Nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds

Article abstract of DOI:10.1016/j.jorganchem.2016.07.026

A nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds is disclosed. This reaction can proceed smoothly under a mild reaction condition, producing the corresponding aryl phosphorus compounds in good to high yields.

Full text of DOI:10.1016/j.jorganchem.2016.07.026

Journal of Organometallic Chemistry 820 (2016) 120e124
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Note
Nickel-catalyzed phosphorylation of aryl triflates with P(O)eH
compounds
,
, **
Jia Yang a, Jing Xiao a, Tieqiao Chen a *, Li-Biao Han b
a State Key Laboratory of Chemo/Biosensing and Chemo Metrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082,
China
b National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A nickel-catalyzed phosphorylation of aryl triflates with P(O)eH compounds is disclosed. This reaction
can proceed smoothly under a mild reaction condition, producing the corresponding aryl phosphorus
compounds in good to high yields.
Received 30 April 2016
Received in revised form
17 June 2016
Accepted 29 July 2016
Available online 12 August 2016
© 2016 Elsevier B.V. All rights reserved.
Keywords:
Phosphorylation
Triflates
PeH compounds
Cross coupling
Nickel catalysis
1. Introduction
2. Result and discussion
The development of efficient methods for preparing aryl phos-
phorus compounds is of great importance because of their wide
application in medicinal chemistry, materials chemistry and
organic synthesis [1]. Though transition metal-catalyzed phos-
phorylation of aryl halides and counterparts with P(O)eH com-
pounds pioneered by Hirao's group has been well established [2],
great efforts are devoted to making the cross coupling greener by
replacing the aryl halides and noble metal catalysts with cheaper,
more readily available and less toxic participants [3,4]. Recently, the
scope of Hirao reaction has been extended to use phenol derivatives
as the substrate [5,6]. Aryl triflates, mesylates and tosylates readily
coupled with P(O)eH compounds in the presence of a noble
palladium catalyst, serving as an efficient procedure for PeC bonds
formation [5]. Herein, we report an efficient nickel-catalyzed
phosphorylation of aryl triflates to produce the corresponding
aryl phosphorous compounds in good to high yields under a mild
reaction condition (Scheme 1) [6].
We initiated our work with examining the reactivity of phenyl
triflate 1a and diphenylphosphine oxide 2a mediated by a nickel/
phosphine catalyst, and the obtained results were compiled in
Table 1. In the presence of 10 mol% Ni(COD)2 (bis(1,5-
cyclooctadiene)nickel(0))/dcype (Cy2PCH2CH2PCy2), the reaction
took place to give the coupling product 3a and its reduced form 3a’
in 81% combined yield (entry 1). Other selected phosphines also
mediated the reaction with 1,10-bis(diphenylphosphino)-ferrocene
(dppf) being the best choice (entries 2e6). The phosphine ligand
was essential to this transformation. In the absence of phosphine
ligand, the yield dramatically decreased to 19% (entry 7). Na2CO3
was found as active as K2CO3. However, a stronger base led to
decrease of yield (entries 9 and 10), which would be ascribed to the
strong hydrolysis of triflate under the reaction conditions. This
reaction also took place smoothly in toluene and DMF (entries 11
and 13), whereas hexane was used as the solvent, poor yield was
afforded (entry 12). The Nickel catalyst is crucial to this reaction. No
reaction was observed in the absence of the catalyst (entry 14).
When the reaction was performed at 60 ꢀC, 80% yield of 3a was
given under similar reaction conditions (entry 15).
* Corresponding author.
Under the optimized reaction conditions, the substrate scope
was investigated. As shown in Table 2, a variety of aryl triflates 1
** Corresponding author.
E-mail addresses: chentieqiao@hnu.edu.cn (T. Chen), libiao-han@aist.go.jp
(L.-B. Han).
http://dx.doi.org/10.1016/j.jorganchem.2016.07.026
0022-328X/© 2016 Elsevier B.V. All rights reserved.

J. Yang et al. / Journal of Organometallic Chemistry 820 (2016) 120e124
121
be used as the substrate to produce the expected triphenylphos-
phine 3a’ in 84% yield under similar reaction conditions (entry 16)
[7].
On the basis of the previous literatures [6,8], a plausible
mechanism was proposed as shown in Scheme 2. Ni(0) complex A
firstly oxidatively adds to aryl triflates to produce species B, which
undergoes ligand exchange with hydrogen phosphoryl compounds
by the aid of a base, giving the intermediate C. Reductive elimina-
tion of C produces the corresponding coupling product 3 and re-
generates complex A.
Scheme 1. Nickel-catalyzed phosphorylation of aryl triflates.
3. Conclusion
In summary, we have developed an efficient nickel-catalyzed
phosphorylation of aryl triflates with hydrogen phosphoryl com-
pounds. A variety of aryl phosphorus compounds are produced
under a mild reaction condition from the readily available starting
materials. This reaction is well complementary to the previous
nickel-catalyzed PeC bonds formation from phenol derivatives [6].
Table 1
Nickel-catalyzed phosphorylation of phenyl triflate.a
4. Experimental section
Entry
Cat. Ni
Ligand
Base
Solvent
Yield (3a/3a’)b
1
2
3
4
5
6
7
8
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
none
dcype
PCy3
dppp
dppb
dppf
BINAP
none
dppf
dppf
dppf
dppf
dppf
dppf
none
dppf
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
Cs2CO3
t-BuONa
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Toluene
Hexane
DMF
81%(97/3)
66%(67/33)
75%(97/3)
88%(98/2)
99%(99/1)
35%(73/27)
19%(49/51)
99%(99/1)
35%(77/23)
n.d.
4.1. General information
All reactions were carried out in the oven-dried Schlenck tubes
under a N2 atmosphere. Dry solvents were obtained by purification
according to standard methods. Reagents were used as received
unless otherwise noted. Column chromatography was performed
using Silica Gel 60 (particle size 37e54
mm). The pure products
9
were obtained by means of column chromatography. 1H NMR, 13
C
10
11
12
13
14
15c
NMR and 31P NMR data were acquired on a Bruker-400 spec-
trometer (400 MHz for 1H, 100 MHz for 13C, and 162 MHz for 31P
NMR spectroscopy). Chemical shifts for 1H NMR are referred to
88%(98/2)
39%(95/5)
89%(98/2)
n.d.
Dioxane
Dioxane
internal Me4Si (0 ppm) and reported as follows: chemical shift (
d
Ni(COD)2
80%(98/2)
ppm), multiplicity, coupling constant (Hz) and integration. Data for
31P NMR were relative to H3PO4 (85% solution in D2O, 0 ppm).
Compounds 3a to 3o and 3a’ have been reported privously [4gei,9].
a
Reaction conditions: 1a (0.2 mmol), Ph2P(O)H (0.2 mmol), 10 mol% Ni(COD)2,
base (0.2 mmol), solvent (2 mL), 80 ꢀC, 20 h.
b
GC yield using tridecane as an internal standard.
60 ꢀC.
c
4.2. Synthesis of starting materials
coupled with hydrogen phosphoryl compounds 2 to produce the
corresponding products in good to high yields. High yields were
obtained with both electron-rich and electron-deficient aryl tri-
flates (entries 2e8). Thus, derivatives of aryl triflates bearing an
electron-donating group like methyl (2-, 3- and 4-position),
methoxy and phenyl group on the benzene ring all gave the
coupling products in good yields (entries 2e6). Aryl-F and Aryl-CN
bonds which could be cleaved by nickel catalyst survived well
under the present reaction conditions (entries 7 and 8). Substrate
with an electron-withdrawing CF3 group also coupled with 2a,
furnishing the product 3i in 79% yields (entry 9). High yield of 3j
was obtained from the reaction of naphthyl triflate 1j with 2a
(entry 10). N-heterocyclic triflates 1k also showed high reactivity in
the catalytic system, generating the coupling product 3k in 85%
yield.
Other hydrogen phosphoryl compounds are also applicable to
this transformation. In addition to diphenylphosphine oxide 2a,
aliphatic n-Bu2P(O)H (Table 2, entry 12), the bulky t-BuPhP(O)H
(entry 13) and Cy2P(O)H (entry 14) coupled with phenyl triflate 1a
readily by elevating the reaction temperature, producing the cor-
responding products in moderate to high yields. Similarly, diiso-
propyl phosphite 2e also served as a good substrate, affording the
product 3o in 70% yield (1.5 equiv 2e was added due to partly hy-
drolytic decomposition of phosphoryl group, entry 15). Worth
noting is that the highly coordinative diphenylphosphine could also
After phenols and pyridine were dissolved in dry DCM, triflic
anhydride was added slowly by syringe over 5 min at 0 ꢀC. Then the
reaction mixture was allowed to be warmed up to 25 ꢀC and further
stirred at 25 ꢀC for 12 h. After the reaction mixture was quenched
with water, the aqueous layer was extracted with CH2Cl2 and the
combined organic layer was dried over Na2SO4 and then filtrated.
The products were purified by regular flash chromatography (pe-
troleum ether/EtOAc mixtures) [10].
4.3. Typical procedure for the nickel-catalyzed phosphorylation of
aryl triflates with P(O)eH compounds
Under a N2 atmosphere, 0.2 mmol aryl triflate1a, 0.2 mmol
Ph2P(O)H 2a, 10 mol% Ni(COD)2,10 mol% dppf, 1.0 equiv Na2CO3 and
2 mL dioxane were charged into a 10 mL schlenck tube. The mixture
was stirred at 80 ꢀC for 20 h. After removal of the volatile, the
residues were passed through a short silica chromatography (par-
ticle size 37e54 mm, petroleum ether/ethyl acetate as eluent) to
afford analytically pure organophosphorus compounds 3.
4.3.1. Triphenylphosphine oxide (3a)
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3a (53.4 mg, 96%) as a white solid. Rf ¼ 0.25
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d
7.69e7.65 (m, 6H), 7.53e7.45 (m, 9H). 13C NMR (100 MHz CDCl3):

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J. Yang et al. / Journal of Organometallic Chemistry 820 (2016) 120e124
Table 2
Ni-catalyzed CeO/PeH cross coupling of aryl triflates 1 with PeH compounds 2.a
d
132.50(d, JC-P ¼ 104.8 Hz), 132.09 (d, JC-P ¼ 9.8 Hz), 131.96 (d, JC-
¼ 2.8 Hz), 128.52 (d, JC-P ¼ 12.0 Hz). 31P NMR (162 MHz CDCl3):
29.18 ppm.
1H),7.03 (dd, J ¼ 7.8 Hz, J ¼ 14.0 Hz, 1H),2.45 (s, 3H). 13C NMR
(100 MHz CDCl3):
d
143.30 (d, JC-P ¼ 8.0 Hz), 133.49 (d, JC-
P
d
¼ 12.9 Hz), 132.68 (d, JC-P ¼ 103.9 Hz), 132.14 (d, JC-P ¼ 2.9 Hz),
P
132.06 (d, JC-P ¼ 19.8 Hz), 131.91 (d, JC-P ¼ 9.6 Hz), 131.82 (d, JC-
¼ 2.8 Hz), 130.73 (d, JC-P ¼ 102.5 Hz), 128.59 (d, JC-P ¼ 12.0 Hz),
4.3.2. Triphenylphosphine (3a’)
P
125.21 (d, JC-P ¼ 12.8 Hz), 21.70 (d, JC-P ¼ 4.7 Hz). 31P NMR (162 MHz
[4h] Purification by chromatography (petroleum ether) afforded
3a’ (44.0 mg, 84%) as a white solid. Rf ¼ 0.43 (petroleum ether); 1H
CDCl3):
d 31.86 ppm.
NMR (400 MHz CDCl3): d
7.317 (br, 15H). 13C NMR (100 MHz CDCl3):
d
137.23 (d, JC-P ¼ 10.7 Hz), 133.80 (d, JC-P ¼ 19.4 Hz), 128.77, 128.56
4.3.4. Diphenyl(m-tolyl)phosphine oxide (3c)
(d, JC-P ¼ 6.9 Hz). 31P NMR (162 MHz CDCl3):
d
ꢁ5.42 ppm.
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3c (53.7 mg, 92%) as a white solid. Rf ¼ 0.41
4.3.3. Diphenyl(o-tolyl)phosphine oxide (3b)
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d 7.67
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3b (44.4 mg, 76%) as a white solid. Rf ¼ 0.34
(dd, J ¼ 7.6 Hz, J ¼ 12.0 Hz, 4H), 7.58e7.53 (m, 3H), 7.48e7.44 (m,
4H), 7.40e7.35 (m, 3H), 2.36 (s, 3H). 13C NMR (100 MHz CDCl3):
(petroleum ether/EtOAc ¼ 1:1);1H NMR (400 MHz CDCl3):
d
7.65
d
138.50 (d, JC-P ¼ 11.9 Hz), 132.61 (d, JC-P ¼ 103.4 Hz), 132.81 (d, JC-
¼ 2.8 Hz), 132.51 (d, JC-P ¼ 9.4 Hz), 132.21 (d, JC-P ¼ 103.2 Hz),
(dd, J ¼ 7.6 Hz, J ¼ 12.0 Hz,4H), 7.54 (t, J ¼ 7.6 Hz, 2H), 7.48e7.40
P
(m,5H), 7.28 (d, J ¼ 6.8 Hz, 1H), 7.12 (dd, J ¼ 6.4 Hz, J ¼ 6.4 Hz,
132.10 (d, JC-P ¼ 9.9 Hz), 131.92 (d, JC-P ¼ 2.7 Hz), 129.19 (d, JC-

J. Yang et al. / Journal of Organometallic Chemistry 820 (2016) 120e124
123
132.17 (d, JC-P ¼ 2.7 Hz), 132.12 (d, JC-P ¼ 104.7 Hz), 132.03 (d, JC-
¼ 9.9 Hz), 128.63 (d, JC-P ¼ 12.2 Hz), 128.41 (dd, JC-P ¼ 105.5 Hz, JC-
P
¼ 3.0 Hz), 128.40 (dd, JC-P ¼ 13.2 Hz, JC-F ¼ 21.3 Hz). 31P NMR
F
(162 MHz CDCl3):
d 28.82 ppm.
4.3.9. 4-(Diphenylphosphoryl)benzonitrile (3h)
[4g] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3h (52.1 mg, 86%) as a white solid. Rf ¼ 0.31
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d
7.83e7.75 (m, 4H), 7.68e7.58 (m, 6H), 7.52e7.48 (m, 4H). 13C NMR
(100 MHz CDCl3):
d
138.30 (d, JC-P ¼ 98.6 Hz), 132.65 (d, JC-
¼ 9.4 Hz),132.62 (d, JC-P ¼ 3.4 Hz),132.04 (d, JC-P ¼ 12.7 Hz),132.02
P
(d, JC-P ¼ 9.9 Hz), 131.00 (d, JC-P ¼ 105.1 Hz), 128.87 (d, JC-
¼ 12.2 Hz), 117.90 (d, JC-P ¼ 1.3 Hz), 115.67 (d, JC-P ¼ 3.1 Hz). 31P
P
NMR (162 MHz CDCl3):
d 28.19 ppm.
Scheme 2. A proposed mechanism for the nickel-catalyzed phosphorylation of aryl
triflates.
4.3.10. Diphenyl(4-(trifluoromethyl)phenyl)phosphine oxide (3i)
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3i (54.7 mg, 79%) as a white solid. Rf ¼ 0.31
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d 7.82 (t,
¼ 10.3 Hz), 128.50 (d, JC-P ¼ 12.0 Hz), 128.33 (d, JC-P ¼ 12.8 Hz),
P
21.45. 31P NMR (162 MHz CDCl3):
d 29.47 ppm.
J ¼ 7.2 Hz, 2H), 7.74e7.62 (m, 6H), 7.59 (t, J ¼ 7.2 Hz, 2H), 7.51e7.49
(m, 4H). 13C NMR (100 MHz CDCl3):
d
137.10 (d, JC-P ¼ 100.0 Hz),
133.56 (dt, JC-P ¼ 2.7 Hz, JC-F ¼ 30.2 Hz), 132.57 (d, JC-P ¼ 10.1 Hz),
4.3.5. Diphenyl(p-tolyl)phosphine oxide (3d)
132.41 (d, JC-P ¼ 2.7 Hz), 132.04 (d, JC-P ¼ 10.0 Hz), 131.56 (d, JC-
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3d (50.8 mg, 87%) as a white solid. Rf ¼ 0.28
¼ 105.5 Hz), 128.76 (d, JC-P ¼ 12.2 Hz), 125.31 (dt, JC-P ¼ 11.8 Hz, JC-
P
¼ 3.1 Hz), 123.56 (d, JC-F ¼ 271.3 Hz). 31P NMR (162 MHz CDCl3):
F
d
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d 7.66
28.22 ppm.
(dd, J ¼ 7.6 Hz, J ¼ 11.6 Hz, 4H), 7.58e7.52 (m, 4H), 7.47e7.43 (m,
4H), 7.28e7.27 (m, 2H), 2.40 (s, 3H). 13C NMR (100 MHz CDCl3):
4.3.11. Naphthalen-2-yldiphenylphosphine oxide (3j)
d
142.47 (d, JC-P ¼ 2.8 Hz), 132.83 (d, JC-P ¼ 103.5 Hz), 132.14 (d, JC-
¼ 10.1 Hz), 132.08 (d, JC-P ¼ 9.9 Hz), 131.84 (d, JC-P ¼ 2.7 Hz), 129.27
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3j (57.7 mg, 88%) as a white solid. Rf ¼ 0.29
P
(d, JC-P ¼ 12.5 Hz), 129.16 (d, JC-P ¼ 106.0 Hz), 128.46 (d, JC-
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d 8.29
¼ 12.1 Hz), 21.63 (d, JC-P ¼ 1.0 Hz). 31P NMR (162 MHz CDCl3):
P
d
(d, J ¼ 14.0 Hz, 1H), 7.91e7.85 (m, 3H), 7.74e7.44 (m, 13H). 13C NMR
29.23 ppm.
(100 MHz CDCl3):
d
134.74 (d, JC-P ¼ 2.2 Hz), 134.05 (d, JC-P ¼ 9.3 Hz),
132.45 (d, JC-P ¼ 103.7 Hz), 132.43 (d, JC-P ¼ 13.2 Hz), 132.17 (d, JC-
4.3.6. (4-Methoxyphenyl)diphenylphosphine oxide (3e)
¼ 9.9 Hz), 132.07 (d, JC-P ¼ 2.8 Hz), 129.47 (d, JC-P ¼ 103.8 Hz),
P
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:2) afforded 3e (52.4 mg, 85%) as a white solid. Rf ¼ 0.50
128.99, 128.60 (d, JC-P ¼ 12.1 Hz), 128.37 (d, JC-P ¼ 10.6 Hz), 128.32,
127.86 (d, JC-P ¼ 0.6 Hz), 127.01, 126.84 (d, JC-P ¼ 10.7 Hz). 31P NMR
(EtOAc); 1H NMR (400 MHz CDCl3):
d
7.66 (dd, J ¼ 8.0 Hz,
(162 MHz CDCl3):
d 29.51 ppm.
J ¼ 12.0 Hz, 4H), 7.61e7.52 (m, 4H), 7.47e7.44 (m, 4H), 6.97 (d,
J ¼ 7.6 Hz, 2H), 3.84 (s, 3H). 13C NMR (100 MHz CDCl3):
d 162.53 (d,
4.3.12. Diphenyl(pyridin-3-yl)phosphine oxide (3k)
JC-P ¼ 2.7 Hz), 133.98 (d, JC-P ¼ 11.2 Hz), 132.89 (d, JC-P ¼ 104.0 Hz),
132.06 (d, JC-P ¼ 9.8 Hz), 131.85 (d, JC-P ¼ 2.7 Hz), 128.48 (d, JC-
[4g] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:2) afforded 3k (47.4 mg, 85%) as a white solid. Rf ¼ 0.33
(EtOAc); 1H NMR (400 MHz CDCl3):
d 8.79e8.78 (m, 2H), 8.05 (t,
¼ 12.0 Hz), 123.48 (d, JC-P ¼ 109.9 Hz), 114.12 (d, JC-P ¼ 13.1 Hz),
P
55.37. 31P NMR (162 MHz CDCl3):
d 29.28 ppm.
J ¼ 9.6 Hz, 1H), 7.71e7.66 (m, 4H), 7.60e7.43 (m, 7H). 13C NMR
(100 MHz CDCl3):
d
152.60 (d, JC-P ¼ 1.7 Hz), 152.49 (d, JC-
4.3.7. [1,10-Biphenyl]-4-yldiphenylphosphine oxide (3f)
¼ 11.8 Hz), 139.77 (d, JC-P ¼ 7.8 Hz), 132.45 (d, JC-P ¼ 2.8 Hz), 131.97
P
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3f (63.7 mg, 90%) as a white solid. Rf ¼ 0.30
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
(d, JC-P ¼ 10.1 Hz), 131.45 (d, JC-P ¼ 105.2 Hz), 129.09 (d, JC-
¼ 100.1 Hz), 128.79 (d, JC-P ¼ 12.3 Hz), 123.52 (d, JC-P ¼ 8.8 Hz). 31
P
P
NMR (162 MHz CDCl3):
d 26.54 ppm.
d
7.77e7.68 (m, 8H), 7.61e7.55 (m, 4H), 7.50e7.44 (m, 6H),
7.41e7.37 (m, 1H). 13C NMR (100 MHz CDCl3):
d 144.79 (d, JC-
4.3.13. Dibutyl(phenyl)phosphine oxide (3l)
¼ 2.8 Hz), 139.88, 132.65 (d, JC-P ¼ 10.2 Hz), 132.36 (d, JC-
P
P
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:2) afforded 3l (42.8 mg, 90%) as a white solid. Rf ¼ 0.53
¼ 104.0 Hz), 132.14 (d, JC-P ¼ 9.9 Hz), 132.08 (d, JC-P ¼ 2.7 Hz),
(EtOAc); 1H NMR (400 MHz CDCl3):
d
7.70 (dd, J ¼ 8.0 Hz, J ¼ 8.0 Hz,
130.87 (d, JC-P ¼ 104.8 Hz), 129.00, 128.40 (d, JC-P ¼ 12.1 Hz), 128.22,
127.30, 127.24 (d, JC-P ¼ 12.4 Hz). 31P NMR (162 MHz CDCl3):
2H), 7.55e7.49 (m, 3H), 2.02e1.80 (m, 4H), 1.67e1.56 (m, 2H),
1.46e1.33 (m, 6H), 0.89e0.86 (t, J ¼ 6.8 Hz, 6H). 13C NMR (100 MHz
d
29.59 ppm.
CDCl3):
d
132.61 (d, JC-P ¼ 90.9 Hz), 131.44 (d, JC-P ¼ 2.7 Hz), 130.40
4.3.8. (4-Fluorophenyl)diphenylphosphine oxide (3g)
(d, JC-P ¼ 8.7 Hz), 128.60 (d, JC-P ¼ 11.0 Hz), 29.66 (d, JC-P ¼ 68.0 Hz),
[4i] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:1) afforded 3g (53.9 mg, 91%) as a white solid. Rf ¼ 0.36
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
24.11 (d, JC-P ¼ 14.5 Hz), 23.50 (d, JC-P ¼ 4.1 Hz), 13.58. 31P NMR
(162 MHz CDCl3):
d 40.83 ppm.
d
7.70e7.63 (m, 6H), 7.58e7.54 (m, 2H), 7.49e7.46 (m, 4H), 7.16 (t,
4.3.14. Tert-butyldiphenylphosphine oxide (3m)
[4h] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:2) afforded 3m (40.2 mg, 78%) as a white solid. Rf ¼ 0.60
J ¼ 8.4 Hz, 2H). 13C NMR (100 MHz CDCl3):
d
165.11 (dd, JC-
¼ 3.2 Hz, JC-F ¼ 252.1 Hz), 134.61 (dd, JC-P ¼ 8.8 Hz, JC-F ¼ 11.3 Hz),
P

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J. Yang et al. / Journal of Organometallic Chemistry 820 (2016) 120e124
(EtOAc); 1H NMR (400 MHz CDCl3):
d
7.96 (dd, J ¼ 8.4 Hz, J ¼ 8.4 Hz,
ꢁ
ꢁ
ꢁ
ꢁ
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(1992) 864;
4H), 7.55e7.46 (m, 6H), 1.25 (d, J ¼ 14.8 Hz, 9H). 13C NMR (100 MHz
ꢁ
}
ꢁ
ꢁ
CDCl3):
d
132.20 (d, JC-P ¼ 8.1 Hz), 131.49 (d, JC-P ¼ 2.7 Hz), 131.17 (d,
ꢁ
JC-P ¼ 89.9 Hz), 128.28 (d, JC-P ¼ 10.9 Hz), 33.97 (d, JC-P ¼ 70.4 Hz),
25.21. 31P NMR (162 MHz CDCl3):
d
38.77 ppm.
(f) K.J. Gagnon, S.J. Teat, Z.J. Beal, A.M. Embry, M.E. Strayer, A. Clearfield, Cryst.
Growth Des. 14 (2014) 3612;
(g) D. Herault, D.H. Nguyen, D. Nuel, G. Buono, Chem. Soc. Rev. 44 (2015)
4.3.15. Dicyclohexyl(phenyl)phosphine oxide (3n)
ꢁ
[9] Purification by chromatography (petroleum ether/
EtOAc ¼ 1:2) afforded 3n (32.5 mg, 56%) as a white solid. Rf ¼ 0.43
2508;
(h) Y. Li, L.-Q. Lu, S. Das, S. Pisiewicz, K. Junge, M. Beller, J. Am. Chem. Soc. 134
(2012) 18325;
(i) W. Tang, X. Zhang, Chem. Rev. 103 (2003) 3029.
(EtOAc); 1H NMR (400 MHz CDCl3):
d
7.59 (dd, J ¼ 7.2 Hz, J ¼ 7.2 Hz,
2H), 7.42e7.40 (m, 3H), 1.98 (br, 4H), 1.75e1.53 (m, 8H), 1.24e1.05
[2] (a) T. Hirao, T. Masunaga, Y. Ohshiro, T. Agawa, Tetrahedron Lett. 21 (1980)
3595;
(b) T. Hirao, T. Masunaga, Y. Ohshiro, T. Agawa, Synthesis (1981) 56.
[3] Significant advances in the phosphorylation of aromatic C-H bonds have been
made, for a review, see: T. Chen, J.-S. Zhang, L.-B. Han, Dalton Trans. 45 (2016)
1843.
(m, 10H). 13C NMR (100 MHz CDCl3):
d
131.46 (d, JC-P ¼ 7.3 Hz),
131.23 (d, JC-P ¼ 0.6 Hz), 129.84 (d, JC-P ¼ 85.9 Hz), 128.24 (d, JC-
¼ 10.1 Hz), 35.10 (d, JC-P ¼ 66.8 Hz), 26.44 (d, JC-P ¼ 11.6 Hz), 26.33
P
(d, JC-P ¼ 11.4 Hz), 25.83, 25.49, 24.58 (d, JC-P ¼ 2.0 Hz). 31P NMR
(162 MHz CDCl3):
d 45.43 ppm.
[4] Selected examples for CeP bond formation, see: (a) J. Yang, T. Chen, Y. Zhou,
S. Yin, L.-B. Han, Chem. Commun. 51 (2015) 3549;
(b) S.M. Rummelt, M. Ranocchiari, J.A. van Bokhoven, Org. Lett. 14 (2012)
2188;
(c) J. Hu, N. Zhao, B. Yang, G. Wang, L.-N. Guo, Y.-M. Liang, S.-D. Yang, Chem.
Eur. J. 17 (2011) 5516;
(d) C.-G. Feng, M. Ye, K.-J. Xiao, S. Li, J.-Q. Yu, J. Am. Chem. Soc. 135 (2013)
9322;
(e) C. Li, T. Yano, N. Ishida, M. Murakami, Angew. Chem. Int. Ed. 52 (2013)
9801;
4.3.16. Diisopropyl phenylphosphonate (3o)
[4i] Purification by chromatography (petroleum ether/
EtOAc ¼ 2:1) afforded 3ꢀ (33.9 mg, 70%) as a colorless oil. Rf ¼ 0.59
(petroleum ether/EtOAc ¼ 1:1); 1H NMR (400 MHz CDCl3):
d 7.82
(dd, J ¼ 7.6 Hz, J ¼ 13.2 Hz, 2H), 7.53 (t, J ¼ 7.2 Hz, 1H), 7.47e7.43 (m,
2H), 4.75e4.63 (m, 2H), 1.37 (d, J ¼ 6.0 Hz, 6H), 1.23 (d, J ¼ 6.4 Hz,
6H). 13C NMR (100 MHz CDCl3):
d
132.05 (d, JC-P ¼ 2.9 Hz), 131.65 (d,
(f) Y. Gao, G. Wang, L. Chen, P. Xu, Y. Zhao, Y. Zhou, L.-B. Han, J. Am. Chem. Soc.
131 (2009) 7956;
JC-P ¼ 9.8 Hz), 129.81 (d, JC-P ¼ 188.6 Hz), 128.28 (d, JC-P ¼ 14.8 Hz),
(g) Y.-L. Zhao, G.-J. Wu, F.-S. Han, Chem. Commun. 48 (2012) 5868;
(h) J.-S. Zhang, T. Chen, J. Yang, L.-B. Han, Chem. Commun. 51 (2015) 7540;
(i) T. Wang, S. Sang, L. Liu, H. Qiao, Y. Gao, Y. Zhao, J. Org. Chem. 79 (2014) 608.
[5] C-P bond formation from phenol derivatives, see: (a) K.S. Petrakis,
T.L. Nagabhushan, J. Am. Chem. Soc. 109 (1987) 2831;
(b) D.A. Holt, J.M. Erb, Tetrahedron Lett. 30 (1989) 5393;
(c) Y. Uozumi, A. Tanahasi, S.-Y. Lee, T. Hayashi, J. Org. Chem. 58 (1993) 1945;
(d) B.H. Lipshutz, D.J. Buzard, C.S. Yun, Tetrahedron Lett. 40 (1999) 201;
(e) W.C. Fu, C.M. So, F.Y. Kwong, Org. Lett. 17 (2015) 5906. All of these re-
actions were catalyzed by noble metal palladium.
70.70 (d, JC-P ¼ 5.5 Hz), 24.02 (d, JC-P ¼ 3.9 Hz), 23.78 (d, JC-
¼ 4.7 Hz). 31P NMR (162 MHz CDCl3):
d 16.64 ppm.
P
Notes
The authors declare no competing financial interest.
[6] Recently, we reported a nickel-catalyzed P-C bond-forming reaction via C-O/
P-H cross coupling; however, phenyl pivalates do not couple with diphenyl-
phosphine oxide under the reaction conditions, see: (a) J. Yang, T. Chen, L.-
B. Han, J. Am. Chem. Soc. 137 (2015) 1782;
(b) J. Yang, J. Xiao, T. Chen, L.-B. Han, J. Org. Chem. 81 (2016) 3911.
[7] Ni-catalyzed cross coupling between triflates and three valent phosphine has
been reported, however, tedious reactions and long reaction time (2-3 days)
were required, see: D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes, T. R. Ver-
hoeven, P. J. Reider, J. Org. Chem. 59 (1994) 7180.
Acknowledgment
Partial financial supports from NFSC (21403062, 21573064,
21373080), HNNSF 2015JJ3039 and the Fundamental Research
Funds for the Central Universities (Hunan University) are gratefully
acknowledged.
[8] For oxidative addition of Ni(0) complex to CAr-O bond, see: (a) K. Muto,
J. Yamaguchi, A. Lei, K. Itami, J. Am. Chem. Soc. 135 (2013) 16384;
(b) R. Takise, K. Muto, J. Yamaguchi, K. Itami, Angew. Chem. Int. Ed. 53 (2014)
6791. For computational mechanistic insights into the nickel-catalyzed C-O
activation, see;
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2016.07.026.
(c) Q. Lu, H. Yu, Y. Fu, J. Am. Chem. Soc. 136 (2014) 8252;
(d) X. Hong, Y. Liang, K.N. Houk, J. Am. Chem. Soc. 136 (2014) 2017. For similar
ligand exchange of palladium complexes with Z-H (Z ¼ P(O), C) compounds,
see;
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