Palladium-catalyzed C–P bond activation of aroyl phosphine oxides without the adjacent “anchoring atom”

Article abstract of DOI:10.1016/j.tet.2020.131912

A novel palladium-catalyzed decarbonylation of aroyl phosphine oxides to prepare phosphine oxides from carboxylic acids is developed. Without the adjacent “anchoring atom”, the challenging C–P bond activation is achieved in high selectivity. The disclosure of this reaction provides a new example of C–P bond activation and helps to extend the understanding of the property of C–P bond.

Full text of DOI:10.1016/j.tet.2020.131912

Tetrahedron 81 (2021) 131912
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Palladium-catalyzed CeP bond activation of aroyl phosphine oxides
without the adjacent “anchoring atom”
Xingyu Chen 1, Xiaoyan Liu 1, Hong Zhu**, Zhiqian Wang*
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel palladium-catalyzed decarbonylation of aroyl phosphine oxides to prepare phosphine oxides
from carboxylic acids is developed. Without the adjacent “anchoring atom”, the challenging CeP bond
activation is achieved in high selectivity. The disclosure of this reaction provides a new example of CeP
bond activation and helps to extend the understanding of the property of CeP bond.
© 2020 Elsevier Ltd. All rights reserved.
Received 30 October 2020
Received in revised form
20 December 2020
Accepted 24 December 2020
Available online 30 December 2020
Keywords:
Aroyl phosphine oxides
Palladium-catalyzed
CeP bond Activation
Decarbonylation
1. Introduction
hypothesize that it is challenging and interesting to pursue
whether the C-X bond activation happens in case of the absence of
Organophosphorus compounds are widely utilized as functional
molecules in the fields of medicinal chemistry [1e6], materials
science [7e11] and catalysis [12e18]. The development of a more
efficient and diverse synthesis of an organophosphorus compound
is of current great concern [19e31]. Recently, transition-metal-
catalyzed CeP bond activation has emerged as a novel strategy in
organic synthesis [32e38]. A series of representative structures
with or without phosphorus atom can be constructed by reactions
involving CeP bond activation as the key step (Fig. 1A) [35,37]. For
example, acylphosphines are converted into differently substituted
phosphines through Ni-catalyzed CeP bond activation and decar-
bonylation process (Fig. 1B) [36]. In this reaction, the lone-pair
the adjacent “anchoring site”. Quite a few examples were reported
on decarbonylative C-X bond activations without the adjacent lone-
pair electrons of heteroatoms [47e51]. For example, Nakazawa and
co-workers reported that acylphosphonates would undergo a
metathesis and decarbonylation catalyzed by palladium complexes
to prepare phosphate derivatives (Fig. 1C) [52e54]. As an explor-
atory study, here we report a decarbonylative CeP(V) bond acti-
vation of aroyl phosphine oxides catalyzed by a palladium complex
(Fig. 1D). To the best of our knowledge, it is the first example of
constructing phosphine oxides via palladium-catalyzed CeP(V)
bond activation process.
electrons of phosphorus atom or the conjugating
p-electron sys-
2. Results and discussion
tem formed by phosphorus and carbonyl group usually participate
in the coordination of Ni and acylphosphine, and promote the
subsequent oxidative addition resulting in the cleavage of CeP
bond. This “anchoring effect” also exists in CeN, CeO, and CeC
bonds activation of amides, esters, and ketones, and is considered
to facilitate the activation of these inert bonds [39e46]. We
The aroyl phosphine oxides can be prepared conveniently from
the oxidation of aroyl phosphines with m-CPBA [55e57]. The aroyl
phosphines are prepared from carboxylic acids and disubstituted
phosphines according to literatures (Scheme 1) [36].
Our study commences with a similar catalytic condition of
decarbonylation of acyl phosphines using naphthoyl phosphine
oxide 1a (Table 1), but the NiCl2(PPh3)2 (5 mol%) shows negative to
this new reaction (entry 1). After a screening of catalysts, Pd(0)
catalysts show positive activity to this CeP bond activation process
and afford the desired product in 45% yield (entry 2, 3). Lowering
the temperature from 150 ꢀC to 130 ꢀC leads an increase of the yield
* Corresponding author.
** Corresponding author.
E-mail addresses: hzhu@mail.buct.edu.cn (H. Zhu), wangzhq@mail.buct.edu.cn
(Z. Wang).
1
These authors contributed equally.
https://doi.org/10.1016/j.tet.2020.131912
0040-4020/© 2020 Elsevier Ltd. All rights reserved.

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
Table 1
Condition Optimization.
Entry
Catalyst
Solvent
Temp. (oC)/time (h)
Yield (%)
1
2
3
4
5
6
7
8
NiCl2(PPh3)2
Pd(PPh3)4
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
toluene
C6H5Cl
dioxane
DMF
xylene
xylene
xylene
xylene
xylene
150/12
150/12
150/12
130/16
130/16
130/16
130/16
130/16
130/16
130/16
130/16
130/16
130/16
110/16
130/16
130/16
130/16
nd
42
nd
72
nd
66
95
nd
92
19
<5
14
Nd
48
e
Pd(PPh3)4
PdCl2(PPh3)2
Pd2(dba)3/dppp
Pd2(dba)3/PCy3
Pd2(dba)3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
PdCl2/Zn/PCy3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
Pd2(dba)3/PCy3
9
10
11
12
13a
14
15b
16b,c,d
17b,f
63
92(87e)
85e
Reaction condition: 1a (0.2 mmol), Ni or Pd (5 mol%), ligand (20 mol%), solvent
（0.5 mL), in N2, in the 2 mL dark vial, yields are determined by 31P NMR with
P(OPh)3 as the inner standard.
Fig. 1. Transition-metal-catalyzed CeP bond activation reactions.
a
Zn (1.0 equiv) is added.
Pd (2 mol%), PCy3 (8 mol%).
Reaction in 25 mL Schlenk tube in dark.
Solvent (1 mL).
b
c
d
e
Isolated yield.
f
1a (1 g), xylene (10 mL), 50 mL Schlenk flask.
Scheme 1. Preparation of aroyl phosphine oxides.
this catalytic condition (2d). 2-Naphthoyl phosphine oxide gives no
desired product (2e), while with a methoxyl group substituted at 1-
position, it works and affords the product in a yield of 80% (2f).
Substrates derived from benzoic acid are also explored. It is found
that the ortho-substituent on benzoic group seems to be essential
to get a higher yield of this reaction. The methyl-, methoxyl- and
methoxycarbonyl-substituted substrates afford the corresponding
products in good yields (2g-2i), but no desired product is obtained
from the chloro-substituted substrate (2j). The heteroarene thio-
phene is also readily available (2k). According to the phenomenon
mentioned above, we propose that the steric effect of ortho-sub-
stituents should have a positive effect on this transformation. 2,4,6-
Trimethylbenzoyl phosphine oxide and 9-anthryl phosphine oxide
are examined and afforded corresponding products in good to
excellent yields (2l,2m). Several sterically bulky phosphine oxides
with arenes substituted on ortho-position to phosphorus are pre-
pared in satisfying yields (2n-2q). With HSiCl3, the representative
phosphine oxide 2a can be reduced to trivalent phosphine 3a in a
yield of 83% [58e60].
Based on the optimized condition, a control reaction to look into
the intermediate of this reaction is carried out. In the presence of a
radical scavenger TEMPO (2 eq), a yield of 80% is still achieved as
shown in Scheme 2. This result suggests that the radical mechanism
can be excluded [31].
Based on this, a plausible mechanism of this reaction is pro-
posed as shown in Fig. 2 [61e63]. Firstly, Pd(0) undergoes an
oxidative addition pathway of CeP bond and generates a Pd(II)
from 42% to 72%. (entry 4). No reaction is observed with changing
Pd(0) to Pd(II) catalyst, which indicates an electron-rich metal
center is essential to initiate this reaction (entry 5). Based on this
result, a series of electron-rich phosphine ligands are employed.
Using bidentate ligand, dppp, the 66% yield is achieved (entry 6).
Using PCy3 (tricyclohexylphosphine), the product is afforded in
almost quantitive yield by 31P NMR (entry 7). The control reaction
shows that no product is obtained in the absence of ligands (entry
8). Optimization on the solvent shows toluene gives as high yield as
xylene (entry 9). However, a significant decrease in yield is
observed when using more polar solvents (entries 10e12). Further
optimization work is carried out for a further understanding of this
reaction. The Pd(0) complexes reduced by Zn dust from Pd(II)
cannot catalyze this reaction (entry 13). Reacting at a lower tem-
perature, such as 110 ꢀC, result in a drop of yield (entry 14). When
the reaction is carried out in 25 mL Schlenk tube instead of 2 mL
vial in dark, with 2 mol% of Pd2(dba)3 and 8 mol% of PCy3, an
excellent yield (92% by 31P NMR and 87% by chromatography
isolation) is achieved (entries 15e16). Under the optimized condi-
tion, a gram scale reaction is carried out, and 85% yield is afforded
(entry 17).
To demonstrate the generality of this novel reaction, we
examined the scope of this palladium-catalyzed CeP bond activa-
tion and decarbonylation of aroyl phosphine oxides. As shown in
Table 2, 1-naphthoyl phosphine oxide, and with 4-methyl, 2-
methoxyl substituents give products in yields around 90%
(Table 2, 2a-2c). However, the bromine atom can not survive from
intermediate B. Then an a-elimination of Pd and aryl group from
2

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
Table 2
Substrate Scopea.
carbonyl group happens on intermediate B, and lead to decar-
bonylated intermediate C. Finally, the intermediate C undergoes
reductive elimination to release product 2 and regenerate the Pd(0)
species.
Scheme 2. Control Reaction with TEMPO.
3. Conclusion
In summary, a synthesis of triarylsubstituted phosphine oxides
is realized through a novel palladium-catalyzed decarbonylation of
aroyl phosphine oxides process. In this reaction, the key step,
activation of the CeP bond, is realized by the oxidative addition of
Pd(0) catalyst followed by decarbonylation and reductive elimina-
tion. Comparing to our previous work and literature work, this
activation of CeP bond without the adjacent “anchoring effect” of
phosphorus atom is quite challenging to achieve a high reaction
selectivity. Prepared from carboxylic acids, various aroyl phosphine
oxides would transform into corresponding trisubstituted phos-
phine oxides in good to high yield, especially the sterically bulky
aryl groups from carboxylic acids are favored. Though this reaction
is hard to compete against traditional coupling reaction on the ef-
ficiency of phosphines preparation, it is still
component of CeP bond activation research and helps chemists to
extend the understanding about the property of CeP bond.
a dispensable
Fig. 2. Plausible mechanism.
3

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
4. Experimental section
CDCl3)
d
8.00 (d, J ¼ 9.1 Hz, 1H), 7.91 (dd, J ¼ 11.1, 7.5 Hz, 4H), 7.78 (t,
J ¼ 9.1 Hz, 2H), 7.60e7.46 (m, 6H), 7.42 (t, J ¼ 7.6 Hz, 1H), 7.35 (t,
4.1. General information
J ¼ 7.4 Hz, 1H), 7.28 (d, J ¼ 9.2 Hz, 1H), 3.76 (s, 3H) ppm; 13C NMR
(101 MHz, CDCl3)
d
212.85 (d, J ¼ 82.8 Hz), 159.35, 135.26, 131.86,
All the reactions were performed in oven-dried glassware under
a nitrogen atmosphere. Reactions were monitored by thin-layer
chromatography (TLC) on GF254 silica gel coated plates by visual-
izing using one or more of the following methods: UV light
(254 nm) and staining with basic potassium permanganate
(KMnO4). NMR spectra were acquired on a Bruker Avance III 400
NMR spectrometer (400 MHz for 1H spectra, 101 MHz for 13C
spectra, and 162 MHz for 31P spectra) and were quoted in ppm for
measurement against referenced to tetramethylsilane (TMS) or
residual solvent as an internal standard. Infrared spectra were ac-
quired on an FT-IR series spectrometer as thin films on potassium
bromide plates. High-resolution mass spectra (HRMS) were ob-
tained under ESI ionization using an LC/MSD TOF mass
spectrometer.
Unless otherwise noted, all commercial materials were pur-
chased from commercial suppliers and used without further puri-
fication. Tetrahydrofuran was freshly distilled over Na and other
solvents were used without further purification. Aroyl phosphines
and carboxylic acids were synthesized according to reported pro-
cedures [36].
131.69 (d, J ¼ 8.9 Hz), 130.90, 129.30, 128.74, 128.46 (d, J ¼ 11.7 Hz),
128.19, 124.45, 123.00, 112.89, 56.59 ppm; 31P NMR (162 MHz,
CDCl3)
d
16.97 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
C
24H19O3P 387.1145; Found387.1155. IR (film): 3054, 2934, 1645,
1512, 1437, 1254, 1200, 812, 725, 694, 543, 518 cmꢂ1
.
4.2.1.4. (4-Bromonaphthalen-1-yl) (diphenylphosphoryl)methanone
(1d). A yellow solid; 1.04 g; 60% yield; 1H NMR (400 MHz, CDCl3)
d
9.15 (d, J ¼ 8.0 Hz, 1H), 8.91e8.84 (m, 1H), 8.40e8.31 (m, 1H),
8.00e7.85 (m, 5H), 7.72e7.62 (m, 2H), 7.62e7.48 (m, 6H) ppm; 13
NMR (101 MHz, CDCl3)
C
d
206.21 (d, J ¼ 79.2 Hz), 135.18, 132.52 (d,
J ¼ 2.4 Hz),132.37,132.10,131.93 (d, J ¼ 9.2 Hz),131.27 (d, J ¼ 7.0 Hz),
130.67, 129.99, 129.71, 129.30, 128.76 (d, J ¼ 12.0 Hz), 128.08 (d,
J ¼ 13.1 Hz), 125.79 ppm; 31P NMR (162 MHz, CDCl3)
d 22.66 ppm.
HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C23H16O2PBr 435.0144;
Found 435.0136.
4.2.1.5. (Diphenylphosphoryl) (naphthalen-2-yl)methanone (1e).
A yellow solid; 0.70 g; 50% yield; 1H NMR (400 MHz, CDCl3)
d 9.61
(s,1H), 8.16 (dd, J ¼ 8.7,1.0 Hz,1H), 8.06 (d, J ¼ 8.1 Hz,1H), 7.99e7.79
(m, 6H), 7.65e7.60 (m, 1H), 7.59e7.54 (m, 3H), 7.54e7.46 (m, 4H)
4.2. Experimental procedure
ppm; 31P NMR (162 MHz, CDCl3)
d 22.69 ppm. HRMS (ESI-QTOF) m/
z: [MþH]þ Calcd for C23H17O2P 357.1044; Found 357.1054.
4.2.1. General procedure for the preparation of aroyl phosphine
oxides (1) [64]
4.2.1.6. (Diphenylphosphoryl)
(1-methoxynaphthalen-2-yl)meth-
The solution of m-CPBA (0.69 g, 4.0 mmol, 1.0 equiv.) in 15 mL
THF was added to an oven-dried round bottom flask charged with
acylphosphine (4 mmol). The resulting reaction mixture was stirred
at 25 ꢀC for 3 h and monitored by TLC. After completion of the
reaction, the reaction mixture was extracted with saturated Na2CO3
(3 ꢁ 15 mL), and the combined extracts were washed with satu-
rated NaCl (1 ꢁ 10 mL) and dried over Na2SO4. After removal of the
solvent, the residue was purified by recrystallization in ethyl ace-
tate or ethyl ether to afford 1.
anone (1f). A yellow solid; 1.03 g; 67% yield; 1H NMR (400 MHz,
CDCl3)
(m, 4H), 7.84 (d, J ¼ 8.1 Hz,1H), 7.63 (d, J ¼ 8.7 Hz,1H), 7.62e7.47 (m,
8H), 3.77 (s, 4H) ppm; 13C NMR (101 MHz, CDCl3)
207.39 (d,
d
8.21 (d, J ¼ 8.3 Hz, 1H), 8.15 (d, J ¼ 8.7 Hz, 1H), 7.98e7.87
d
J ¼ 81.7 Hz), 158.51, 137.63, 132.27 (d, J ¼ 2.2 Hz), 131.79 (d,
J ¼ 9.2 Hz), 130.98, 130.02, 129.13, 128.66 (d, J ¼ 11.9 Hz), 128.16,
127.90, 126.62, 125.71, 124.09 (d, J ¼ 2.1 Hz), 64.14 ppm; 31P NMR
(162 MHz, CDCl3)
d
21.62 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
Calcd for C24H19O3P 387.1145; Found 387.1135. IR (film): 3057, 2938,
1654, 1437, 1372, 1193, 820, 728, 692, 525 cmꢂ1
.
4.2.1.1. (1-Naphthoyl) diphenylphosphine oxide (1a). A yellow green
solid; 0.99 g; 70% yield; 1H NMR (400 MHz, CDCl3)
d
9.32 (d,
4.2.1.7. 2-Methylbenzoyldiphenylphosphine oxide (1g). A yellow
green solid; 0.68 g; 56% yield; 1H NMR (400 MHz, CDCl3)
8.80 (d,
J ¼ 7.2 Hz, 1H), 8.90 (d, J ¼ 8.0 Hz, 1H), 8.08 (d, J ¼ 8.4 Hz, 1H), 7.96
d
(dd, J ¼ 11.5, 7.3 Hz, 4H), 7.88 (d, J ¼ 8.0 Hz, 1H), 7.65e7.47 (m, 10H)
J ¼ 7.7 Hz,1H), 7.87 (dd, J ¼ 11.5, 7.0 Hz, 4H), 7.49 (ddd, J ¼ 28.2,19.6,
ppm; 13C NMR (101 MHz, CDCl3)
d
206.36 (d, J ¼ 78.3 Hz), 135.88 (d,
7.5 Hz, 7H), 7.32 (t, J ¼ 7.5 Hz,1H), 7.25 (d, J ¼ 5.1 Hz,1H), 2.50 (s, 3H)
J ¼ 8.0 Hz), 133.93 (d, J ¼ 2.7 Hz), 132.71, 132.38 (d, J ¼ 2.9 Hz),
ppm; 13C NMR (101 MHz, CDCl3)
d
207.10 (d, J ¼ 77.2 Hz), 140.10 (d,
132.23, 131.96 (d, J ¼ 9.2 Hz), 131.02, 130.24 (d, J ¼ 7.2 Hz), 130.06,
J ¼ 5.9 Hz), 135.74, 135.28, 133.57 (d, J ¼ 11.1 Hz), 132.35 (d,
J ¼ 2.8 Hz), 132.23 (d, J ¼ 3.0 Hz), 131.85 (d, J ¼ 9.3 Hz), 130.83,
129.88, 128.67 (d, J ¼ 11.9 Hz), 126.06, 21.68 ppm; 31P NMR
129.35, 128.83, 128.69 (d, J ¼ 12.0 Hz), 126.9, 125.4, 124.8 ppm; 31
P
NMR (162 MHz, CDCl3)
d 22.46 ppm. HRMS (ESI-QTOF) m/z:
[MþH]þ Calcd for C23H17O2P 357.1039; Found 357.1049. IR (film):
(162 MHz, CDCl3)
d
22.15 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
3046, 1632, 1435, 1195, 779, 727, 694, 540,477 cmꢂ1
.
Calcd for C20H17O2P 321.1039; Found 321.1046. IR (film): 3058,
2969, 2924, 1640, 1435, 1215, 695, 542 cmꢂ1
.
4.2.1.2. (Diphenylphosphoryl) (4-methylnaphthalen-1-yl)methanone
(1b). A yellow solid; 1.00 g; 68% yield; 1H NMR (400 MHz, CDCl3)
4.2.1.8. (2,4-Dimethoxyphenyl)
(1h). A light yellow solid; 1.21 g; 86% yield; 1H NMR (400 MHz,
CDCl3)
(diphenylphosphoryl)methanone
d
9.28 (d, J ¼ 7.5 Hz, 1H), 8.99 (d, J ¼ 8.0 Hz, 1H), 8.17e8.03 (m, 1H),
7.99e7.86 (m, 4H), 7.72e7.37 (m, 10H), 2.75 (s, 4H) ppm; 13C NMR
(101 MHz, CDCl3)
d
8.29 (d, J ¼ 8.8 Hz, 1H), 7.93e7.66 (m, 4H), 7.57e7.36 (m,
d
205.42 (d, J ¼ 78.8 Hz), 143.84, 136.15,
6H), 6.55 (dd, J ¼ 8.8, 2.0 Hz,1H), 6.42 (d, J ¼ 2.0 Hz,1H), 3.85 (s, 3H),
133.01,132.29 (d, J ¼ 2.3 Hz), 131.97 (d, J ¼ 9.2 Hz), 131.25, 130.29,
128.94, 128.64 (d, J ¼ 11.9 Hz), 126.75, 125.99 (d, J ¼ 11.8 Hz), 124.60,
3.71 (s, 3H) ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
C
21H19O4P 367.1094; Found 367.1101.
20.51 ppm; 31P NMR (162 MHz, CDCl3)
d 22.64 ppm. HRMS (ESI-
QTOF) m/z: [MþH]þ Calcd for C24H19O2P 371.1195; Found 371.1192.
IR (film): 3054, 2947,1627, 1580, 1513, 1436, 1225, 1188, 1116, 1073,
4.2.1.9. Methyl
A white solid; 0.96 g; 66% yield; 1H NMR (400 MHz, CDCl3)
8.01e7.88 (m, 1H), 7.60e7.44 (m, 2H), 7.21e7.13 (m, 1H), 3.78 (s,
1H) ppm; 13C NMR (101 MHz, CDCl3)
2-((diphenylphosphoryl)carbonyl)benzoate
(1i).
835, 697, 533 cmꢂ1
.
d
d
211.94 (d, J ¼ 86.8 Hz),
4.2.1.3. (Diphenylphosphoryl)
(2-methoxynaphthalen-1-yl)meth-
167.04, 132.81, 132.27 (d, J ¼ 2.3 Hz), 131.93 (d, J ¼ 9.1 Hz), 131.45,
anone(1c). A yellow solid; 1.27 g; 82% yield; 1H NMR (400 MHz,
130.74, 130.53, 129.78, 129.37, 128.58 (d, J ¼ 11.9 Hz), 127.20,
4

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
53.00 ppm; 31P NMR (162 MHz, CDCl3)
d
16.93 ppm. HRMS (ESI-
Calcd for C29H21O2P 433.1352; Found 433.1351. IR(film) 3049, 1657,
QTOF) m/z: [MþH]þ Calcd for C21H17O4P 365.0937; Found
365.0938. IR(film): 3063, 2960, 1706, 1677, 1434, 1293, 1210, 1115,
1555, 1437, 1320, 1187, 1117, 1034, 819, 756, 730, 695, 534, 499 cmꢂ1
.
746, 701, 562, 506 cmꢂ1
.
4.2.1.16. (Diphenylphosphoryl) (1-(4-(trifluoromethyl)phenyl)naph-
thalen-2-yl)methanone(1q). A yellow solid; 0.80 g; 40% yield; 1H
4.2.1.10. (2-Chlorophenyl) (diphenylphosphoryl)methanone (1j).
A yellow solid; 0.60 g; 45% yield; 1H NMR (400 MHz, CDCl3)
8.35
NMR (400 MHz, CDCl3)
d
8.12 (d, J ¼ 8.6 Hz, 1H), 7.99 (d, J ¼ 8.6 Hz,
d
1H), 7.93 (d, J ¼ 8.2 Hz, 1H), 7.76e7.67 (m, 4H), 7.62e7.52 (m, 3H),
7.49 (d, J ¼ 8.3 Hz, 3H), 7.44 (td, J ¼ 7.7, 3.3 Hz, 6H), 7.29 (d,
(d, J ¼ 7.5 Hz, 1H), 7.93e7.81 (m, 4H), 7.63e7.56 (m, 2H), 7.55e7.48
(m, 4H), 7.45 (d, J ¼ 3.7 Hz, 2H), 7.37 (dt, J ¼ 12.2, 4.3 Hz, 1H) ppm;
J ¼ 8.0 Hz, 2H) ppm; 13C NMR (101 MHz, CDCl3)
d 212.38 (d,
13C NMR (101 MHz, CDCl3)
d
206.71 (d, J ¼ 81.3 Hz), 133.70, 132.63
J ¼ 77.3 Hz), 140.91, 138.61, 135.01, 132.46, 131.69 (d, J ¼ 9.2 Hz),
131.32, 129.99, 129.04, 128.65 (d, J ¼ 12.0 Hz), 128.54, 128.22 (d,
J ¼ 6.5 Hz), 127.22 (d, J ¼ 4.6 Hz), 124.66 (d, J ¼ 3.5 Hz), 124.33 ppm;
(d, J ¼ 2.9 Hz), 132.42 (d, J ¼ 3.2 Hz), 132.29, 131.88 (d, J ¼ 9.4 Hz),
131.37 (d, J ¼ 1.9 Hz), 129.52 (d, J ¼ 97.2 Hz), 128.78 (d, J ¼ 12.1 Hz),
126.79 ppm; 31P NMR (162 MHz, CDCl3)
d 21.10 ppm. HRMS (ESI-
31P NMR (162 MHz, CDCl3) 18.24 ppm; 19F NMR (377 MHz, CDCl3)
d
QTOF) m/z: [MþH]þ Calcd for C19H14O2PCl 341.0493; Found
d
ꢂ62.42 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
341.0497.
C
30H20O2PF3 501.1226; Found 501.1229. IR(film): 3059, 1654,
1436,1405, 1325, 1209, 1166, 1066, 817, 695, 547, 493 cmꢂ1
.
4.2.1.11. (Diphenylphosphoryl)
(thiophen-2-yl)methanone
(1k).
A yellow solid; 0.38 g; 31% yield; 1H NMR (400 MHz, CDCl3)
d
8.95
4.2.2. General experimental procedure for synthesis of compound 2
through the palladium-catalyzed decarbonylation of aroyl
phosphine oxides (1)
(dd, J ¼ 3.9, 0.9 Hz, 1H), 7.97e7.86 (m, 4H), 7.82 (ddd, J ¼ 4.8, 1.8,
1.1 Hz, 1H), 7.57 (td, J ¼ 7.3, 1.4 Hz, 2H), 7.49 (ddd, J ¼ 7.2, 5.4, 2.5 Hz,
4H), 7.21 (dd, J ¼ 4.7, 4.1 Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3)
The aroyl phosphine oxide (0.20 mmol), Pd2(dba)3 (1.8 mg,
0.002 mmol, 1 mol%) and xylene (1.0 mL) were added to an oven-
dried Schlenk tube. The tube was evacuated and backfilled with
N2 three times. The mixture was stirred at 130 ꢀC for 16 h in an oil
bath. After cooling to room temperature, the solvent was removed
under vacuum and the residue was purified by flash chromatog-
raphy eluting with DCM/CH3OH (100:1 v/v) on silica gel to afford
corresponding phosphine oxides 2.
d
196.10 (d, J ¼ 86.4 Hz), 143.93 (d, J ¼ 58.8 Hz), 139.31, 137.45,
132.57 (d, J ¼ 2.4 Hz), 131.92 (d, J ¼ 9.4 Hz),130.27, 129.30, 128.71 (d,
J ¼ 12.1 Hz) ppm; 31P NMR (162 MHz, CDCl3)
d 20.07 ppm. HRMS
H 13O2PS 313.0447; Found
(ESI-QTOF) m/z: [MþH]þ Calcd for C17
3113.0449. IR (film): 3065, 1609, 1503, 1437, 1404, 1352, 1249, 1186,
1111, 1046, 746, 603, 537 cmꢂ1
.
4.2.1.12. Anthracen-9-yl(diphenylphosphoryl)methanone
(1m).
d 8.54
An orange solid; 1.45 g; 89% yield; 1H NMR (400 MHz, CDCl3)
(s, 1H), 8.10e7.96 (m, 6H), 7.64e7.47 (m, 8H), 7.47e7.38 (m, 2H),
4.2.2.1. Naphthalen-1-yldiphenylphosphine oxide (2a). A white
7.36e7.29 (m, 2H) ppm; 13C NMR (101 MHz, CDCl3)
d
219.82 (d,
solid; 57.1 mg; 87% yield; 1H NMR (400 MHz, CDCl3)
d 8.58 (d,
J ¼ 73.8 Hz), 132.64 (d, J ¼ 2.3 Hz), 132.13 (d, J ¼ 8.9 Hz), 130.89 (d,
J ¼ 10.5 Hz), 129.91, 128.97, 128.90, 128.78, 128.52, 127.15, 125.64,
J ¼ 8.4 Hz, 1H), 8.02 (d, J ¼ 8.2 Hz, 1H), 7.89 (d, J ¼ 8.1 Hz, 1H),
7.73e7.64 (m, 4H), 7.59e7.51 (m, 2H), 7.49e7.43 (m, 6H), 7.39 (ddd,
124.55 ppm; 31P NMR (162 MHz, CDCl3)
d 15.19 ppm. HRMS (ESI-
J ¼ 10.7, 7.2, 2.0 Hz, 1H), 7.30 (ddd, J ¼ 15.8, 7.1, 1.2 Hz, 1H) ppm; 13
C
QTOF) m/z: [MþH]þ Calcd for C27H19O2P 407.1195; Found 407.1195.
NMR (101 MHz, CDCl3)
d 133.97, 133.84, 133.72, 133.37, 133.30 (d,
IR (film): 3050, 1645, 1435, 1206, 1072, 724, 694, 529, 429 cmꢂ1
.
J ¼ 2.3 Hz), 132.34, 132.18 (t, J ¼ 14.1 Hz), 131.91 (d, J ¼ 2.1 Hz),
129.46, 128.78, 128.61 (d, J ¼ 12.2 Hz), 128.45, 127.64 (d, J ¼ 5.7 Hz),
127.38, 126.52, 124.16 (d, J ¼ 14.3 Hz) ppm; 31P NMR (162 MHz,
4.2.1.13. (Diphenylphosphoryl)
(40-methoxy-[1,10-biphenyl]-2-yl)
methanone(1n). A light yellow solid; 1.15 g; 70% yield; 31P NMR
CDCl3)
d
32.32 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
(162 MHz, CDCl3)
d
15.94 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
C
20H17O2P 329.1090; Found 329.1089. IR (film): 3058, 1433, 1189,
1116, 828, 801, 776, 697, 545 cmꢂ1
.
Calcd for C26H21O3P 413,1301; Found: 413.1296.
4.2.1.14. (40-chloro-[1,10-biphenyl]-2-yl) (diphenylphosphoryl)meth-
4.2.2.2. (4-Methylnaphthalen-1-yl)diphenylphosphine oxide (2b).
A white solid; 61.6 mg; 90% yield; 1H NMR (400 MHz, CDCl3)
8.61
(d, J ¼ 8.5 Hz, 1H), 8.06 (d, J ¼ 8.4 Hz, 1H), 7.68 (dd, J ¼ 11.9, 7.6 Hz,
4H), 7.54 (t, J ¼ 5.7 Hz, 3H), 7.45 (dt, J ¼ 11.7, 4.6 Hz, 5H), 7.20 (dt,
J ¼ 15.1, 5.7 Hz, 2H), 2.74 (s, 4H) ppm; 13C NMR (101 MHz, CDCl3)
anone(1o). A yellow solid; 0.87 g; 52% yield; 1H NMR (400 MHz,
d
CDCl3)
3H), 7.50e7.41 (m, 6H), 7.36 (d, J ¼ 7.6 Hz, 1H), 7.10e6.96 (m, 4H)
ppm; 13C NMR (101 MHz, CDCl3)
d
7.99 (d, J ¼ 7.6 Hz, 1H), 7.79e7.69 (m, 4H), 7.61e7.51 (m,
d
212.51 (d, J ¼ 77.4 Hz), 140.95 (d,
J ¼ 2.2 Hz), 138.35, 137.47 (d, J ¼ 44.0 Hz), 133.89, 132.48, 132.30 (d,
J ¼ 2.9 Hz), 131.57 (d, J ¼ 9.0 Hz), 130.74, 130.64, 130.40, 129.66,
129.45, 128.62 (d, J ¼ 11.9 Hz), 128.35, 127.76 ppm; 31P NMR
d
140.28 (d, J ¼ 2.4 Hz), 133.78 (d, J ¼ 11.2 Hz), 133.58 (s), 133.19 (d,
J ¼ 9.1 Hz),132.54,132.12 (d, J ¼ 9.8 Hz),131.82 (d, J ¼ 2.1 Hz),128.56
(d, J ¼ 12.1 Hz), 128.26 (d, J ¼ 5.8 Hz), 127.43, 126.98, 126.37, 125.12
(d, J ¼ 14.4 Hz), 124.70, 19.80 ppm; 31P NMR (162 MHz, CDCl3)
(162 MHz, CDCl3)
d
16.50 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
Calcd for C25 H18 O2 PCl 417.0806; Found 417.0810. IR(film): 3050,
d
32.57 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C24H19O2P
1650, 1591, 1474, 1436, 1210, 1089, 834, 763, 691, 539 cmꢂ1
.
343.1246; Found 343.1243. IR (film): 3068, 2922, 1587, 1509, 1436,
1182, 1117, 1029, 935,754, 700,542 cmꢂ1
.
4.2.1.15. (Diphenylphosphoryl)
anone(1p). A yellow solid; 0.52 g; 30% yield; 1H NMR (400 MHz,
CDCl3)
(1-phenylnaphthalen-2-yl)meth-
d
8.11 (d, J ¼ 8.6 Hz, 1H), 7.91 (dd, J ¼ 16.0, 8.4 Hz, 2H),
4.2.2.3. (2-Methoxynaphthalen-1-yl)diphenylphosphine oxide (2c).
A white solid; 64.5 mg; 90% yield; 1H NMR (400 MHz, CDCl3)
9.51
7.75e7.68 (m, 4H), 7.60 (d, J ¼ 8.6 Hz, 1H), 7.58e7.49 (m, 3H),
7.47e7.37 (m, 5H), 7.34e7.21 (m, 4H), 7.16 (dd, J ¼ 8.0, 1.5 Hz, 2H)
d
(d, J ¼ 8.8 Hz, 1H), 8.02 (d, J ¼ 9.1 Hz, 1H), 7.80 (d, J ¼ 8.1 Hz, 1H),
ppm; 13C NMR (101 MHz, CDCl3)
d
211.87 (d, J ¼ 77.2 Hz), 140.42,
7.77e7.62 (m, 4H), 7.59e7.31 (m, 8H), 7.15 (dd, J ¼ 9.1, 4.8 Hz, 1H),
137.01, 135.22, 135.04, 134.78, 132.53, 132.25 (d, J ¼ 2.4 Hz), 131.84
(d, J ¼ 9.2 Hz), 130.87, 130.29, 129.34, 128.54 (d, J ¼ 12.0 Hz), 128.02
(d, J ¼ 10.8 Hz), 127.84, 127.76, 126.83, 124.40 ppm; 31P NMR
3.25 (s, 3H) ppm; 31P NMR (162 MHz, CDCl3)
d 31.69 ppm. HRMS
(ESI-QTOF) m/z: [MþH]þ Calcd for C23H19O2P 359.1195; Found
359.1190. IR (film): 3073, 2922, 1505, 1431, 1328, 1253, 1173, 824,
(162 MHz, CDCl3)
d
18.65 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
751, 695, 548, 480 cmꢂ1
.
5

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
4.2.2.4. (1-Methoxynaphthalen-2-yl)diphenylphosphine oxide (2f).
4.2.2.10. Anthracen-9-yldiphenylphosphine oxide (2m). A light yel-
A white solid; 57.3 mg; 80% yield; 1H NMR (400 MHz, CDCl3)
low solid; 60.5 mg; 80% yield; 1H NMR (400 MHz, CDCl3)
d 8.70 (s,
d
8.17e8.09 (m,1H), 7.94e7.89 (m,1H), 7.85e7.76 (m, 4H), 7.70e7.37
1H), 8.60 (d, J ¼ 9.2 Hz, 2H), 8.03 (d, J ¼ 8.5 Hz, 2H), 7.80e7.64 (m,
(m, 10H), 3.70 (s, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d
160.80 (d,
4H), 7.50 (td, J ¼ 7.3, 1.4 Hz, 2H), 7.44e7.36 (m, 6H), 7.25 (t,
J ¼ 2.4 Hz), 137.52 (d, J ¼ 1.8 Hz), 134.06, 133.00, 131.83 (d,
J ¼ 10.0 Hz), 131.64 (d, J ¼ 2.8 Hz), 128.53, 128.48, 128.43, 128.36,
128.27,127.70 (d, J ¼ 7.7 Hz),126.49, 63.47 ppm; 31P NMR (162 MHz,
J ¼ 7.8 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d 136.37, 135.32 (d,
J ¼ 4.2 Hz), 135.22, 134.56 (d, J ¼ 3.4 Hz), 131.56 (d, J ¼ 10.1 Hz),
131.39, 131.28, 129.27, 128.76 (d, J ¼ 12.3 Hz), 127.39 (d, J ¼ 7.0 Hz),
126.55, 125.07, 122.19, 121.21 ppm; 31P NMR (162 MHz, CDCl3)
CDCl3)
d
27.00 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
C
24H19O3P 387.1145; Found 387.1135. IR (film): 3054, 2937, 1627,
d
31.42 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C26H19OP
1558, 1438, 1365, 1176, 983, 851, 820, 755 cmꢂ1
.
379.1246; Found 379.1248.
4.2.2.5. Diphenyl(o-tolyl)phosphine oxide (2g). A white solid;
43.8 mg; 75% yield; 1H NMR (400 MHz, CDCl3)
7.71e7.60 (m, 4H),
7.54 (t, J ¼ 7.9 Hz, 2H), 7.47 (td, J ¼ 7.4, 2.7 Hz, 4H), 7.41 (t, J ¼ 7.5 Hz,
1H), 7.28 (dd, J ¼ 8.1, 3.3 Hz, 1H), 7.13 (t, J ¼ 6.4 Hz, 1H), 7.03 (dd,
J ¼ 14.4, 8.0 Hz, 1H), 2.46 (s, 3H) ppm; 13C NMR (101 MHz, CDCl3)
4.2.3. (40-methoxy-[1,10-biphenyl]-2-yl)diphenylphosphine oxide
(2n)
d
A white solid; 59.9 mg; 78% yield; 1H NMR (400 MHz, CDCl3)
d
7.63e7.48 (m, 5H), 7.44e7.27 (m, 9H), 7.14 (d, J ¼ 8.7 Hz, 2H), 6.58
(d, J ¼ 8.7 Hz, 2H), 3.72 (s, 3H) ppm; 13C NMR (101 MHz, CDCl3)
d
143.34 (d, J ¼ 8.0 Hz),133.49 (d, J ¼ 12.9 Hz),133.33,132.30,132.08
d
158.75, 147.52 (d, J ¼ 8.5 Hz), 134.09 (d, J ¼ 12.3 Hz), 133.74, 132.89
(d, J ¼ 1.9 Hz), 131.93 (d, J ¼ 9.7 Hz), 131.77 (d, J ¼ 2.2 Hz), 131.37,
131.37, 130.35, 130.35, 128.56 (d, J ¼ 12.1 Hz), 125.18 (d, J ¼ 12.8 Hz),
(d, J ¼ 4.0 Hz),132.70,132.38,132.03 (d, J ¼ 9.8 Hz),131.75,131.58 (d,
J ¼ 9.3 Hz),131.40,131.10 (d, J ¼ 2.0 Hz),112.70, 55.23 ppm; 31P NMR
21.70 (d, J ¼ 4.6 Hz) ppm; 31P NMR (162 MHz, CDCl3)
d
31.60 ppm.
(162 MHz, CDCl3)
d
27.83 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C19H17OP 293,1090;
Found 293.1090. IR (film): 3060, 2960, 2925, 1589, 1438, 1282, 1180,
Calcd for C25H21O2P 385.1352; Found 385.1352. IR (film): 3051,
2932, 1609, 1513, 1463, 1436, 1238, 1188, 1110, 1031, 830, 742, 697,
1117, 764, 702, 546 cmꢂ1
.
543 cmꢂ1
.
4.2.2.6. (2,4-Dimethoxyphenyl)diphenylphosphine oxide (2h). A
4.2.3.1. (40-chloro-[1,10-biphenyl]-2-yl)diphenylphosphine oxide (2o).
white solid; 54.1 mg; 80% yield; 1H NMR (400 MHz, CDCl3)
A white solid; 66.1 mg; 86% yield; 1H NMR (400 MHz, CDCl3)
d
7.74e7.62 (m, 5H), 7.54e7.36 (m, 6H), 6.64e6.50 (m, 1H), 6.44 (dd,
d
7.62e7.52 (m, 3H), 7.35 (tdt, J ¼ 11.8, 7.6, 5.8 Hz, 5H), 7.13 (d,
J ¼ 4.6, 2.2 Hz, 1H), 3.83 (s, 3H), 3.53 (s, 3H) ppm; 31P NMR
J ¼ 8.5 Hz, 1H), 7.00 (d, J ¼ 8.5 Hz, 1H) ppm; 13C NMR (101 MHz,
(162 MHz, CDCl3)
Calcd for C20H19O3P 339.1145; Found 339.1136. IR (film): 3087,
d
27.02 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
CDCl3)
d
142.55 (dd, J ¼ 775.4, 6.2 Hz), 134.00 (d, J ¼ 12.1 Hz), 133.33
(d, J ¼ 5.3 Hz), 132.60, 132.32, 132.06e131.07 (m), 128.19 (d,
3048, 2990, 2926, 2854,1596,1438,1302,1180,1105,1026, 836, 698,
J ¼ 12.1 Hz), 127.25, 126.92 (d, J ¼ 12.4 Hz) ppm; 31P NMR (162 MHz,
525 cmꢂ1
.
CDCl3)
C
d
27.61 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for
24H18OPCl 389.0587; Found 389.0859. IR(film): 3052, 2923, 2853,
4.2.2.7. Methyl 2-(diphenylphosphoryl)benzoate (2i). A white solid;
55.2 mg; 82% yield; 1H NMR (400 MHz, CDCl3)
7.90 (dd, J ¼ 7.5,
3.8 Hz, 1H), 7.72e7.59 (m, 5H), 7.58e7.41 (m, 8H), 3.48 (s, 3H) ppm;
13C NMR (101 MHz, CDCl3)
1591, 1462, 1434, 1197, 830, 780, 752, 716, 547, 519 cmꢂ1
.
d
4.2.3.2. Diphenyl(1-phenylnaphthalen-2-yl)phosphine oxide (2p).
A white solid; 75.2 mg; 93% yield; 1H NMR (400 MHz, CDCl3)
7.88
d
167.70, 135.97 (d, J ¼ 6.1 Hz), 134.75 (d,
d
J ¼ 10.5 Hz), 133.83, 132.89, 132.76, 131.90, 131.87 (d, J ¼ 2.4 Hz),
131.70 (d, J ¼ 9.9 Hz), 131.61 (d, J ¼ 2.9 Hz), 130.94 (d, J ¼ 11.8 Hz),
130.48 (d, J ¼ 8.6 Hz), 128.38 (d, J ¼ 12.4 Hz), 52.17 ppm; 31P NMR
(d, J ¼ 8.2 Hz, 1H), 7.85 (dd, J ¼ 8.6, 2.2 Hz, 1H), 7.64e7.50 (m, 6H),
7.36 (ddt, J ¼ 10.2, 7.3, 4.8 Hz, 8H), 7.17 (t, J ¼ 6.7 Hz, 1H), 7.07 (t,
J ¼ 7.6 Hz, 2H), 7.04e7.00 (m, 2H) ppm; 31P NMR (162 MHz, CDCl3)
(162 MHz, CDCl3)
d
30.83 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ
d
27.81 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C28 H21O P
Calcd for C21H17O4P 365.0937; Found 365.0938. IR (film): 3058,
405.1403; Found 405.1406. IR (film): 3056, 2923, 2853, 1551, 1435,
2948, 1729, 1435, 1294, 1252, 1184, 1130, 797, 760, 730, 538 cmꢂ1
.
1373, 1197, 1112, 819, 756, 697, 558, 534 cmꢂ1
.
4.2.2.8. Diphenyl(thiophen-2-yl)phosphine oxide (2k). A white
solid; 55.2 mg; 97% yield; 1H NMR (400 MHz, CDCl3)
7.74 (dd,
4.2.3.3. Diphenyl(1-(4-(trifluoromethyl)phenyl)naphthalen-2-yl)
phosphine oxide (2q). A white solid; 80.3 mg; 85% yield; 1H NMR
d
J ¼ 12.4, 7.5 Hz, 5H), 7.56 (t, J ¼ 7.3 Hz, 2H), 7.47 (td, J ¼ 7.5, 2.9 Hz,
(400 MHz, CDCl3)
d
7.90 (t, J ¼ 9.5 Hz, 1H), 7.56 (dd, J ¼ 20.1, 8.2 Hz,
5H), 7.20 (t, J ¼ 3.2 Hz,1H) ppm; 13C NMR (101 MHz, CDCl3)
d
136.97
3H), 7.44 (dd, J ¼ 14.2, 7.0 Hz, 1H), 7.41e7.29 (m, 4H), 7.17 (d,
(d, J ¼ 10.0 Hz), 134.53, 133.94 (d, J ¼ 5.1 Hz), 133.51, 133.42, 132.41,
J ¼ 7.9 Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3)
d 142.55 (dd,
132.19 (d, J ¼ 2.8 Hz), 131.80 (d, J ¼ 10.4 Hz), 128.51 (d, J ¼ 12.6 Hz),
J ¼ 776.1, 6.3 Hz), 134.01 (d, J ¼ 12.1 Hz), 133.33 (d, J ¼ 5.9 Hz),
128.26 (d, J ¼ 13.8 Hz) ppm; 31P NMR (162 MHz, CDCl3)
d
21.73 ppm.
132.61, 132.33, 131.84, 131.74, 131.66, 131.56, 131.53,131.34, 131.32,
HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C16
H
13OPS 285.0497;
128.19 (d, J ¼ 12.1 Hz),127.25,126.92 (d, J ¼ 12.3 Hz), 29.71 ppm; 31
P
Found 285.0507. IR(film): 3056, 2854, 2925, 1436, 1404, 1219, 1189,
NMR (162 MHz, CDCl3) d
27.26 ppm; 19F NMR (376 MHz, CDCl3)
1116, 1004, 853, 728, 697, 576, 547 cmꢂ1
.
d
62.71 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C29H20F3OP
473.1277; Found 473.1290. IR (film): 3053, 2924, 1615, 1438, 1320,
4.2.2.9. Mesityldiphenylphosphine oxide (2l). A white solid;
60.2 mg; 97% yield; 1H NMR (400 MHz, CDCl3)
1115, 1064, 1021, 874, 822, 754, 726, 699, 601, 520 cmꢂ1
.
d
7.66 (dd, J ¼ 12.0,
7.2 Hz, 4H), 7.53e7.47 (m, 2H), 7.43 (td, J ¼ 7.4, 2.6 Hz, 4H), 6.88 (d,
4.2.4. Synthesis of compound 3a
J ¼ 3.4 Hz, 2H), 2.30 (s, 3H), 2.12 (s, 6H) ppm; 13C NMR (101 MHz,
Naphthalen-1-yldiphenylphosphine oxide 2a (39.4 mg,
0.12 mmol), HSiCl3 (34.2 mg, 0.252 mmol, 2.1 eq), Et3N (26.7 mg,
0.264 mmol, 2.2 eq) and toluene (2 mL) were added to an oven-
dried Schlenk tube. The tube was evacuated and backfilled with
N2 three times. The mixture was stirred at 130 ꢀC for 6 h in an oil
bath. After cooling to room temperature, 2 mL of 30% aqueous so-
dium hydroxide solution was carefully added. The mixture was
CDCl3)
d
143.46 (d, J ¼ 10.1 Hz), 141.76, 135.77 (d, J ¼ 101.7 Hz),
131.56 (d, J ¼ 10.0 Hz), 131.45, 131.42, 131.07 (d, J ¼ 11.2 Hz), 128.63
(d, J ¼ 12.0 Hz), 24.06, 21.07 ppm; 31P NMR (162 MHz, CDCl3)
d
30.34 ppm. HRMS (ESI-QTOF) m/z: [MþH]þ Calcd for C21H21OP
321.1403; Found 321.1391. IR (film): 3053, 2923, 1601, 1436, 1175,
1114, 755, 730, 699, 626, 565, 512 cmꢂ1
.
6

X. Chen, X. Liu, H. Zhu et al.
Tetrahedron 81 (2021) 131912
[15] J.H. Xie, Q.L. Zhou, Acc. Chem. Res. 41 (2008) 581e593.
[16] W. Zhang, Y. Chi, X. Zhang, Acc. Chem. Res. 40 (2007) 1278e1290.
[17] V.V. Grushin, Chem. Rev. 104 (2004) 1629e1662.
[18] J. Yang, X. Chen, Z. Wang, Tetrahedron Lett. 56 (2015) 5673e5675.
[19] A.S. Balueva, E.I. Musina, A.A. Karasik, In Organophosphorus Chemistry, 2018,
pp. 1e49.
[20] I. Wauters, W. Debrouwer, C.V. Stevens, Beilstein J. Org. Chem. 10 (2014)
1064e1096.
[21] J.L. Montchamp, Acc. Chem. Res. 47 (2014) 77e87.
[22] C.S. Demmer, N. Krogsgaard-Larsen, L. Bunch, Chem. Rev. 111 (2011)
7981e8006.
then stirred at 60 ꢀC until the organic and aqueous layers became
clear. The organic layer was separated, and the aqueous layer was
extracted with CH2Cl2 (2ⅹ10 mL). The combined organic layer was
washed with brine (10 mL), dried over Na2SO4, and concentrated
under reduced pressure. The residue was purified by flash chro-
matography on silica gel (petroleum ether/ethyl acetate, 50/1) to
afford naphthalen-1-yldiphenylphosphine 3a (31.1 mg, 83% yield).
1H NMR (CDCl3, 400 MHz)
d
8.41 (dd, J ¼ 8.0, 4.0 Hz, 1H), 7.85 (t,
J ¼ 8.0 Hz, 2H), 7.50e7.41 (m, 2H), 7.37e7.28 (m, 11H), 7.02e6.98
[23] A.K. Bhattacharya, Chem. Rev. 81 (1981) 415e430.
(m, 1H); 31P NMR (CDCl3, 162 MHz)
d
ꢂ14.18. MS (ESI) m/z: [MþH]þ
[24] H. Zhang, X.-Y. Zhang, D.-Q. Dong, Z.-L. Wang, RSC Adv.
5 (2015)
52824e52831.
Calcd for C22H17P 313; Found 313. IR (film): 3051, 1433, 1265, 796,
[25] M. Oestreich, F. Tappe, V. Trepohl, Synthesis 2010 (2010) 3037e3062.
[26] A.L. Schwan, Chem. Soc. Rev. 33 (2004) 218e224.
774, 743, 696, 501, 446 cmꢂ1
.
[27] K. Xu, L. Liu, Z. Li, T. Huang, K. Xiang, T. Chen, J. Org. Chem. (2020), https://
doi.org/10.1021/acs.joc.0c01557.
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Declaration of competing interest
The authors declare that they have no known competing
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Acknowledgments
We thank the National Natural Science Foundation of China
(NSFC 21302010, 21571015), Beijing Municipal Natural Science
Foundation (Z200012) and the Fundamental Research Funds for the
Central Universities (buctrc 201321) for their generous support.
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