, CDCl
3
)
127.5, 126.9, 125.9, 118.5, 115.1, 59.0, 58.0, 52.4, 42.0, 25.9.
d
: 7.42e7.26 (m, 6H), 7.12 (d, J ¼ 8.0 Hz, 2H), 7.05 (t, J ¼ 7.2 Hz, 1H),
5
1
.55 (s, 1H), 3.83e3.78 (m, 1H), 3.56e3.49 (m, 1H), 3.23e3.15 (m,
5.17. Dimethyl-2-(2-(p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)
malonate (7b) [11e]
1
3
H), 3.03e2.97 (m, 1H); C NMR (100 MHz, CDCl
3
)
d: 148.3, 134.6,
1
2
29.6, 129.5, 129.3, 128.7, 127.0, 126.8, 121.8, 117.7, 117.6, 53.2, 44.2,
8.5.
1
Colourless oil (76.9 mg, 87% yield); H NMR (400 MHz, CDCl
3
)
d
:
7.21e7.19 (m, 1H), 7.17e7.14 (m, 1H), 7.11e7.07 (m, 2H), 7.01 (d,
5
.11. 2-(4-Methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline-1-
J ¼ 8.4 Hz, 2H), 6.88 (d, J ¼ 8.4 Hz, 2H), 5.61 (d, J ¼ 9.6 Hz, 1H), 3.96
carbonitrile (5b) [8a]
(d, J ¼ 8.4 Hz, 1H), 3.70e3.61 (m, 2H), 3.64 (s, 3H), 3.58 (s, 3H),
13
3
.11e3.02 (m, 1H), 2.83e2.76 (m, 1H), 2.22 (s, 3H); C NMR
Pale yellow solid (52.2 mg, 79% yield); 1H NMR (400 MHz,
3
(100 MHz, CDCl ) d: 168.3, 167.4, 146.7, 135.5, 134.8, 129.6, 129.0,
CDCl
3
)
d
: 7.30e7.22 (m, 4H), 7.09 (d, J ¼ 8.4 Hz, 2H), 6.92 (d,
128.1, 127.5, 127.0, 125.9, 115.8, 59.1, 58.5, 52.5, 42.3, 25.7, 20.3.
J ¼ 8.8 Hz, 2H), 5.37 (s, 1H), 3.80 (s, 3H), 3.60e3.56 (m, 1H),
13
3
.47e3.40 (m, 1H), 3.21e3.12 (m, 1H), 2.95e2.91 (m, 1H); C NMR
5.18. Dimethyl-2-(2-(4-chlorophenyl)-1,2,3,4
(
100 MHz, CDCl : 155.7, 142.6, 134.3, 129.7, 129.4, 128.6, 127.1,
3
)
d
tetrahydroisoquinolin-1-yl)malonate (7c) [10a]
126.7, 121.0, 117.6, 114.8, 55.6, 55.5, 44.9, 28.7.
1
Colourless oil (78.5 mg, 84% yield); H NMR (400 MHz, CDCl
3
)
d
:
5
.12. 2-(p-Tolyl)-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile (5c)
7.21e7.18 (m, 2H), 7.17e7.10 (m, 4H), 6.90 (d, J ¼ 9.2 Hz, 2H), 5.64 (d,
[
11b]
J ¼ 9.6 Hz, 1H), 3.91 (d, J ¼ 9.6 Hz, 1H), 3.70e3.63 (m, 1H), 3.66 (s,
3
H), 3.59e3.52 (m, 1H), 3.55 (s, 3H), 3.09e3.01 (m, 1H), 2.93e2.86
Pale yellow solid (44.7 mg, 72% yield); 1H NMR (400 MHz,
CDCl
: H: 7.32e7.21 (m, 4H), 7.16 (d, J ¼ 8.4 Hz, 2H), 7.01 (d,
J ¼ 8.4 Hz, 2H), 5.45 (s, 1H), 3.72e3.68 (m, 1H), 3.47e3.41 (m, 1H),
13
3
(m, 1H); C NMR (100 MHz, CDCl ) d: 168.1, 167.2, 147.3, 135.4,
3
)
d
134.5, 128.9, 128.8, 127.8, 127.0, 126.2, 123.2, 116.1, 59.0, 58.1, 52.6,
42.4, 26.0.
13
3
.19e3.11 (m, 1H), 2.96e2.92 (m, 1H), 2.31 (s, 3H); C NMR
(
100 MHz, CDCl : 146.3, 134.5, 131.8, 130.1, 129.7, 129.4, 128.7,
3
)
d
5.19. Dimethyl-2-(2-(o-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)
127.1, 126.7, 118.3, 117.7, 54.1, 44.4, 28.6, 20.5.
malonate (7d) [11e]
1
5.13. 2-(4-Chlorophenyl)-1,2,3,4-tetrahydroisoquinoline-1-
Colourless oil (71.6 mg, 81% yield); H NMR (400 MHz, CDCl
3
)
d
:
carbonitrile (5d) [11c]
7.25e7.20 (m, 2H), 7.17e7.11 (m, 3H), 6.96e6.93 (m, 2H), 6.74e6.71
m, 1H), 5.15 (d, J ¼ 9.6 Hz, 1H), 4.04 (d, J ¼ 9.6 Hz, 1H), 3.66 (s, 3H),
3.62 (s, 3H), 3.61e3.56 (m, 1H), 3.18 (dd, J ¼ 5.2 Hz and 14.0 Hz, 1H),
(
Pale yellow solid (49.72 mg, 74% yield); 1H NMR (400 MHz,
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

P. Li et al. / Tetrahedron xxx (xxxx) xxx
7
2
.81e2.72 (m, 1H), 2.58 (dd, J ¼ 2.0 Hz and 14.0 Hz,1H), 2.26 (s, 3H);
3.60e3.57 (m, 1H), 2.97 (br, 2H), 2.24 (s, 3H); 13C NMR (100 MHz,
CDCl
J ¼ 4.2 Hz), 136.2 (d, J ¼ 6.0 Hz), 130.2, 129.6, 128.8 (d, J ¼ 2.6 Hz),
128.3 (d, J ¼ 8.0 Hz), 128.1, 128.1, 128.0, 127.9 (d, J ¼ 8.8 Hz), 127.3 (d,
J ¼ 3.5 Hz), 125.8 (d, J ¼ 2.9 Hz), 115.3, 68.5 (d, J ¼ 7.2 Hz), 67.5 (d,
J ¼ 7.8 Hz), 59.1 (d, J ¼ 156.7 Hz), 43.8, 26.5, 20.3.
13
C NMR (100 MHz, CDCl
3
)
d
: 168.2, 167.4, 149.5, 135.7, 135.4, 132.7,
3
)
d
: 147.1 (d, J ¼ 6.5 Hz), 136.4 (d, J ¼ 3.8 Hz), 136.3 (d,
131.0, 129.4, 127.3, 126.6, 126.3, 126.1, 123.6, 122.3, 60.2, 59.8, 52.3,
4
3.7, 24.9, 17.8.
5.20. Diethyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)
phosphonate (9a) [8a]
5
.25. Diethyl (2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-
1
Pale yellow oil (82.9 mg, 96% yield); H NMR (400 MHz, CDCl
.37e7.36 (m, 1H), 7.26e7.22 (m, 2H), 7.19e7.12 (m, 3H), 6.97 (d,
J ¼ 8.0 Hz, 2H), 6.78 (t, J ¼ 7.2 Hz, 1H), 5.18 (d, J ¼ 20 Hz, 1H),
.11e3.86 (m, 5H), 3.65e3.59 (m, 1H), 3.09e2.97 (m, 2H), 1.23 (t,
3
) d:
yl)-phosphonate (9f) [9c]
7
1
3
Pale yellow oil (82.7 mg, 87% yield); H NMR (400 MHz, CDCl ) d:
4
7.36e7.34 (m, 1H), 7.19e7.17 (m, 5H), 6.88 (d, J ¼ 8.8 Hz, 2H), 5.10 (d,
J ¼ 19.2 Hz,1H), 4.11e3.84 (m, 5H), 3.54e3.51 (m, 1H), 3.15e3.11 (m,
1H), 2.97e2.93 (m, 1H), 1.23 (t, J ¼ 7.2 Hz, 3H), 1.13 (d, J ¼ 7.2 Hz,
1
3
J ¼ 7.2 Hz, 3H), 1.13 (t, J ¼ 7.2 Hz, 3H); C NMR (100 MHz, CDCl
49.3 (d, J ¼ 5.7 Hz), 136.3 (d, J ¼ 5.5 Hz), 130.5 (d, J ¼ 0.9 Hz), 129.0,
28.6 (d, J ¼ 2.6 Hz), 128.0 (d, J ¼ 4.7 Hz), 127.3 (d, J ¼ 3.5 Hz), 125.7
3
) d:
1
1
(
13
3H); C NMR (100 MHz, CDCl
3
)
d: 147.8 (d, J ¼ 5.0 Hz), 136.1 (d,
d, J ¼ 2.8 Hz), 118.4, 114.7 (d, J ¼ 1.0 Hz), 63.2 (d, J ¼ 7.2 Hz), 62.2 (d,
J ¼ 5.4 Hz), 130.3, 128.7, 128.5 (d, J ¼ 2.7 Hz), 127.9 (d, J ¼ 4.8 Hz),
127.4 (d, J ¼ 3.5 Hz), 125.8 (d, J ¼ 2.8 Hz), 123.0, 115.5 (d, J ¼ 0.8 Hz),
63.1 (d, J ¼ 7.3 Hz), 62.3 (d, J ¼ 7.7 Hz), 58.7 (d, J ¼ 159.5 Hz), 43.6,
J ¼ 7.7 Hz), 59.5, 57.9, 43.4, 26.6, 16.3 (d, J ¼ 5.5 Hz), 16.2 (d,
J ¼ 5.7 Hz).
2
6.8, 16.3 (d, J ¼ 5.4 Hz), 16.2 (d, J ¼ 5.8 Hz).
5
.21. Dibenzyl (2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phos-
phonate (9b) [8a]
5.26. Dibenzyl (2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinolin-
-yl)phosphonate (9g) [9c]
1
1
Pale yellow oil (113.9 mg, 97% yield); H NMR (400 MHz, CDCl
3
)
1
d
: 7.28e7.10 (m, 16H), 6.96 (d, J ¼ 8.0 Hz, 2H), 6.79 (t, J ¼ 7.2 Hz, 1H),
Pale yellow oil (118.4 mg, 94% yield); H NMR (400 MHz, CDCl
: 7.31e7.11 (m, 16H), 6.83 (d, J ¼ 8.4 Hz, 2H), 5.19 (d, J ¼ 18.4 Hz,
1H), 4.98e4.72 (m, 4H), 3.96-3.90 (m, 1H), 3.51e3.46 (m, 1H),
3
)
5
3
1
(
1
.28 (d, J ¼ 19.6 Hz, 1H), 5.03e4.74 (m, 4H), 4.04e3.98 (m, 1H),
d
13
.62e3.59 (m,1H), 3.08e2.95 (m, 2H); C NMR (100 MHz, CDCl
49.1 (d, J ¼ 5.6 Hz), 136.4 (d, J ¼ 5.6 Hz), 136.3 (d, J ¼ 5.9 Hz), 136.1
d, J ¼ 5.9 Hz), 130.3, 129.1, 128.7 (d, J ¼ 2.7 Hz), 128.3 (d, J ¼ 8.4 Hz),
3
) d:
13
3
3.12e3.08 (m, 1H), 2.95e2.91 (m, 1H); C NMR (100 MHz, CDCl ) d:
147.6 (d, J ¼ 4.7 Hz), 136.2 (d, J ¼ 5.5 Hz), 136.0 (d, J ¼ 5.7 Hz), 135.9
(d, J ¼ 5.3 Hz), 130.0, 128.8, 128.6 (d, J ¼ 2.7 Hz), 128.3, 128.3, 128.2,
128.2, 128.0 (d, J ¼ 4.8 Hz), 127.9 (d, J ¼ 2.2 Hz), 127.6 (d, J ¼ 3.5 Hz),
126.0 (d, J ¼ 2.9 Hz), 123.2, 115.7 (d, J ¼ 0.9 Hz), 68.5 (d, J ¼ 7.4 Hz),
28.2, 128.1, 128.1, 127.9 (d, J ¼ 4.9 Hz), 127.5 (d, J ¼ 3.6 Hz), 125.9 (d,
J ¼ 2.9 Hz), 123.1, 118.8, 118.5, 114.7, 68.5 (d, J ¼ 7.3 Hz), 67.6 (d,
J ¼ 7.7 Hz), 59.7, 58.1, 43.5, 26.7.
67.8 (d, J ¼ 7.7 Hz), 59.0 (d, J ¼ 156.8 Hz), 43.6, 26.9.
5
1
.22. Diethyl (2-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinolin-
-yl)phosphonate (9c) [8a]
5.27. Diethyl (2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinolin-1-
yl)phosphonate (9h) [8a]
1
Pale yellow oil (90.1 mg, 96% yield); H NMR (400 MHz, CDCl
3
)
d:
1
7
.40e7.38 (m,1H), 7.19e7.12 (m, 3H), 6.92 (d, J ¼ 8.8 Hz, 2H), 6.81 (d,
J ¼ 8.8 Hz, 2H), 5.02 (d, J ¼ 21.6 Hz, 1H), 4.13e3.91 (m, 5H), 3.74 (s,
H), 3.56e3.51 (m, 1H), 2.93 (br, 2H), 1.25 (t, J ¼ 7.2 Hz, 3H), 1.16 (t,
Pale yellow oil (102.8 mg, 97% yield); H NMR (400 MHz, CDCl
3
)
d
: 7.36e7.30 (m, 3H), 7.21e7.15 (m, 3H), 6.84 (d, J ¼ 8.8 Hz, 2H), 5.10
3
(d, J ¼ 19.2 Hz, 1H), 4.10e3.84 (m, 5H), 3.56e3.50 (m, 1H), 3.17e3.13
(m, 1H), 2.98e2.94 (m, 1H), 1.23 (t, J ¼ 7.2 Hz, 3H), 1.14 (t, J ¼ 7.2 Hz,
13
J ¼ 7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) d: 153.0, 144.1 (d,
1
3
J ¼ 8.2 Hz), 136.3 (d, J ¼ 5.8 Hz), 130.4 (d, J ¼ 1.1 Hz), 128.8 (d,
J ¼ 2.6 Hz), 128.1 (d, J ¼ 4.4 Hz), 127.2 (d, J ¼ 3.5 Hz), 125.7 (d,
J ¼ 2.9 Hz), 117.5, 114.4, 63.3 (d, J ¼ 7.2 Hz), 62.2 (d, J ¼ 7.6 Hz), 59.4
3H); C NMR (100 MHz, CDCl
3
)
d
: 148.2 (d, J ¼ 4.9 Hz), 136.2 (d,
J ¼ 5.4 Hz), 131.7, 130.3, 128.5 (d, J ¼ 2.8 Hz), 128.0 (d, J ¼ 4.8 Hz),
127.5 (d, J ¼ 3.5 Hz), 125.9 (d, J ¼ 2.8 Hz), 116.0 (d, J ¼ 1.0 Hz), 110.2
(d, J ¼ 0.9 Hz), 63.2 (d, J ¼ 7.3 Hz), 62.4 (d, J ¼ 7.6 Hz), 58.7 (d,
J ¼ 158.6 Hz), 43.5, 26.9, 16.4 (d, J ¼ 5.4 Hz), 16.3 (d, J ¼ 5.8 Hz).
(
d, J ¼ 157.7 Hz), 55.6, 44.6, 26.0, 16.4 (d, J ¼ 5.5 Hz), 16.3 (d,
J ¼ 5.9 Hz).
5.23. Diethyl (2-(p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)phos-
5.28. Diethyl (2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinolin-1-
phonate (9d) [9c]
yl)phosphonate (9h) [8a]
1
1
Pale yellow oil (77.1 mg, 86% yield); H NMR (400 MHz, CDCl
.38e7.37 (m, 1H), 7.17e7.11 (m, 3H), 7.04 (d, J ¼ 8.0 Hz, 2H), 6.88 (d,
J ¼ 8.4 Hz, 2H), 5.12 (d, J ¼ 20.8 Hz, 1H), 4.13e3.88 (m, 5H),
.62e3.56 (m, 1H), 2.98 (br, 2H), 2.24 (s, 3H), 1.25 (t, J ¼ 7.2 Hz, 3H),
3
)
d
:
Pale yellow oil (130.3 mg, 95% yield); H NMR (400 MHz, CDCl
3
)
7
d
: 7.30e7.12 (m,14H), 7.10e7.09 (m, 2H), 6.79 (d, J ¼ 8.4 Hz, 2H), 5.18
(d, J ¼ 18.8 Hz, 1H), 4.98e4.82 (m, 3H), 4.77e4.72 (m, 1H),
3
1
3.96e3.89 (m, 1H), 3.53e3.47 (m, 1H), 3.14e3.10 (m, 1H), 2.96e2.92
13
13
.14 (t, J ¼ 7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
)
d
: 147.3 (d,
(m, 1H); C NMR (100 MHz, CDCl
3
)
d
: 148.0 (d, J ¼ 4.5 Hz), 136.2 (d,
J ¼ 7.0 Hz), 136.3 (d, J ¼ 5.7 Hz), 130.5 (d, J ¼ 1.1 Hz), 129.5, 128.7 (d,
J ¼ 2.6 Hz), 128.0 (d, J ¼ 4.6 Hz), 127.8, 127.2 (d, J ¼ 3.5 Hz), 125.7 (d,
J ¼ 2.9 Hz), 115.2, 63.2 (d, J ¼ 7.1 Hz), 62.1 (d, J ¼ 7.6 Hz), 58.9 (d,
J ¼ 158.4 Hz), 43.7, 26.3, 20.3, 16.4 (d, J ¼ 5.4 Hz), 16.3 (d, J ¼ 5.8 Hz).
J ¼ 5.5 Hz), 136.1 (d, J ¼ 4.0 Hz), 136.0 (d, J ¼ 4.1 Hz), 131.7, 130.0,
128.6 (d, J ¼ 2.8 Hz), 128.4, 128.4, 128.3, 128.2, 128.1 (d, J ¼ 4.9 Hz),
127.9 (d, J ¼ 1.3 Hz), 127.7 (d, J ¼ 2.2 Hz), 127.6, 126.0 (d, J ¼ 2.7 Hz),
116.2, 110.4, 68.5 (d, J ¼ 7.4 Hz), 67.8 (d, J ¼ 7.8 Hz), 58.8 (d,
J ¼ 156.9 Hz), 43.6, 26.9.
5
.24. Dibenzyl (2-(p-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)
phos-phonate (9e) [9c]
5.29. Dibenzyl (2-(m-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)
phos-phonate (9j) [8a]
1
Pale yellow oil (111.2 mg, 92% yield); H NMR (400 MHz, CDCl
: 7.32e7.12 (m, 14H), 7.02 (d, J ¼ 8.0 Hz, 2H), 6.87 (d, J ¼ 8.0 Hz,2H),
.23 (d, J ¼ 19.6 Hz, 1H), 5.04e4.75 (m, 4H), 4.05e3.99 (m, 1H),
3
)
1
d
Pale yellow oil (82.7 mg, 92% yield); H NMR (400 MHz, CDCl
7.38e7.37 (m, 1H), 7.17e7.11 (m, 4H), 6.80e6.77 (m, 2H), 6.61 (d,
3
)
d
:
5
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071

8
P. Li et al. / Tetrahedron xxx (xxxx) xxx
Lett. 53 (2012) 1456;
J ¼ 7.2 Hz, 1H), 5.18 (d, J ¼ 20 Hz, 1H), 4.12e3.87 (m, 5H), 3.66e3.60
(
(
(
b) H.E. Ho, Y. Ishikawa, N. Asao, Y. Yamamoto, T. Jin, Chem. Commun. 51
2015) 12764;
c) Y. Liu, C. Wang, D. Xue, M. Xiao, C. Li, J. Xiao, Chem. Eur. J. 23 (2017) 3051.
(
(
1
m, 1H), 3.07e2.96 (m, 2H), 2.31 (s, 3H), 1.25 (t, J ¼ 7.2 Hz, 3H), 1.14
13
t, J ¼ 7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
)
d
: 149.4 (d, J ¼ 6.0 Hz),
38.7, 136.3 (d, J ¼ 5.6 Hz), 130.6 (d, J ¼ 1.1 Hz), 128.9, 128.6 (d,
[7] D.B. Freeman, L. Furst, A.G. Condie, C.R.J. Stephenson, Org. Lett. 14 (2012) 94.
[
8] (a) D.P. Hari, B. K o€ nig, Org. Lett. 13 (2011) 3852;
J ¼ 2.6 Hz), 128.0 (d, J ¼ 4.5 Hz), 127.2 (d, J ¼ 3.4 Hz), 125.7 (d,
J ¼ 2.8 Hz), 119.3, 115.4 (d, J ¼ 0.9 Hz), 111.8 (d, J ¼ 0.9), 63.2 (d,
J ¼ 7.2 Hz), 62.2 (d, J ¼ 7.7 Hz), 58.8 (d, J ¼ 158.0 Hz), 43.3, 26.6, 21.8,
(
b) T. Mitkina, C. Stanglmair, W. Setzer, M. Gruber, H. Kisch, B. K o€ nig, Org.
Biomol. Chem. 10 (2012) 3556;
(c) D.P. Hari, B. K o€ nig, Chem. Commun. 50 (2014) 6688.
[9] (a) M. Rueping, S. Zhu, R.M. Koenigs, Chem. Commun. 47 (2011) 8679;
1
6.3 (d, J ¼ 5.5 Hz), 16.2 (d, J ¼ 5.8 Hz).
(
(
b) M. Rueping, S. Zhu, R.M. Koenigs, Chem. Commun. 47 (2011) 12709;
c) M. Rueping, J. Zoller, D.C. Fabry, K. Poscharny, R.M. Koenigs, T.E. Weirich,
5
.30. Dibenzyl (2-(m-tolyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)
J. Mayer, Chem. Eur. J. 18 (2012) 3478;
d) M. Rueping, C. Vila, T. Bootwicha, ACS Catal. 3 (2013) 1676.
10] (a) Q. Liu, Y.-N. Li, H.-H. Wang, B. Chen, C.-H. Tung, L.-Z. Wu, Chem. Eur. J. 18
2012) 620;
(
phos-phonate (9k) [19]
[
(
1
Pale yellow oil (116.0 mg, 96% yield); H NMR (400 MHz, CDCl
: 7.34e7.11 (m, 15H), 6.78 (br, 2H), 6.61 (d, J ¼ 7.2 Hz, 1H), 5.28 (d,
J ¼ 19.6 Hz, 1H), 5.03e4.75 (m, 4H), 4.05e3.98 (m, 1H), 3.65e3.60
3
)
(b) Q.-Y. Meng, J.-J. Zhong, Q. Liu, X.-W. Gao, H.-H. Zhang, T. Lei, Z.-J. Li, C.-
H. Tung, L.-Z. Wu, J. Am. Chem. Soc. 135 (2013) 19052;
d
(c) C.-J. Wu, J.-J. Zhong, Q.-Y. Meng, T. Lei, X.-W. Gao, C.-H. Tung, L.-Z. Wu, Org.
Lett. 17 (2015) 884.
13
(
d
m, 1H), 3.07e2.96 (m, 2H), 2.26 (s, 3H); C NMR (100 MHz, CDCl
: 149.2 (d, J ¼ 5.7 Hz), 138.8, 136.5 (d, J ¼ 5.6 Hz), 136.3 (d,
J ¼ 6.1 Hz), 136.2 (d, J ¼ 6.1 Hz), 130.3, 128.9, 128.7 (d, J ¼ 2.6 Hz),
28.3 (d, J ¼ 9.0 Hz), 128.2 (d, J ¼ 11.6 Hz), 128.1 (d, J ¼ 4.7 Hz), 127.9
d, J ¼ 7.6 Hz), 127.4 (d, J ¼ 3.5 Hz), 125.8 (d, J ¼ 2.8 Hz), 119.5, 115.7,
12.0, 68.6 (d, J ¼ 7.2 Hz), 67.6 (d, J ¼ 7.7 Hz), 59.0 (d, J ¼ 157.0 Hz),
3.5, 26.8, 21.8.
3
)
[11] For selected examples, see: (a) Y. Pan, C.W. Kee, L. Chen, C.-H. Tan, Green
Chem. 13 (2011) 2682;
(
b) Y. Pan, S. Wang, C.W. Kee, E. Dubuisson, Y. Yang, K.P. Loh, C.-H. Tan, Green
Chem. 13 (2011) 3341;
c) W.-P. To, G. So-M. Tong, W. Lu, C. Ma, J. Liu, A.L.-F. Chow, C.-M. Che, Angew.
Chem. Int. Ed. 51 (2012) 2654;
1
(
1
4
(
(d) M. Neumann, K. Zeitler, Org. Lett. 14 (2012) 2658;
(e) L. Moehlmann, M. Baar, J. Riess, M. Antonietti, X. Wang, S. Blechert, Adv.
Synth. Catal. 354 (2012) 1909;
(
(
f) D. Shi, C. He, B. Qi, C. Chen, J. Niu, C. Duan, Chem. Sci. 6 (2015) 1035;
g) B. Wang, D.P. Shelar, X.-Z. Han, T.-T. Li, X. Guan, W. Lu, K. Liu, Y. Chen, W.-
Acknowledgements
F. Fu, C.-M. Che, Chem. Eur. J. 21 (2015) 1184;
h) M.N. Gandy, C.L. Raston, K.A. Stubbs, Chem. Commun. 51 (2015) 11041;
(
We gratefully acknowledge the National Natural Science Foun-
dation of China (21772062), the Young Talent Key Project of Anhui
Province (170808J02) and the Scientific Research Project of Anhui
Provincial Education Department (KJ2015TD002) for financial
support.
(i) X. Li, Y. Li, Y. Huang, T. Zhang, Y. Liu, B. Yang, C. He, X. Zhou, J. Zhang, Green
Chem. 19 (2017) 2925;
(j) T. Ide, K. Shimizu, H. Egami, Y. Hamashima, Tetrahedron Lett. 59 (2018)
3258.
[12] (a) Z. Xie, C. Wang, K.E. DeKrafft, W. Lin, J. Am. Chem. Soc. 133 (2011) 2056;
(
(
b) M. Liras, M. Pintado-Sierra, M. Iglesias, F. S aꢀ nchez, J. Mater. Chem. A 4
2016) 17274.
[
[
13] J.-X. Jiang, Y. Li, X. Wu, J. Xiao, D.J. Adams, A.I. Cooper, Macromolecules 46
(2013) 8779.
14] (a) L. Pan, M.-Y. Xu, L.-J. Feng, Q. Chen, Y.-J. He, B.-H. Han, Polym. Chem. 7
Appendix A. Supplementary data
(
(
4
2016) 2299;
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2019.04.071.
b) C.-A. Wang, Y.-W. Li, X.-L. Cheng, J.-P. Zhang, Y.-F. Han, RSC Adv. 7 (2017)
08.
[
[
15] W.-J. Yoo, S. Kobayashi, Green Chem. 16 (2014) 2438.
16] For selected reviews, see: (a) K.V.S. Ranganath, F. Glorius, Catal. Sci. Technol. 1
References
(
(
2011) 13;
b) V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset, Chem.
[1] For selected reviews, see: (a) A. Gini, T. Brandhofer, O.G. Mancheno, Org.
Rev. 111 (2011) 3036;
Biomol. Chem. 15 (2017) 1294;
(
(
c) M.B. Gawande, P.S. Brancoa, R.S. Varma, Chem. Soc. Rev. 42 (2013) 3371;
d) M.B. Gawande, S.N. Shelke, R. Zboril, R.S. Varma, Acc. Chem. Res. 47 (2014)
(
(
(
b) Y. Wei, P. Hu, M. Zhang, W.P. Su, Chem. Rev. 117 (2017) 8864;
c) C.S. Yeung, V.M. Dong, Chem. Rev. 111 (2011) 1215;
d) C. Liu, H. Zhang, W. Shi, A. Lei, Chem. Rev. 111 (2011) 1780.
1338;
(
(
(
(
(
e) D. Wang, D. Astruc, Chem. Rev. 114 (2014) 6949;
f) F. Zhang, H. Li, Chem. Sci. 5 (2014) 3695;
g) R. Dalpozzo, Green Chem. 17 (2015) 3671;
h) D. Wang, C. Deraedt, J. Ruiz, D. Astruc, Acc. Chem. Res. 48 (2015) 1871;
i) R.K. Sharma, S. Dutta, S. Sharma, R. Zboril, R.S. Varma, M.B. Gawande, Green
[
[
2] For selected reviews, see: (a) C.-J. Li, Acc. Chem. Res. 42 (2009) 335;
(
(
b) S.A. Girard, T. Knauber, C.-J. Li, Angew. Chem. Int. Ed. 53 (2014) 74;
c) C.J. Scheuermann, Chem. Asian J. 5 (2010) 436.
3] For selected examples, see: (a) Z. Li, C.-J. Li, J. Am. Chem. Soc. 127 (2005) 6968;
(
(
(
b) Z. Li, C.-J. Li, Eur. J. Org. Chem. (2005) 3173;
c) E. Boess, C. Schmitz, M. Klussmann, J. Am. Chem. Soc. 134 (2012) 5317;
d) M.O. Ratnikov, X. Xu, M.P. Doyle, J. Am. Chem. Soc. 135 (2013) 9475.
Chem. 18 (2016) 3184.
[
17] (a) P. Li, L. Wang, L. Zhang, G.-W. Wang, Adv. Synth. Catal. 354 (2012) 1307;
(b) L. Zhang, P. Li, H. Li, L. Wang, Catal. Sci. Technol. 2 (2012) 1859;
(c) L. Zhang, P. Li, J. Yang, M. Wang, L. Wang, ChemPlusChem 79 (2014) 217;
(d) L. Zhang, P. Li, C. Liu, J. Yang, M. Wang, L. Wang, Catal. Sci. Technol. 4
(2014) 1979.
[
[
4] For selected examples, see: (a) Z. Li, C.-J. Li, J. Am. Chem. Soc. 127 (2005) 3672;
b) E. Shirakawa, T. Yoneda, K. Moriya, K. Ota, N. Uchiyama, R. Nishikawa,
T. Hayashi, Chem. Lett. 40 (2011) 1041;
c) J. Xie, H. Li, J. Zhou, Y. Cheng, C. Zhu, Angew. Chem. Int. Ed. 51 (2012) 1252.
5] For selected examples, see: (a) S.-I. Murahashi, N. Komiya, H. Terai, T. Nakae,
J. Am. Chem. Soc. 125 (2003) 15312;
(
(
[
[
18] (a) Y.-H. Deng, C.-H. Deng, D.-W. Qi, C. Liu, J. Liu, X.-M. Zhang, D.-Y. Zhao, Adv.
Mater. 21 (2009) 1377;
b) Y.-H. Deng, D.-W. Qi, C.-H. Deng, X.-M. Zhang, D.-Y. Zhao, J. Am. Chem. Soc.
30 (2008) 28.
19] H. Wang, X. Li, F. Wu, B. Wan, Tetrahedron Lett. 53 (2012) 681.
(
1
(
(
b) W. Han, A.R. Ofial, Chem. Commun. 45 (2009) 5024;
c) Y. Zhang, H. Peng, M. Zhang, Y. Cheng, C. Zhu, Chem. Commun. 47 (2011)
2354.
[6] For selected examples, see: (a) K. Alagiri, P. Devadig, K.R. Prabhu, Tetrahedron
Please cite this article as: P. Li et al., Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible
light oxidative CeC and CeP bond formation, Tetrahedron, https://doi.org/10.1016/j.tet.2019.04.071