Experimental and theoretical study on palladium-catalyzed c-p bond formation via direct coupling of triarylbismuths with p(o)-h compounds

Article abstract of DOI:10.1021/jo402392t

A novel and highly efficient Pd-catalyzed cross-coupling of triarylbismuths with a variety of P(O)-H compounds has been developed that proceeds smoothly without exclusion of moisture or air and provides a general and powerful tool for the preparation of various valuable arylphosphonates, arylphosphinates, and arylphosphine oxides, with high atom-economy, operational simplicity of the procedure, and good to high yield. The coupling reaction is the first example of transition-metal-catalyzed C-P bond construction using triarylbismuth compounds as substrates. DFT calculations reveal that C-P bond formation is the rate-determing step.

Full text of DOI:10.1021/jo402392t

Article
pubs.acs.org/joc
Experimental and Theoretical Study on Palladium-Catalyzed C−P
Bond Formation via Direct Coupling of Triarylbismuths with P(O)−H
Compounds
Tao Wang,† Shuai Sang,† Liu Liu,†,§ Hongwei Qiao,† Yuxing Gao,*,† and Yufen Zhao†,‡
†Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical
Engineering, and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University, Xiamen 361005,
Fujian, China
‡Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry,
Tsinghua University, Beijing 100084, China
§Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0343, United States
S
* Supporting Information
ABSTRACT: A novel and highly efficient Pd-catalyzed cross-coupling of
triarylbismuths with a variety of P(O)−H compounds has been
developed that proceeds smoothly without exclusion of moisture or air
and provides a general and powerful tool for the preparation of various
valuable arylphosphonates, arylphosphinates, and arylphosphine oxides,
with high atom-economy, operational simplicity of the procedure, and
good to high yield. The coupling reaction is the first example of
transition-metal-catalyzed C−P bond construction using triarylbismuth
compounds as substrates. DFT calculations reveal that C−P bond
formation is the rate-determing step.
according to the reported methods,12a were used efficiently in
INTRODUCTION
■
Pd-catalyzed C- and N-arylation reactions.15 Notably, in some
Organophosphorus compounds are an extremely important
cases the transfer of all of the aryl groups from triarylbismuth
class of chemicals, which are widely used in biological, catalytic,
was observed in these arylation reactions,15a−g in line with the
Principles of Green Chemistry.16 Recently, a number of
experimental studies of transition-metal-catalyzed cross-cou-
pling of organobismuth favored palladium catalysts,15 such as
Pd(PPh3)4 and Pd(OAc)2. Since the C−Bi bond is weak,17 it
may easily add to Pd(0) species. To support our hypothesis, we
first performed gas-phase density functional theory (DFT)
calculations at the B3LYP/6-31+G(d)+LanL2DZ level (Table
1). The transition states (TS) appeared to be only 2.4 and 4.4
kcal/mol (free energy) relative to the corresponding model
substrates A, respectively,18 indicating that oxidative addition of
organobismuth compounds to Pd(0) catalyst is a very facile
step. Inspired by these results, our ongoing interests7a,b,8a,19 in
transition-metal-catalyzed C−P bond-forming reactions have
led us to investigate a novel, atom-economical, operationally
simple Pd-catalyzed cross-coupling reaction of triarylbismuths
with P(O)−H compounds (Scheme 1). To the best of our
knowledge, this method is the first example of transition-metal-
catalyzed cross-coupling of triarylbismuths with P(O)−H
compounds leading to arylphosphonates, arylphosphinates,
and arylphosphine oxides.
pharmaceutical, and material sciences with desired properties.1,2
In particular, arylphosphorus compounds such as arylphosph-
onates, arylphosphinates, and arylphosphine oxides have
attracted considerable attention due to their prime application
as ligands3 in transition-metal-catalyzed reactions, as retardant
materials,4 and as valuable synthetic intermediates.5 In the
1980s, Hirao and co-workers described the first examples of
aryl and vinyl halide couplings with dialkyl phosphites under
catalysis of Pd(0).6 Following this, remarkable progress in the
development of Csp2−P bond formation by cross-coupling has
been reported in the past decade, including the methods of
nickel-,7 copper-,8 manganese-,9 and palladium-catalyzed10
direct activation of the P−H bond. However, most of these
methods suffer from relatively strict reaction conditions or poor
substrate scope, and there is still a strong need for preparation
of arylphosphorus compounds from readily available starting
materials.
The last two decades have witnessed rapid development of
bismuth chemistry.11 Organobismuth compounds are nontoxic
and easily available building blocks among the heavy non-
radioactive main group elements.12 Undoubtedly, these
attractive features of bismuth compounds occupy a special
place in medicinal chemistry13 and organic synthesis and
catalysis.14 For instance, trivalent organobismuth compounds,
especially for triarylbismuth which could be easily obtainable
Received: October 26, 2013
Published: December 16, 2013
© 2013 American Chemical Society
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a
Table 1. Oxidative Addition of Various Organobismuth
Compounds to Pd(0)PPh3 (Free Energy Units: kcal/mol, L=
PPh3)
Table 2. Optimization of the Reaction Conditions
b
entry
catalyst
ligand
solvent
toluene
base
yield (%)
1
Pd(PPh3)4
Pd(OAc)2
PdCl2
Ni(OAc)2
NiCl2
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
pyridine
Et3N
29
2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMSO
DMF
0
3
37
4
0
5
0
6
CuI
25
Scheme 1. Pd-Catalyzed Preparation of Arylphosphonates,
Arylphosphinates, and Arylphosphine Oxides
7
CuO
0
8
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
0
9
0
10
11
12
13
14
15
16
17
18
19
20
21
22
23
0
86
46
CH3CN
1,4-dioxane
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
toluene
7
43
83
K2CO3
72
(i-Pr)2NEt
(i-Pr)2NEt
(i-Pr)2NEt
(i-Pr)2NEt
pyridine
95 (80)
[c]
RESULTS AND DISCUSSION
28
■
[d]
80
Based on our calculations, we selected the Pd-catalyzed cross-
coupling reaction of diisopropyl phosphonate 1a with
triphenylbismuth 2a as the standard reaction to optimize the
catalysis conditions, as shown in Table 2. Taking into account
atom efficiency,20 we directly used 1/3 equiv of triphenylbis-
muth to start our study. Initially, when 1a (0.2 mmol, 1 equiv,
33 mg) was added to a mixture of 2a (0.067 mmol, 1/3 equiv,
29 mg), Pd(PPh3)4 (0.006 mmol, 7 mg), 2,2′-bipyridine (0.012
mmol, 2 mg), and pyridine (0.3 mmol, 0.024 mL) in toluene at
100 °C for 24 h under an air atmosphere, the desired P-
arylation product 3a was obtained in 29% yield determined by
the 31P NMR signal-integration method (Table 2, entry 1).
Encouraged by this result, we further examined the effect of
catalyst, solvent, ligand, temperature, and base on the reaction
yield. Under similar reaction conditions, various transition-
metal complexes including Pd, Ni, and Cu salts were examined,
with the finding that palladium salts, especially PdCl2, were the
most effective catalyst to produce the desired product 3a
(Table 2, entries 1−3). In contrast, other metal salts such as
Ni(OAc)2, NiCl2, CuI, and CuO did not or only sluggishly
catalyze this reaction (Table 2, entries 4−7). The type of ligand
was vital to the present catalytic reaction. 2,2′-Bipyridine (bpy)
L1 was found to be the best choice (Table 2, entries 3 and 8−
11). Gratifyingly, further exploration suggested that a good 86%
yield of 3a was afforded when DMSO was employed as a
solvent (Table 2, entry 12). Other solvents including DMF,
CH3CN, and 1,4-dioxane were less effective (Table 2, entries
13−15). We next turned our attention to further improve the
yield of 3a by investigating the effect of bases. Among the
various bases screened, (i-Pr)2NEt turned out to be the best
[e]
81 (71)
[e]
98 (81)
a
Reaction conditions: diisopropyl phosphonate (0.2 mmol), triphe-
nylbismuth (0.067 mmol), catalyst (0.006 mmol), ligand (0.012
mmol), base (0.3 mmol), solvent (0.8 mL) at 100 °C for 24 h, under
b
air. Determined by 31P NMR. Yields are based on 1a. Yields in
parentheses are isolated yields. At 80 °C. Under argon. Using
diphenylphosphine oxide (0.2 mmol).
[c]
[d]
[e]
base and promoted the coupling to provide 3a in 95% yield
(Table 2, entry 18), along with a trace of homocoupling
product biphenyl.15e Other bases and corresponding yields of
3a were as follows: pyridine, 86%; Et3N, 83%; and K2CO3, 72%
(Table 2, entries 12, 16, and 17). The choice of temperature
also highly affected this reaction. The coupling did not occur at
room temperature; however, the yield of product 3a increased
slowly when the temperature was raised to 80 °C (Table 2,
entry 19), and the catalytic reaction proceeded quite well,
affording the corresponding product 3a in an excellent yield of
95% when the temperature was raised to 100 °C (Table 2,
entry 18). In contrast to the yield of 95% under air, the
coupling of diisopropyl phosphonate 1a with triphenylbismuth
2a gave a lower 80% NMR yield under an argon atmosphere,
indicating that oxygen might be involved in the reaction
process.
Under the optimized conditions shown in footnote a, Table
3, we next explored the cross-coupling of various H-
phosphonate diesters with 2a to understand the scope of the
reaction. As shown in Table 3, in regard to the reactant, in
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a
Table 3. Pd-Catalyzed Cross-Coupling of Triarylbismuth with Dialkyl H-Phosphite
a
Reaction conditions: P(O)−H (0.4 mmol), triarylbismuth (0.13 mmol), PdCl2 (0.012 mmol), bpy (0.024 mmol), (i-Pr)2NEt (0.6 mmol), DMSO
(1 mL), 100 °C for 24 h, under air.
addition to diisopropyl (1a), diethyl (1b), dibutyl (1c),
didodecyl (1d), and dibenzyl phosphonate (1e) all could be
efficiently coupled with 2a to afford the corresponding aryl
phosphonates in good yields, demonstrating that this Pd-
catalyzed coupling is a general and practically useful method for
the synthesis of aryl phosphonates. It is particularly noteworthy
that each phenyl group from triphenylbismuth can be involved
in this transformation. For example, diethyl phosphonate and
didodecyl phosphonate coupled with 1/3 equiv triphenylbis-
muth, giving the desired products in 70% and 72% yields,
respectively (Table 3, entries 2 and 4). However, some
reported carbon−heteroatom bond-forming reactions could
not completely transfer the three aryl groups of triarylbismuth
into the desired products.15h Tris(4-fluorophenyl)bismuth 2b
and tri([1,1′-biphenyl]-4-yl)bismuth 2c as substrates were
suitable for this protocol, and the corresponding products
were obtained in 81% and 74% yields, respectively (Table 3,
entries 6 and 7).
To gain more insight into the substrate scope of the reaction,
various phosphine oxides and H-phosphinate as cross-coupling
partners were investigated (Table 4). Initially, under the above
optimized reaction conditions (footnote a, Table 3), the cross-
coupling of diphenylphosphine oxide with triphenylbismuth
using (i-Pr)2NEt as a base in DMSO was performed and
afforded only an 81% NMR yield (Table 2, entry 21).
Gratifyingly, the cross-coupling of diphenylphosphine oxide
with triphenylbismuth using pyridine as a base in toluene
proceeded quite well, and the expected product 3g was
obtained in a quantitative yield (Table 2, entry 22). Thus, using
pyridine as a base and toluene as a solvent as the standard
conditions (footnote a, Table 4), we first surveyed the cross-
coupling of various substituted triarylbismuths with diphenyl-
phosphine oxide 1f to understand the scope of the organo-
bismuth source. As demonstrated in Table 4, a variety of
arylphosphine oxides could be conveniently and efficiently
afforded by this novel Pd-catalyzed cross-coupling of
triarylbismuth with diphenylphosphine oxide (Table 4, entries
1−6). In general, various functional groups were well tolerated,
and the desired coupling products were obtained in moderate
to good yields. Noting that triarylbismuth with the electron-rich
substituents (Table 4, entries 2 and 3) such as o-Me and p-
OMe gave lower yields than those with electron-deficient
substituents such as p-F, p-Cl and p-CF3 (Table 4, entries 4−6).
Both tri(naphthalen-1-yl)bismuth 2h and tri([1,1′-biphenyl]-4-
yl)bismuth 2c were also found to be suitable reaction partners
with high yields (Table 4, entries 7 and 8), clearly indicating
that steric hindrance was not evident in this reaction. In regard
to aromatic secondary phosphine oxides, in addition to 1f,g
with an electron-donating MeO group on the benzene ring also
could be used as the substrate, generating the corresponding
products in good yields (Table 4, entries 9 and 10). It is
noteworthy that H-phosphinate 1h (Table 4, entries 11 and 12)
and secondary phosphine oxides 1i (Table 4, entries 13 and 14)
also reacted well with triarylbismuth, affording the correspond-
ing alkyl diarylphosphinates and alkyl diarylphosphine oxides in
moderate to good yields. Moreover, heterocycle-substituted
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a
Table 4. Pd-Catalyzed Cross-Coupling of Triarylbismuths with P(O)−H Compounds
a
Reaction conditions: P(O)−H (0.4 mmol), triarylbismuth (0.13 mmol), PdCl2 (0.012 mmol), bpy (0.024 mmol), pyridine (0.6 mmol), toluene (1
mL), 100 °C for 24 h, under air.
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Figure 1. Mechanistic studies.
Figure 2. Structure of located transition states.28
triarylbismuth could also be used as the substrate to give 3v in a
63% yield (Table 4, entry 15). Interestingly, diphenylphosphine
could also be used in this coupling reaction to afford the desired
product 3h in high yield (Table 4, entry 16, 86%), without
observing the generation of triphenylphosphine, and the
reaction process might involve the cross-coupling of
diphenylphosphine with 2a and oxidation of triphenylphos-
phine to triphenylphosphine oxide by air under the catalysis of
Pd(0).21 Notably, this Pd-catalyzed coupling reaction pro-
ceeded smoothly without exclusion of moisture or air.
Transition-metal-catalyzed C−P bond-forming reactions
involving a variety of substrates have been studied computa-
tionally by some groups.22 The commonly acceptable
mechanism involves three basic steps: oxidative addition,
transmetalation, and reductive elimination. Based on the
previous palladium-catalyzed cross-coupling reaction mecha-
nisms,23 we report a possible mechanism of the Pd-catalyzed
cross-coupling of triarylbismuths with P(O)−H compounds
and the first theoretical study of the catalytic cycles using
(DFT) (Figure 1). The model substrates triphenylbismuth,
diphenylphosphine oxide, and catalyst Pd(0)(bpy)2 (IN0) were
chosen. Relative free energies in solution are employed to
analyze the reaction mechanism. Initially, the catalyst precursor
PdCl2 was reduced in the presence of base at elevated
temperature, resulting in the generation of the active catalytic
species Pd(0).15e The approach of BiPh3 toward IN0 leads to
the formation of an η2 complex IN1 by removal of one bpy
ligand. From IN1 a three-centered transition state TS1 (Figure
2, left) is located for the oxidative addition. Not surprisingly,
the activation barrier from IN0 to TS1 is only 2.0 kcal/mol,
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with a mixed basis set employing 6-311++G(2d,p)35 for C, H, N, O, P,
and SDD36 for Ni and Bi were used. The default self-consistent
reaction field (SCRF) polarizable continuum model (PCM) was used
with toluene as solvent (dielectric constant ε = 2.3741), while Bondi
radii37 were chosen as the atomic radii to define the molecular cavity.
The gas-phase geometry was used for all of the solution phase
calculations. The dispersion correction calculations using the
corresponding B3LYP-D functional were performed with the DFT-
D3 program of Grimme.38 The Gibbs energy corrections from
frequency calculations and dispersion corrections were added to the
single-point energies to obtain the Gibbs energies in solution. All the
solution-phase free energies reported in the paper correspond to the
reference state of 1 mol/L, 298 K.
indicating that oxidative addition is not energy-demanding. The
product of oxidative addition is a tetracoordinated Pd(II)
intermediate IN2 (−25.3 kcal/mol relative to IN0). The
transmetalation step takes place when diphenylphosphine oxide
via the form of the hydroxydiphenylphosphine24,25 coordinates
to IN2, giving a four-coordinated Pd(II) intermediate IN3 with
a negative energy of −8.6 kcal/mol, where the bpy uses only
one nitrogen atom to coordinate to the Pd(II) center.
Subsequently, a very late transition state TS2 (Figure 2,
middle) is identified with an activation barrier of +18.3 kcal/
mol, concomitant with the hydrogen migrating from O to Bi
centers and the cleavage of Pd−Bi bond. After the removal of
neutral Ph2BiH species,26 a square planar Pd(II) intermediate
IN4 is formed exergonically. Noting that Ph2BiH might
EXPERIMENTAL SECTION
■
26
disproportionate to Ph3Bi and BiH3 which could involve in
General Procedure for the Synthesis of 3a−f. For 3a−f:
P(O)−H (0.4 mmol, 1 equiv) was added to a mixture of PdCl2 (0.012
mmol, 0.03 equiv, 2 mg), 2,2′-bipyridine (bpy) (0.024 mmol, 0.06
equiv, 4 mg), N,N-diisopropylethylamine (0.6 mmol, 1.5 equiv, 0.10
mL), and Ar3Bi (0.13 mmol, 0.33 equiv) in commercial dimethyl
sulfoxide (1 mL) in a Schlenk tube and stirred at 100 °C for 24 h in an
air atmosphere. The resulting mixture was cooled and then
concentrated under vacuum, and the crude product was purified by
silica gel chromatography using a mixture of petroleum ether and ethyl
acetate as eluent.
next catalytic cycle and be oxidized by air to provide Bi−O
compounds, respectively.26 Next, the reductive elimination of
IN4 proceeds through a three-centered transition state TS3
(Figure 2, right).23 In TS3, the bond lengths of C−P, Pd−C,
and Pd−P are 1.997, 2.083, and 2.600 Å, respectively. The free
energy of TS3 is +29.4 kcal/mol higher than that of IN4,
illustrating that the reductive elimination is a rate-limiting step
for the overall catalytic cycle, in line with the experimental
observation that this Pd(II)-catalyzed reaction was carried out
at 100 °C.23,27 Finally, the C−P bond formation and ligand
exchange give the desired product and complete the catalytic
cycle by regenerating IN0 as a catalytically active species.
General Procedure for the Synthesis of 3g−u. For 3g−u:
P(O)−H (0.4 mmol, 1 equiv) was added to a mixture of PdCl2 (0.012
mmol, 0.03 equiv, 2 mg), 2,2′-bipyridine (bpy) (0.024 mmol, 0.06
equiv, 4 mg), pyridine (0.6 mmol, 1.5 equiv, 0.048 mL), and Ar3Bi
(0.13 mmol, 0.33 equiv) in toluene (1 mL) in a Schlenk tube and
stirred at 100 °C for 24 h in an air atmosphere. The resulting mixture
was cooled and then concentrated under vacuum, and the crude
product was purified by silica gel chromatography using a mixture of
petroleum ether and ethyl acetate as eluent.
CONCLUSION
■
In summary, we first developed the cross-coupling reaction of
readily available P(O)−H compounds with various triarylbis-
muths leading to versatile arylphosphorus compounds includ-
ing arylphosphonates, arylphosphinates, and arylphosphine
oxides. This coupling has many notable features, such as: (i)
triarylbismuths act as nontoxic, nonradioactive and atom-
efficient coupling reagents; (ii) 1 equiv of triarylbismuths gives
3 equiv of coupling products; (iii) the reaction is tolerant of
moisture and air; (iv) various valuable products can be
conveniently obtained using the simply operating procedure;
(v) DFT calculations provide key insight into the mechanism of
Pd-catalyzed C−Bi bond cleavage to C−P functionalization and
open a new avenue to the design of efficient catalysts. Further
mechanistic details and synthetic applications in the con-
struction of bioactive molecule, valuable ligands, and advanced
materials are currently underway.
Diisopropyl phenylphosphonate (3a, CAS No.: 7237-16-3): light
1
yellow oil; 77 mg, 80% yield; H NMR (400 MHz, CDCl3) δ 7.84−
7.78 (m, 2H), 7.54−7.50 (m, 1H), 7.46−7.41 (m, 2H), 4.73−4.64 (m,
2H), 1.36 (d, J = 6.2 Hz, 6H), 1.22 (d, J = 6.2 Hz, 6H); 13C NMR
(100 MHz, CDCl3) δ 132.0 (d, J = 2.2 Hz), 131.7 (d, J = 9.5 Hz),
130.0 (d, J = 189.2 Hz), 128.2 (d, J = 14.7 Hz), 70.6 (d, J = 5.9 Hz),
24.0 (d, J = 4.4 Hz), 23.8 (d, J = 5.1 Hz); 31P NMR (CDCl3, 162
MHz) δ 16.3; ESI-MS [M + Na]+ m/z for C12H19O3PNa+ 264.6.
Diethyl phenylphosphonate (3b, CAS No.: 1754-49-0): colorless
1
oil; 60 mg, 70% yield; H NMR (400 MHz, CDCl3) δ 7.84−7.78 (m,
2H), 7.57−7.52 (m, 1H), 7.48−7.43 (m, 2H), 4.18−4.04 (m, 4H),
1.32 (t, J = 7.14 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 132.3 (d, J
= 3.6 Hz), 131.7 (d, J = 10.3 Hz), 128.4 (d, J = 14.7 Hz), 128.3 (d, J =
188.5 Hz), 62.0 (d, J = 5.1 Hz), 16.3 (d, J = 5.9 Hz); 31P NMR (162
MHz, CDCl3) δ 18.9; ESI-MS [M + Na]+ m/z for C10H15O3PNa+
237.2.
Dibutyl phenylphosphonate (3c, CAS No.: 1024-34-6): light yellow
oil; 72 mg, 67% yield; H NMR (400 MHz, CDCl3) δ 7.83−7.77 (m,
COMPUTATIONAL METHODS
■
1
The calculations were performed with the Gaussian 03 programs.29
The gas-phase geometries of all compounds were optimized without
any constraint by the density functional theory (DFT) method
B3LYP.30 The 6-31+G(d)31 basis set was used for C, H, N, and O. Pd,
Bi, and P atoms were described by the effective core potentials of Hay
and Wadt with a valence double-ζ basis set (LANL2DZ).32
2H), 7.57−7.52 (m, 1H), 7.48−7.43 (m, 2H), 4.11−3.96 (m, 4H),
1.68−1.61 (quint, J = 7.1 Hz, 4H), 1.43−1.34 (sext, J = 7.4 Hz, 4H),
0.90 (t, J = 7.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 132.2 (d, J =
2.88 Hz), 131.7 (d, J = 9.7 Hz), 128.4 (d, J = 15.0 Hz), 128.3 (d, J =
188.3 Hz), 65.7 (d, J = 5.7 Hz), 32.4 (d, J = 6.4 Hz), 18.7, 13.5. ;31P
NMR (CDCl3, 162 MHz) δ 19.0; ESI-MS [M + Na]+ m/z for
C14H23O3PNa+ 293.1.
Polarization functions were added for Pd (ξf =1.472), Bi (ξd
=
0.202) and P (ξd = 0.387) to the standard LanL2DZ basis set.33
Frequency analysis was performed after optimization to verify the
minima and transition states. Transition states were examined by
vibrational analysis and then submitted to intrinsic reaction coordinate
(IRC)34 calculations to determine two corresponding minima. The
results from these IRC calculations are provided in the Supporting
Information. For compounds that had multiple conformations, efforts
were made to find the lowest energy conformation by comparing the
structures optimized from different starting geometries. To calculate
the single-point electronic energies in solution, the B3LYP method
Didodecyl phenylphosphonate (3d, CAS No.: 82594-76-1): light
1
yellow oil; 142 mg, 72% yield; H NMR (400 MHz, CDCl3) δ 7.83−
7.78 (m, 2H), 7.57−7.53 (m, 1H), 7.49−7.45 (m, 2H), 4.11−3.96 (m,
4H), 1.67 (m, 4H), 1.36−1.25 (m, 36H), 0.89 (t, J = 6.8 Hz, 6H); 13C
NMR (100 MHz, CDCl3) δ 146.1 (d, J = 3.7 Hz), 136.0, 133.6 (d, J =
17.8 Hz), 133.3, 132.2, 131.9 (d, J = 2.2 Hz), 131.3 (d, J = 10.0 Hz),
129.0 (d, J = 14.7 Hz), 128.6 (d, J = 12.2 Hz), 120.1 (d, J = 103.3 Hz);
31P NMR (CDCl3, 162 MHz) δ 24.2; ESI-MS [M + Na]+ m/z for
C30H55O3PNa+ 517.4.
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Dibenzyl phenylphosphonate (3e, CAS No.: 19236-61-4): light
yellow oil; 98 mg, 73% yield; H NMR (400 MHz, CDCl3) δ 7.87−
(4-(Trifluoromethyl)phenyl)diphenylphosphine oxide (3m, CAS
No.: 374674-98-3): light yellow oil; 122 mg, 88% yield; 1H NMR (400
MHz, CDCl3) δ 7.85−7.80 (m, 2H), 7.73−7.64 (m, 4H), 7.59−7.55
(m, 2H), 7.51−7.46 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 137.2
(d, J = 101.1 Hz), 133.6 (d, J = 35.4 Hz), 132.5 (d, J = 10.3 Hz), 132.3
(d, J = 2.9 Hz), 131.9 (d, J = 9.9 Hz), 131.6 (d, J = 104.9 Hz), 128.6
(d, J = 12.3 Hz), 125.3−125.1 (m), 123.5 (d, J = 272.9 Hz); 31P NMR
(CDCl3, 162 MHz) δ 27.9; ESI-MS [M + H]+ m/z for C19H14OF3PH+
347.1.
1
7.82 (m, 2H), 7.58−7.54 (m, 1H), 7.49−7.44 (m, 2H), 7.38−7.31 (m,
10H), 5.16−5.03 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 136.1 (d, J
= 6.8 Hz), 132.5, 131.8 (d, J = 10.1 Hz), 128.5, 128.3 (d, J = 15.2 Hz),
128.2, 127.8 (d, J = 189.7 Hz), 126.9, 67.5 (d, J = 5.4 Hz); 31P NMR
(CDCl3, 162 MHz) δ 19.6; ESI-MS [M + Na]+ m/z for
C20H19O3PNa+ 361.1.
Diisopropyl (4-fluorophenyl)phosphonate (3f, new compound):
1
1-Naphthyldiphenylphosphine oxide (3n, CAS No.: 3095-33-8):
yellow oil; 84 mg, 81% yield; H NMR (400 MHz, CDCl3) δ 7.84−
1
white solid; 114 mg, 87% yield; H NMR (400 MHz, CDCl3) δ 8.61
7.77 (m, 2H), 7.15−7.09 (m, 2H), 4.71−4.63 (m, 2H), 1.36 (d, J = 6.2
Hz, 6 H), 1.21 (d, J = 6.2 Hz, 6 H); 13C NMR (100 MHz, CDCl3) δ
165.1 (dd, J = 252.9 Hz, 3.8 Hz), 134.2 (dd, J = 11.4 Hz, 8.8 Hz),
126.1 (dd, J = 193.4 Hz, 3.3 Hz), 115.5 (dd, J = 21.4 Hz, 16.3 Hz),
70.8 (d, J = 5.6 Hz), 24.0 (d, J = 4.1 Hz), 23.7 (d, J = 4.9 Hz); 31P
NMR (CDCl3, 162 MHz) δ 15.5; HR-ESI-MS [M + H]+ m/z calcd for
C12H18O3FPH+ 261.1056, found 261.1055. Anal. Calcd for
C12H18O3FP: C, 55.38; H, 6.97. Found: C, 55.60; H, 7.01.
(d, J = 8.3 Hz, 1H), 7.98 (d, J = 7.7 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H),
7.71−7.67 (m, 4H), 7.52−7.47 (m, 2H), 7.45−7.40 (m, 6H), 7.39−
7.35 (m, 1H), 7.34−7.29 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
133.7, 133.6 (d, J = 11.9 Hz), 133.5, 133.4, 133.3 (d, J = 9.9 Hz),
131.8, 128.6, 128.4 (d, J = 12.3 Hz), 127.4 (d, J = 5.7 Hz), 126.7,
124.0, 123.9 (d, J = 14.3 Hz); 31P NMR (CDCl3, 162 MHz) δ 32.4;
ESI-MS [M + Na]+ m/z for C22H17OPNa+ 351.1.
(4-Biphenylyl)diphenylphosphine oxide (3o, CAS No.: 1942-83-2):
white solid; 120 mg, 85% yield; 1H NMR (400 MHz, CDCl3) δ 7.78−
7.67 (m, 8H), 7.61−7.58 (m, 2H), 7.57−7.52 (m, 2H), 7.49−7.42 (m,
6H), 7.39−7.35 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 144.6 (d, J
= 2.9 Hz), 139.7, 133.0, 132.4 (d, J = 10.2 Hz), 132.0, 131.9, 131.8 (d,
J = 2.9 Hz), 131.0 (d, J = 104.9 Hz), 128.8, 128.4 (d, J = 12.5 Hz),
127.5 (d, J = 107.1 Hz), 127.1; 31P NMR (CDCl3, 162 MHz) δ 28.9;
ESI-MS [M + Na]+ m/z for C24H19OPNa+ 377.1.
Bis(4-methoxyphenyl)phenylphosphine oxide (3p, CAS No.: 799-
55-3): light yellow oil; 107 mg, 79% yield; 1H NMR (400 MHz,
CDCl3) δ 7.64−7.59 (m, 2H), 7.56−7.51 (m, 4H), 7.47−7.43 (m,
1H), 7.42−7.35 (m, 2H), 6.97−6.85 (dd, J = 8.8 Hz, 2.0 Hz 4H), 3.76
(s, 6H); 13C NMR (100 MHz, CDCl3) δ 162.2 (d, J = 2.7 Hz), 133.6
(d, J = 11.2 Hz), 132.1 (d, J = 106.3 Hz), 131.7 (d, J = 10.0 Hz), 131.4
(d, J = 2.2 Hz), 128.1 (d, J = 12.1 Hz), 123.7 (d, J = 110.7 Hz), 113.8
(d, J = 13.2 Hz), 55.1; 31P NMR (CDCl3, 162 MHz) δ 28.8; ESI-MS
[M + Na]+ m/z for C20H19O3PNa+ 361.1.
(4-fluorophenyl)bis(4-methoxyphenyl)phosphine oxide (3q, CAS
No.: 302595-04-6): light yellow oil; 119 mg, 84% yield; 1H NMR (400
MHz, CDCl3) δ 7.68−7.62 (m, 2H), 7.59−7.53 (m, 4H), 7.16−7.11
(m, 2H), 6.98−6.95 (m, 4H), 3.85 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 164.9 (d, J = 253.0 Hz), 162.5 (d, J = 2.8 Hz), 134.5 (d, J =
2.4 Hz), 134.4 (d, J = 20.0 Hz), 133.8 (d, J = 11.2 Hz), 123.8 (d, J =
111.7 Hz), 115.7 (dd, J = 21.3 Hz, 13.2 Hz), 114.1 (d, J = 13.3 Hz),
55.3; 31P NMR (CDCl3, 162 MHz) δ 28.2; ESI-MS [M + Na]+ m/z
for C20H18O3FPNa+ 379.1.
Diisopropyl biphenyl-4-ylphosphonate (3g, new compound): color-
less oil; 94 mg, 74% yield; H NMR (400 MHz, CDCl3) δ 7.91−7.87
1
(m, 2H), 7.70−7.61 (m, 2H), 7.62−7.61 (m, 2H), 7.48−7.45 (m, 2H),
7.41−7.37 (m, 1H), 4.77−4.69 (m, 2H), 1.40 (d, J = 6.1 Hz, 6H), 1.27
(d, J = 6.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 144.8 (d, J = 3.1
Hz), 140.0, 132.2 (d, J = 10.2 Hz), 128.8, 128.6 (d, J = 190.2 Hz),
128.0, 127.2, 126.9 (d, J = 15.2 Hz), 70.7 (d, J = 5.6 Hz), 24.0 (d, J =
3.8 Hz), 23.8 (d, J = 4.8 Hz); 31P NMR (CDCl3, 162 MHz) δ 16.1;
HR-ESI-MS [M + H]+ m/z calcd for C18H23O3PH+ 319.1463, found
319.1465. Anal. Calcd for C18H23O3P: C, 67.91; H, 7.28. Found: C,
68.04; H, 7.25.
Triphenylphosphine oxide (3h, CAS No.: 791-28-6): white solid; 90
1
mg; 81% yield; H NMR (400 MHz, CDCl3) δ 7.70−7.66 (m, 6H),
7.57−7.53 (m, 3H), 7.49−7.45 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ 132.6 (d, J = 104.1 Hz), 132.1 (d, J = 9.9 Hz), 131.9 (d, J =
2.7 Hz), 128.5 (d, J = 12.0 Hz); 31P NMR (CDCl3, 162 MHz) δ 29.1;
ESI-MS [M + Na]+ m/z for C18H15OPNa+ 301.1.
(o-Tolyl)diphenylphosphine oxide (3i, CAS No.: 6840-26-2): light
yellow solid; 78 mg, 67% yield; 1H NMR (400 MHz, CDCl3) δ 7.69−
7.64 (m, 4H), 7.58−7.54 (m, 2H), 7.50−7.41 (m, 5H), 7.31−7.28 (m,
1H), 7.16−7.01 (m, 2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 143.3 (d, J = 8.1 Hz), 133.4 (d, J = 12.5 Hz), 132.7 (d, J = 103.4 Hz),
132.1 (d, J = 2.1 Hz), 131.9 (d, J = 10.3 Hz), 131.7 (d, J = 2.9 Hz),
130.7 (d, J = 103.4 Hz), 128.5 (d, J = 11.7 Hz), 125.1 (d, J = 12.5 Hz),
21.6 (d, J = 4.4 Hz); 31P NMR (CDCl3, 162 MHz) δ 32.0; ESI-MS [M
+ Na]+ m/z for C19H17OPNa+: 315.2.
Ethyl diphenylphosphinate (3r, CAS No.: 1733-55-7): light yellow
(p-Methoxyphenyl)diphenylphosphine oxide (3j, CAS No.: 795-44-
1
oil; 82 mg, 83% yield; H NMR (400 MHz, CDCl3) δ 7.81−7.76 (m,
1
8): yellow oil; 74 mg, 60% yield; H NMR (400 MHz, CDCl3) δ
4H), 7.48−7.44 (m, 2H), 7.42−7.37 (m, 4H), 4.11−4.03 (m, 2H),
1.32 (t, J = 7.1 Hz 3H); 13C NMR (100 MHz, CDCl3) δ 131.9 (d, J =
2.4 Hz), 131.5 (d, J = 137.0 Hz), 131.4 (d, J = 10.2 Hz), 128.3 (d, J =
13.1 Hz), 60.9 (d, J = 5.9 Hz), 16.3 (d, J = 6.6 Hz); 31P NMR (CDCl3,
162 MHz) δ 31.4; ESI-MS [M + H]+ m/z for C14H15O2PH+ 247.1.
(4-Fluorophenyl)ethyl phenyl phosphinate (3s, new compound):
7.68−7.62 (m, 4H), 7.60−7.55(m, 2H), 7.53−7.49 (m, 2H), 7.45−
7.41 (m, 4H), 6.97−6.94 (m, 2H), 3.81 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 162.4 (d, J = 2.8 Hz), 133.8 (d, J = 11.2 Hz), 132.8 (d, J =
104.5 Hz), 131.9 (d, J = 10.0 Hz), 131.7 (d, J = 2.7 Hz), 128.3 (d, J =
12.2 Hz), 123.4 (d, J = 100.4 Hz). 114.0 (d, J = 13.2 Hz), 113.9; 31P
NMR (CDCl3, 162 MHz) δ 29.1; ESI-MS [M + Na]+ m/z for
C19H17O2PNa+ 331.1.
(p-Fluorophenyl)diphenylphosphine oxide (3k, CAS No.: 18437-
73-5): white solid; 96 mg; 81% yield; 1H NMR (400 MHz, CDCl3) δ
7.72−7.65 (m, 6H), 7.59−7.55 (m, 2H), 7.51−7.46 (m, 4H), 7.19−
7.14 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 165.1 (d, J = 256.7
Hz), 134.6 (d, J = 20.5 Hz), 134.5 (d, J = 2.9 Hz), 132.4 (d, J = 104.9
Hz), 132.0 (d, J = 9.8 Hz), 128.6 (d, J = 106.5 Hz), 128.5 (d, J = 12.5
Hz), 115.9 (dd, J = 21.4 Hz, 13.2 Hz); 31P NMR (162 MHz, CDCl3) δ
28.4; ESI-MS [M + Na]+ m/z for C18H14OFPNa+ 319.0.
1
light yellow oil; 84 mg, 80% yield; H NMR (400 MHz, CDCl3) δ
7.87−7.78 (m, 4H), 7.56−7.52 (m, 1H), 7.49−7.45 (m, 2H), 7.18−
7.12 (m, 2H), 4.16−4.09 (m, 2H), 1.39 (t, J = 7.0 Hz 3H); 13C NMR
(100 MHz, CDCl3) δ 165.2 (d, J = 250.2 Hz), 134.2 (d, J = 2.9 Hz),
134.1 (d, J = 20.6 Hz), 132.2 (d, J = 2.6 Hz), 131.6 (d, J = 10.2 Hz),
131.5 (d, J = 138.4 Hz), 128.6 (d, J = 13.2 Hz), 115.9 (dd, J = 21.4 Hz,
14.3 Hz), 61.2 (d, J = 5.8 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3,
162 MHz) δ 30.5; HR-ESI-MS [M + Na]+ m/z calcd for
C14H14O2FPNa+ 287.06077, found 287.06078. Anal. Calcd for
C14H14O2FP: C, 63.64; H, 5.34. Found: C, 63.70; H, 5.35.
(p-Chlorophenyl)diphenylphosphine oxide (3l, CAS No.: 34303-
18-9): white solid; 103 mg, 83% yield; 1H NMR (400 MHz, CDCl3) δ
7.68−7.63 (m, 5H), 7.61−7.54 (m, 4H), 7.49−7.43 (m, 5H); 13C
NMR (100 MHz, CDCl3) δ 138.5 (d, J = 3.2 Hz), 133.4 (d, J = 10.7
Hz), 132.1 (d, J = 2.7 Hz), 132.0 (d, J = 104.9 Hz), 131.9 (d, J = 9.7
Hz), 131.1 (d, J = 104.7 Hz), 128.8 (d, J = 12.6 Hz), 128.5 (d, J = 12.1
Hz); 31P NMR (CDCl3, 162 MHz) δ 28.5; ESI-MS [M + Na]+ m/z
for C18H14OClPNa+ 335.0.
(4-Fuorophenyl)ethyl phenylphosphine oxide (3t, new compound):
colorless oil; 67 mg, 68% yield; 1H NMR (400 MHz, CDCl3) δ 7.78−
7.71 (m, 4H), 7.57−7.47 (m, 3H), 7.20−7.15 (m, 2H), 2.33−2.24 (m,
2H), 1.27−1.17 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 164.9 (d, J
= 249.5 Hz), 133.4, 133.3 (d, J = 19.1 Hz), 132.1, 131.9 (d, J = 3.0
Hz), 130.8 (d, J = 9.1 Hz), 128.7 (d, J = 11.7 Hz), 116.0 (dd, J = 21.4
Hz, 12.5 Hz), 22.8 (d, J = 73.7 Hz), 5.5 (d, J = 5.1 Hz); 31P NMR
(CDCl3, 162 MHz) δ 33.7; HR-ESI-MS [M + Na]+ m/z calcd for
614
dx.doi.org/10.1021/jo402392t | J. Org. Chem. 2014, 79, 608−617

The Journal of Organic Chemistry
Article
C14H14OFPNa+ 271.06585, found 271.06532. Anal. Calcd for
C14H14O2FP: C, 67.74; H, 5.68. Found: C, 69.94; H, 5.65.
Q.-F.; Chu, X.-P.; Ge, F.-F.; Wang, Y.; Lu, T. Adv. Synth. Catal. 2013,
355, 2787−2792. (d) Xiao, H.; Chai, Z.; Yao, R.-S.; Zhao, G. J. Org.
(4-(Trifluoromethyl)phenyl)ethylphenylphosphine oxide (3u, new
Chem. 2013, 78, 9781−9790. (e) Enders, D.; Rembiak, A.; Stockel, B.
̈
1
compound): colorless oil; 75 mg, 63% yield; H NMR (400 MHz,
A. Adv. Synth. Catal. 2013, 355, 1937−1942. (f) Li, Y.; Lu, L. Q.; Das,
S.; Pisiewicz, S.; Junge, K.; Beller, M. J. Am. Chem. Soc. 2012, 134,
18325−18329. (g) Jiajun, M.; Junxiao, Y.; Yawen, H.; Ke, C. J. Mater.
Chem. 2012, 22, 2007−2017. (h) Joly, D.; Tondelier, D.; Deborde, V.;
Delaunay, W.; Thomas, A.; Bhanuprakash, K.; Geffroy, B.; Hissler, M.;
CDCl3) δ 7.92−7.87 (m, 2H), 7.78−7.73 (m, 4H), 7.59−7.49 (m,
3H), 2.38−2.29 (m, 2H), 1.27−1.19 (m, 3H); 13C NMR (100 MHz,
CDCl3) δ 138.9 (d, J = 37.3 Hz), 137.5 (d, J = 93.8 Hz), 133.5 (d, J =
32.7 Hz, 2.8 Hz), 132.1 (d, J = 2.5 Hz), 131.9 (d, J = 99.0 Hz), 131.3
(d, J = 9.5 Hz), 130.8 (d, J = 9.4 Hz), 128.9 (d, J = 11.6 Hz), 125.5−
125.3 (m), 22.5 (d, J = 73.3 Hz), 5.4 (d, J = 5.2 Hz); 31P NMR
(CDCl3, 162 MHz) δ 27.9; HR-ESI-MS [M + Na]+ m/z calcd for
C15H14OF3PNa+ 321.06266, found 321.06283. Anal. Calcd for
C15H14OF3P: C, 60.41; H, 4.73. Found: C, 60.53; H, 4.75.
2-Thienyldiphenylphosphine oxide (3v, CAS No.: 56966-27-9);
colorless oil; 72 mg, 63% yield; 1H NMR (400 MHz, CDCl3) δ 7.76−
7.73 (m, 4H), 7.72−7.71 (m, 1H), 7.58−7.53 (m, 1H), 7.49−7.45 (m,
6H), 4.32−4.22 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 136.9 (d, J
= 10.0 Hz), 133.9 (d, J = 5.0 Hz), 133.8 (d, J = 112.2 Hz), 132.8 (d, J
= 110.0 Hz), 132.1 (d, J = 2.6 Hz), 131.7 (d, J = 10.3 Hz), 128.4 (d, J
= 12.7 Hz), 128.2 (d, J = 13.9 Hz); 31P NMR (CDCl3, 162 MHz) δ
21.8; ESI-MS [M + H]+ m/z for C16H13OSPH+ 285.0.
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Triphenylphosphine oxide (3h, CAS No.: 791-28-6): white solid; 96
1
mg; 86% yield; H NMR (400 MHz, CDCl3) δ 7.70−7.65 (m, 6H),
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7.56−7.51 (m, 3H), 7.48−7.43 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ 133.0, 132.0 (d, J = 10.0 Hz), 131.8 (d, J = 2.5 Hz), 128.4
(d, J = 12.1 Hz); 31P NMR (CDCl3, 162 MHz) δ 29.1; ESI-MS [M +
Na]+ m/z for C18H15OPNa+ 301.1.
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ASSOCIATED CONTENT
■
S
* Supporting Information
The Cartesian coordinates and 3D structures for the optimized
1
structures. H, 31P, and 13C NMR spectra. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: gaoxingchem@xmu.edu.cn.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Chinese National Natural
Science Foundation (21202135), NFFTBS (No. J1210014),
and the National Basic Research Program of China
(2012CB821600, 2013CB910700). Thanks are also due to
the China Scholarship Council for a Graduate Fellowship
(L.L.) and UCSD-CNRS Joint Research Laboratory (UMI
3555) for DFT-D3 calculations.
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2006, 8, 407−409. (b) Mu, X.-J.; Zou, J.-P.; Qian, Q.-F.; Zhang, W.
Org. Lett. 2006, 8, 5291−5293.
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Li, S.; Yu, J.-Q. J. Am. Chem. Soc. 2013, 135, 9322−9325. (b) Berger,
O.; Petit, C.; Deal, E. L.; Montchamp, J.-L. Adv. Synth. Catal. 2013,
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