Nickel-catalyzed C-P coupling of aryl mesylates and tosylates with H(O)PR1R2

Article abstract of DOI:10.1039/c2ob25225b

A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H(O)PR¹R². To the best of our knowledge, this is the first example of nickel-catalyzed C-P coupling of aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic system.

Full text of DOI:10.1039/c2ob25225b

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PAPER
Nickel-catalyzed C–P coupling of aryl mesylates and tosylates with H(O)
PR1R2†
Chaoren Shen, Guoqiang Yang and Wanbin Zhang*
Received 31st January 2012, Accepted 19th February 2012
DOI: 10.1039/c2ob25225b
A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H
(O)PR1R2. To the best of our knowledge, this is the first example of nickel-catalyzed C–P coupling of
aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic
system.
In addition, aryl mesylates and tosylates are more stable in
comparison to their corresponding triflates and can be readily
Introduction
Aromatic organophosphorus compounds have attracted consider-
able interest due to their wide applications in organic synthesis,1
polymers,2 medicinal chemistry,3 and photoelectric materials.4
Particularly in organic synthesis, arylphosphines play an impor-
tant role in organometallic catalysis5 and organocatalysis.6 Conti-
nuing efforts have been made to construct C–P bonds directly
through the coupling of aryl halides with secondary phosphines,
their boranes, stannanes, potassium and lithium salts.7 Much
attention has also been concentrated on the development of
metal-catalyzed C–P couplings to obtain arylphosphonates and
arylphosphine oxides.8 The transition-metal-catalyzed Arbuzov
reaction9 and Hirao reaction10 are the two most widely-used
methods employed for the synthesis of arylphosphonates. In
addition, oxidative phosphonylations of alkynes, arylboronic
acids and aryltrifluoroborates to prepare alkynyl and aryl phos-
phonates catalyzed by Pd or Cu have recently become feasible.11
The synthesis of vinyl phosphonates has also been realized by
various transition-metal catalyzed additions of the H–P bond.12
For the preparation of arylphosphine oxides, one of the most
frequently employed methods involves the treatment of diaryl
phosphoryl chloride with Li or Mg aromatics,13 however this
method suffers from a lack of tolerance for functional groups.
Another method is the metal-catalyzed coupling of aryl halides
and triflates with air-stable diarylphosphine oxides,10n,z,14 which
avoids the use of very air sensitive reagents. Alternatively, the
utilization of aryl mesylates and tosylates as substrates is attrac-
tive in cross-coupling reactions,15–18 because phenol derivatives
are readily available and may be used as a directing group for
the introduction of other functional groups on the aromatic ring.
prepared from common and cheap industrial chemicals, thus
allowing access to a wider substrate scope. Although aryl
mesylates and tosylates have been used in nickel-catalyzed
cross-coupling reactions to form C–C,16 C–N,17 C–B18 and
C–S16a bonds, to the best of our knowledge, these substrates
have not been studied in transition metal-catalyzed cross-
coupling reactions to construct C–P bonds. P-arylation using aryl
mesylates and tosylates as coupling partners remains a challenge
in this field, however we envisage that it would greatly expand
the scope of transition-metal-catalyzed C–P couplings.
Results and discussion
Our initial studies to achieve the construction of C(sp2)–P bonds
with aryl sulfonates were performed using phenyl mesylate with
diphenylphosphine oxide. Through the evaluation of several
kinds of ligands (see Table 1 and Table S1 in ESI†), we found
that NiCl2(dppf) with an excess of dppf was the only catalyst
that exhibited activity in the cross-coupling of phenyl mesylates
with diphenylphosphine oxide (Table 1, entry 1). It is note-
worthy that NiCl2(dppp) with an excess of dppp was not effec-
tive in this reaction (Table 1, entry 2), which is probably due the
smaller bite angle of Ni–dppp compared to Ni–dppf.19 Reducing
the quantity of dppf resulted in a very low reaction yield
(Table 1, entries 3–4), which was caused by premature decompo-
sition of the catalyst.15c,16a A significant difference in product
yield was observed when using readily prepared NiCl2(dppf) as
catalyst and generation of this complex in situ in DMF (Table 1,
entries 1, 5), which perhaps indicated that the Ni–dppf complex
could not be formed sufficiently in the aforementioned solvent.
Several dipolar aprotic solvents were screened (Table 1, entries
6–11) and the highest yield was obtained when DMF was used
as the reaction solvent. DMSO completely inhibited the reaction
and the use of HMPA resulted in a poor yield (Table 1, entries
9–10), the results of which were due to the rapid decomposition
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong
University, 800 Dongchuan Road, Shanghai 200240, P. R. China.
E-mail: wanbin@sjtu.edu.cn; Fax: +86-21-5474-3265; Tel: +86-21-
5474-3265
†Electronic supplementary information (ESI) available. See DOI:
10.1039/c2ob25225b
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Table 1 Reaction condition screeninga
Table 2 Substrate scope of the nickel-catalyzed coupling of aryl
mesylates and tosylates with diarylphosphine oxidesab
Entry
Base
T (°C)
Solvent
Yield (%)
1
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
100
100
100
100
100
100
100
100
100
100
80
120
80
100
100
100
100
100
DMF
DMF
DMF
DMF
74
0
2b
3c
4d
5e
6
14
52
26
30
30
50
0
31
27
57
69
0
DMF
1,4-Dioxane
DMA
NMP
DMSO
HMPA
DME
DMF
DMF
DMF
DMF
DMF
7
8
9
10
11
12
13
14f
15g
16
17
18
74
87
78
84
DIPEA
NEt3
DABCO
DMF
DMF
a Unless otherwise stated, reaction conditions: phenyl mesylate
(0.50 mmol), Ph2P(O)H (0.60 mmol), NiCl2(dppf) (50 μmol), dppf
(0.10 mmol), zinc dust (0.50 mmol), base (1.0 mmol), solvent (3 mL)
under N2, reaction time was 36 h. b NiCl2(dppp) (10 mol%) instead of
NiCl2(dppf), dppp (20 mol%) instead of dppf. c Without added dppf.
d dppf (0.05 mmol). e NiCl2 (10 mol%) instead of NiCl2(dppf), and
added dppf (0.15 mmol). f No zinc dust. g Zinc dust (1.0 mmol).
of nickel catalyst in these solvents.20 The solvent DME also gave
a poor result (Table 1, entry 11). Changes in reaction temperature
had an effect on the reaction outcome with both increases and
decreases in temperature leading to a drop in yield (Table 1,
entries 12–13). The cross-coupling reaction with diphenylpho-
sphine oxide did not occur in the absence of zinc dust (Table 1,
entry 14). However, increasing the amount of zinc dust had no
effect on the reaction yield (Table 1, entry 15). This may mean
excess zinc dust is functionalized as a reducing agent for in situ
generating Ni(0) catalyst before the start of catalytic cycle. In
consideration of the possibility of nickel-catalyzed cross-coup-
lings of aryl mesylates with primary amines and secondary
amines to form C–N bonds, some tertiary amines were chosen as
bases, and the results revealed that the added-base promoted the
cross coupling of C–P bond formation (Table 1, entries 16–18).
Among these tertiary amines, DIPEA provided the best result.
Through the screening of reaction conditions, NiCl2(dppf)/dppf/
Zn/DIPEA/DMF was found to be the optimized catalytic system
for the cross-coupling of aryl mesylate with diarylphosphine
oxide.
With the optimized reaction conditions in hand, a variety of
aryl mesylates and tosylates were examined for the nickel-
catalyzed coupling of C–P bonds with diarylphosphine oxides
(Table 2). We found that there was no remarkable difference in
reactivity between phenyl mesylate and phenyl tosylate (Table 2,
3a). For the cross coupling of aryl mesylates and tosylates
with diarylphosphine oxide, temperature plays a prominent role
in determining reaction yield when using substituted phenyl
tosylates (Table 2, 3b, 3f). For example, an increase in reaction
a Reaction conditions: 1 (0.50 mmol), 2 (0.60 mmol), NiCl2(dppf)
(50 μmol), dppf (0.10 mmol), DIPEA (95 μL, 1.0 mmol), zinc dust
(0.50 mmol), 3 mL DMF, under N2, reaction time was 36 h. b Isolated
yields.
temperature improved the product yield when using p-tolyl
tosylate. However, when the reaction was performed at 160 °C,
the yield decreased sharply, probably resulting from the
decomposition of the Ni–dppf complex. The catalysis of elec-
tron-rich and deficient substrates gave lower yields than the cor-
responding electron-neutral substrates (Table 2, 3a, 3b, 3e, 3f).
It is well known that electron-donating groups usually hinder the
oxidative addition step whilst electron-withdrawing groups retard
the reductive elimination step. Thus, the results may suggest that
both the oxidative addition and reductive elimination are the
kinetically important steps for our catalytic system. The meta-
substituted substrates showed moderate reactivity, while the
ortho-substituted substrate showed reduced reactivity (Table 2,
3c, 3d, 3g). Fused-ring aromatic mesylates and tosylates gave
the corresponding products in moderate yields (Table 2, 3h, 3i).
Substituent effects of diarylphosphine oxides on the reaction
outcome were also investigated. The introduction of an
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Table 3 Scope of the nickel-catalyzed coupling of aryl mesylates and
chiral phosphine ligands can be synthesized from compounds
tosylates with diethyl phosphonate and ethyl phenylphosphinateab
3j,13b 5c, 5g.21
Conclusions
In summary, we have developed a method for C(sp2)–P coupling
via nickel-catalyzed coupling of aryl mesylates and tosylates
with H(O)PR1R2 to prepare arylphosphonates, diarylphosphi-
nates, and arylphosphine oxides. Our studies have expanded the
scope of transition-metal-catalyzed P-arylation. The catalytic
system of this reaction with tolerance to a broader range of sub-
stituents on the substrates is under further investigation.
Experimental section
General details
Unless otherwise noted, all reagents were purchased from com-
mercial suppliers and used without purification. All reactions
were performed in flame-dried glassware under an atmosphere of
dry nitrogen, and the workup was carried out in air, unless other-
wise stated. CH2Cl2, DMF, NMP, DMSO, HMPA, toluene, pyri-
dine and NEt3 were distilled at atmospheric or reduced pressure
over CaH2 prior to use. Solvents 1,4-dioxane, DME and THF
were distilled from sodium benzophenone ketyl prior to use.
NaH (65% in mineral oil) was degreased with n-hexane under
N2 prior to use. Activated zinc dust was prepared prior to use
according to a literature procedure.22 Column chromatographic
purification of products was carried out using silica gel 60
(200–300 mesh). NMR spectra were recorded on a Varian
a Reaction conditions: 1 (0.50 mmol), 2 (0.60 mmol), NiCl2(dppf)
(50 μmol), dppf (0.10 mmol), DIPEA (95 μL, 1.0 mmol), zinc dust
(0.50 mmol), 3 mL DMF, under N2, reaction time was 36 h, reaction
temperature was 100 °C. b Isolated yields. c No zinc dust.
1
MERCURY plus-400 (400 MHz, H; 100 MHz, 13C; 162 MHz,
31P) spectrometer with chemical shifts reported in ppm relative
to the residual deuterated solvent, the internal standard tetra-
methylsilane, or external 85% H3PO4 for 31P. Mass spectrometry
analysis was carried out using an electrospray spectrometer
Waters 4 micro quadrupole. Melting points were measured with
SGW X-4 micro melting point apparatus.
electron-neutral group and an electron-donating group at the
para-position of the aromatic ring did not significantly affect the
yields of the C–P coupling products (Table 2, 3k, 3l). However
when the strong electron-withdrawing trifluoromethyl group was
present at the para-position of the phenyl ring, an inseparable
mixture of products were obtained (Table 2, 3m). The cross-
coupling of di(3,5-dimethylphenyl)phosphine oxide gave a
moderate yield (Table 2, 3n).
This catalytic system was also adapted to the cross coupling
reaction of aryl mesylates and tosylates with diethyl phosphonate
and ethyl phenylphosphinate (Table 3). For most examples, the
Ni-catalyzed reaction of aryl mesylates and tosylates with diethyl
phosphonate furnished the corresponding arylphosphonates in
good yields. When diethyl phosphinate was utilized in the reac-
tion using optimized conditions with a substrate possessing a
para-substituted electron-neutral group, the desired phosphonate
was isolated in good yield (Table 3, 5a, 5b). Meta-substituted
substrates and fused-ring aryl substrate also gave good yields
(Table 3, 5c, 5g, 5h). Ortho-steric effects make the reaction slug-
gish (Table 3, 5d, 5i). This method is not suitable for substrates
bearing an electron-donating group or an electron-withdrawing
group in the para-position of the phenyl ring (Table 3, 5e, 5f),
probably due to similar reasons (as discussed previously) for the
reaction with diarylphospine oxides. Ethyl diarylphosphinates
could also be prepared in good yields by employing the same
catalytic system for the cross coupling of tosylates with ethyl
arylphosphinate (Table 3, 5j, 5k). In addition, some well-known
General procedure for Ni-catalyzed cross-coupling of aryl
mesylates or tosylates with H(O)PR1R2
In a typical reaction, to an oven-dried 25 mL Schlenk tube was
added NiCl2(dppf) (50 μmol), dppf (0.10 mmol) and activated
Zn dust (0.50 mmol). The tube was sealed with a rubber septum
and then degassed by pumping and backfilling with nitrogen
three times. DMF (1 mL) was added via a syringe. The reaction
mixture was stirred at 80 °C for 0.5 h. During this time, the sol-
ution of mixture turned from yellow to red. DMF (2 mL) sol-
ution containing aryl mesylates or tosylates (0.50 mol), H(O)
PR1R2 (0.60 mmol), and DIPEA (95 μL, 1.0 mmol) was added
via a syringe through the rubber septum. The reaction mixture
was stirred at 100 °C under a nitrogen atmosphere for 36 h.
The reaction mixture was allowed to cool to room temperature
and the DMF was evaporated in vacuo. The residue was
dissolved in CH2Cl2 (10 mL) and then washed with 5% HCl
(3 × 5 mL) and H2O (3 × 3 mL), and dried by Na2SO4. Solvent
was evaporated in vacuo and the residue was purified by column
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chromatography (silica gel, petroleum ether–ethyl acetate–
EtOH). Products 3c, 3k, 3l and 3n are new compounds.
8.0 Hz, 1H), 7.07 (d, J = 11.4 Hz, 1H), 6.88 (dd, J = 7.9, 2.1
Hz, 1H), 6.02 (s, 2H).
Phosphoryl triphenyl (3a).10aa White solid, 31P NMR
(CDCl3, 162 MHz): δ = 29.45; H NMR (CDCl3, 400 MHz): δ
Bis(4-methylphenyl)phenyl phosphine oxide (3k).27 Colorless
slurry, 31P NMR (CDCl3, 162 MHz): δ = 30.53; 1H NMR
(CDCl3, 400 MHz): δ = 7.68–7.62 (m, 2H), 7.53 (dd, J = 11.8,
8.0 Hz, 4H), 7.48 (m, 1H), 7.24 (dd, J = 8.4, 2.4 Hz, 4H), 2.38
(s, 6H); 13C NMR (CDCl3, 100 MHz): δ = 142.6 (d, J = 2.9
Hz), 133.0 (d, J = 102.5 Hz), 132.2 (d, J = 10.2 Hz), 132.0 (d,
J = 8.7 Hz), 131.9 (d, J = 3.2 Hz), 129.4 (d, J = 106.9 Hz),
129.4 (d, J = 12.6 Hz), 128.6 (d, J = 11.8 Hz), 21.7.
1
= 7.64–7.70 (m, 6H), 7.52–7.56 (m, 3H), 7.43–7.48 (m, 6H).
(4-Methylphenyl)diphenyl phosphine oxide (3b).10aa White
solid, 31P NMR (CDCl3, 162 MHz): δ = 27.73; 1H NMR
(CDCl3, 400 MHz): δ = 7.64–7.69 (m, 4H), 7.49–7.58 (m, 4H),
7.41–7.46 (m, 4H), 7.25–7.28 (m, 2H), 2.39 (s, 3H).
(3-Methylphenyl)diphenyl phosphine oxide (3c). White solid,
mp: 123.7–124.2 °C; 31P NMR (CDCl3, 162 MHz): δ = 30.53;
1H NMR (CDCl3, 400 MHz): δ = 7.68–7.63 (m, 4H), 7.56–7.52
(m, 3H), 7.48–7.43 (m, 4H), 7.37–7.33 (m, 3H), 2.36 (s, 3H);
13C NMR (CDCl3, 100 MHz): δ = 138.7 (d, J = 12.7 Hz), 132.8
(d, J = 142.1 Hz), 133.0 (d, J = 3.6 Hz), 132.4 (d, J = 102.5),
132.7 (d, J = 9.5 Hz), 132.3 (d, J = 10.0 Hz), 132.1 (d, J = 1.9
Hz), 129.4 (d, J = 11.3 Hz), 128.7 (d, J = 12.4 Hz), 128.5 (d,
J = 12.9 Hz), 21.66; HR-ESI-MS: [M + H]+ m/z calcd for:
293.1095, found: 293.1108.
Bis(4-methoxypheny1)phenylphosphine oxide (3l).28 White
solid, mp: 96.5–97.4 °C; 31P NMR (CDCl3, 162 MHz): δ =
1
30.36; H NMR (CDCl3, 400 MHz): δ = 7.61–7.54 (m, 2H),
7.56 (dd, J = 11.2, 8.4 Hz, 4H), 7.51–7.49 (m, 1H), 7.45–7.41
(m, 2H), 6.94 (dd, J = 6.4, 1.8 Hz, 4H), 3.83 (s, 6H); 13C NMR
(CDCl3, 100 MHz): δ = 162.6 (d, J = 1.8 Hz), 134.1 (d, J = 11.7
Hz), 133.3 (d, J = 104.3 Hz), 132.2 (d, J = 9.8 Hz), 131.9 (d,
J = 2.7 Hz), 128.6 (d, J = 12.4 Hz), 124.0 (d, J = 110.2 Hz),
114.2 (d, J = 12.9 Hz), 55.5.
(2-Methylphenyl)diphenyl phosphine oxide (3d).23 White
solid, 31P NMR (CDCl3, 162 MHz): δ = 31.71; 1H NMR
(CDCl3, 400 MHz): 7.68–7.61 (m, 4H), 7.56–7.38 (m, 7H), 7.27
(ddd, J = 14.0, 7.6, 0.4 Hz, 1H), 7.11 (m, 1H), 7.02 (ddd, J =
14.0, 7.6, 1.2 Hz, 1H), 2.45 (s, 3H).
Bis(3,5-bismethylphenyl)phenylphosphine oxide (3n). White
solid, mp: 158.6–159.2 °C; 31P NMR (CDCl3, 162 MHz): δ =
30.89; H NMR (CDCl3, 400 MHz): δ = 7.68–7.63 (m, 2H),
7.55–7.51 (m, 1H), 7.47–7.42 (m, 2H), 7.26 (d, J = 12.4 Hz,
4H), 7.15 (s, 2H), 2.31 (s, 12H); 13C NMR (CDCl3, 100 MHz):
δ = 138.3 (d, J = 12.2 Hz), 133.9 (d, J = 2.3 Hz), 133.1 (d, J =
102.7 Hz), 132.4 (d, J = 102.6 Hz), 132.3 (d, J = 9.7 Hz), 131.9
(d, J = 2.2 Hz), 129.8 (d, J = 10.0 Hz), 128.6 (d, J = 11.7 Hz),
21.56; HR-ESI-MS: [M + H]+ m/z calcd for: 335.1565, found:
335.1574.
1
(4-Methoxyphenyl)diphenyl phosphine oxide (3e).10aa White
solid, 31P NMR (CDCl3, 162 MHz): δ = 32.91; 1H NMR
(CDCl3, 400 MHz): δ = 7.64–7.70 (m, 4H), 7.50–7.54 (m, 2H),
7.42–7.46 (m, 4H), 7.28–7.37 (m, 2H), 7.12–7.17 (m, 1H), 7.06
(dd, J = 8.9, 2.6 Hz), 3.77 (s, 3H).
1
Diethyl phenylphosphonate (5a).9j Oil, H NMR (400 MHz,
(4-Carbomethoxyphenyl)diphenyl
phosphine
oxide
CDCl3): δ = 7.82 (m, 2H), 7.55 (tq, J = 7.5, 1.4 Hz, 1H), 7.47
(m, 2H), 4.12 (m, 4H), 1.32 (td, J = 7.0, 0.5 Hz, 6H).
1
(3f).24 White solid, 31P NMR (100 MHz, CDCl3): δ = 28.9; H
NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 8.2 Hz, 2H), 7.77
(dd, J = 11.4, 8.4 Hz, 2H), 7.64–7.69 (m, 4H), 7.46–7.60
(m, 6H), 3.93 (s, 3H).
1
Diethyl p-tolylphosphonate (5b).9j Oil, H NMR (400 MHz,
CDCl3): δ = 7.68 (d, J = 8.9 Hz, 2H), 7.26 (d, J = 8.9 Hz, 2H),
4.04–4.18 (m, 4H), 2.41 (s, 3H), 1.31 (t, J = 6.9 Hz, 6H).
(3-Methoxyphenyl)diphenyl phosphine oxide (3g).10aa White
solid, 31P NMR (CDCl3, 162 MHz): δ = 32.91; 1H NMR
(CDCl3, 400 MHz): δ = 7.64–7.70 (m, 4 H), 7.50–7.54 (m, 2H),
7.42–7.46 (m, 4H), 7.28–7.37 (m, 2H), 7.12–7.17 (m, 1H), 7.06
(dd, J = 8.9, 2.6 Hz), 3.77 (s, 3 H).
1
Diethyl m-tolylphosphonate (5c).9j Oil, H NMR (400 MHz,
CDCl3): δ = 7.57–7.67 (m, 2H), 7.27–7.36 (m, 2H), 4.12–4.20
(m, 4H), 2.37 (s, 3H), 1.32 (t, J = 7.0 Hz, 6H).
1
Diethyl o-tolylphosphonate (5d).9j Oil, H NMR (400 MHz,
2-Naphthalenyldiphenyl phosphine oxide (3h).25 White solid,
CDCl3): δ = 7.88–7.96 (m, 1H), 7.42–7.46 (m, 1H), 7.23–7.28
(m, 2H), 4.12 (m, 4H), 2.57 (s, 3H), 1.33 (t, J = 6.9 Hz, 6H).
1
31P NMR (CDCl3, 162 MHz): δ = 31.32; H NMR (400 MHz,
CDCl3): δ = 8.27 (d, J = 13.6 Hz, 1H), 7.88 (d, J = 9.6 Hz, 2H),
7.73–7.68 (m, 4H), 7.64–7.46 (m, 10H).
Diethyl p-methoxyphenylphosphonate (5e).9j Oil, 1H NMR
(400 MHz, CDCl3): δ = 7.72 (dd, J = 13.0, 9.0 Hz, 2H), 6.97
(dd, J = 9.0, 3.0 Hz, 2H), 4.04–4.13 (m, 4H), 3.83 (s, 3H), 1.30
(t, J = 7.3 Hz, 6H).
1-Naphthalenyldiphenyl phosphine oxide (3i).7h White solid,
31P NMR (CDCl3, 162 MHz): δ = 33.12; 1H NMR (CDCl3,
400 MHz): δ = 8.58 (d, J = 8.2 Hz, 1H), 8.01 (d, J = 8.1 Hz,
1H), 7.88 (d, J = 8.2 Hz, 1H), 7.66–7.71 (m, 4H), 7.52–7.56
(m, 2H), 7.43–7.50 (m, 6H), 7.35–7.39 (m, 1H), 7.26–7.32
(m, 1H).
Diethyl 3-methoxyphenylphosphonate (5g).9j Oil, 1H NMR
(400 MHz, CDCl3): δ = 7.32–7.40 (m, 3H), 7.07–7.10 (m, 1H),
4.05–4.18 (m, 4H), 3.85 (s, 3H), 1.33 (t, J = 6.9 Hz, 6H).
1,3-Benzodioxol-5-yldiphenyl phosphine oxide (3j).26 White
solid, 31P NMR (CDCl3, 162 MHz): δ = 34.53; 1H NMR
(CDCl3, 400 MHz): δ = 7.66 (dd, J = 11.6, 7.5 Hz, 4H), 7.54
(d, J = 7.1 Hz, 2H), 7.46 (t, J = 7.1 Hz, 4H), 7.18 (dd, J = 12.6,
Diethyl naphthalen-2-yl phosphonate (5h).9j Oil, 1H NMR
(400 MHz, CDCl3): δ = 8.41 (d, J = 16.4 Hz, 1H), 7.84–7.93
(m, 3H), 7.71–7.76 (m, 1H), 7.51–7.59 (m, 2H), 4.17–4.23
(m, 4H), 1.32 (t, J = 7.3 Hz, 6H).
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Diethyl naphthalen-1-yl phosphonate (5i).9j Oil, 1H NMR
(400 MHz, CDCl3): δ = 8.47 (d, J = 8.0 Hz, 1H), 8.22 (dd, J =
16.2, 7.0 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 7.2 Hz,
1H), 7.49–7.61 (m, 3H), 4.02–4.24 (m, 2H), 1.31 (t, J = 7.1 Hz,
6H).
Trans., 2005, 1952; (f) N. F. Blank, K. C. McBroom, D. S. Glueck,
W. S. Kassel and A. L. Rheingold, Organometallics, 2006, 25, 1742;
(g) T. J. Brunker, B. J. Anderson, N. F. Blank, D. S. Glueck and
A. L. Rheingold, Org. Lett., 2007, 9, 1109; (h) M. Bonaterra, R. A. Rossi
and S. E. Martín, Organometallics, 2009, 28, 933; (i) R. Lindner, B. van
den Bosch, M. Lutz, N. H. R. Joost and J. I. van der Vlugt, Organometal-
lics, 2011, 30, 499; ( j) A. Franzke and A. Pfaltz, Chem.–Eur. J., 2011,
17, 4131.
Ethyl diphenylphosphinate (5j).10n Oil, 31P NMR (CDCl3,
162 MHz): δ = 25.01; 1H NMR (CDCl3, 400 MHz): δ =
7.64–7.66 (m, 4H), 7.47 (d, J = 7.6 Hz, 4H), 4.16 (m, 2H), 1.38
(m, 3H).
8 D. S. Glueck, Top. Organomet. Chem., 2010, 31, 65.
9 For examples of Ni-catalyzed Arbuzov reaction, see (a) P. Tavs, Chem.
Ber., 1970, 103, 2428; (b) T. M. Balthazor, J. A. Miles and B. R. Stults,
J. Org. Chem., 1978, 43, 4538; (c) T. M. Balthazor, J. Org. Chem., 1980,
45, 2519; (d) J. Heinicke, N. Gupta, A. Surana, N. Peulecke, B. Witt,
K. Steinhauser, R. K. Bansal and P. J. Jones, Tetrahedron, 2001, 57,
9963; (e) D. Villemin, A. Elbilali, F. Simeon, P.-A. Jaffrès, G. Maheut,
M. Mosaddak and A. Hakiki, J. Chem. Res., 2003, 436; (f) G. Von Mäkl,
K. Gschwendner, I. Rözer and P. Kreitmeier, Helv. Chim. Acta, 2004, 87,
825; (g) Q. Yao and S. Levchik, Tetrahedron Lett., 2006, 47, 277;
(h) E. Montoneri, G. Viscardi, S. Bottigliengo, R. Gobetto, M.
R. Chierotti, R. Buscaino and P. Quagliotto, Chem. Mater., 2007, 19,
2671; (i) M. V. Reddington, Bioconjugate Chem., 2007, 18, 2178;
( j) G. Yang, C. Shen and W. Zhang, Tetrahedron Lett., 2011, 52, 5032.
For examples of Cu- and Pd-catalyzed Arbuzov reactions: (k) G. Axelrad,
S. Laosooksathit and R. Engel, J. Org. Chem., 1981, 46, 5200;
(l) R. Berrino, S. Cacchi, G. Fabrizi, A. Goggiamani and P. Stabile, Org.
Biomol. Chem., 2010, 8, 4518.
10 (a) T. Hirao, T. Masunaga, Y. Ohshiro and T. Agawa, Tetrahedron Lett.,
1980, 21, 3595; (b) T. Hirao, T. Masunaga, Y. Ohshiro and T. Agawa,
Synthesis, 1981, 56; (c) T. Hirao, T. Masunaga, N. Yamada, Y. Ohshiro
and T. Agawa, Bull. Chem. Soc. Jpn., 1982, 55, 909. For examples of
further development and modification to Hirao reaction: (d) P.-A. Jaffres,
N. Bar and D. J. Villemin, J. Chem. Soc., Perkin Trans. 1, 1998, 2083;
(e) T. Ogawa, N. Usuki and N. Ono, J. Chem. Soc., Perkin Trans. 1,
1998, 2953; (f) M. Lera and C. J. Hayes, Org. Lett., 2000, 2, 3873;
(g) A. M. Levine, R. A. Stockland Jr., R. Clark and I. Guzei, Organome-
tallics, 2002, 21, 3278; (h) A. Stadler and C. O. Kappe, Org. Lett., 2002,
4, 3541; (i) D. Gelman, L. Jiang and S. L. Buchwald, Org. Lett., 2003, 5,
2315; ( j) D. Van Allen and D. Venkataraman, J. Org. Chem., 2003, 68,
4590; (k) K. Haaf, Comb. Chem. High Throughput Screening, 2005, 8,
637; (l) S. Thielges, P. Bisseret and J. Eustache, Org. Lett., 2005, 7, 681;
(m) R. A. Stockland Jr. and N. P. Rath, Organometallics, 2006, 25, 5746;
(n) C. Huang, X. Tang, H. Fu, Y. Jiang and Y. Zhao, J. Org. Chem.,
2006, 71, 5020; (o) H. Rao, Y. Jin, H. Fu, Y. Jiang and Y. Zhao, Chem.–
Eur. J., 2006, 12, 3636; (p) M. Kalek and J. Stawinski, Organometallics,
2007, 26, 5840; (q) N. F. Blank, J. R. Moncarz, T. J. Brunker, C. Scriban,
B. J. Anderson, O. Amir, D. S. Glueck, L. N. Zakharov, J. A. Golen,
C. D. Incarvito and A. L. Rheingold, J. Am. Chem. Soc., 2007, 129,
6847; (r) M. Kalek, A. Ziadi and J. Stawinski, Org. Lett., 2008, 10,
4637; (s) M. Kalek and J. Stawinski, Organometallics, 2008, 27, 5876;
(t) Y. Belabassi, S. Alzghari and J. Montchamp, J. Organomet. Chem.,
2008, 693, 3171; (u) M. C. Kohler, J. G. Sokol and R. A. Stockland Jr.,
Tetrahedron Lett., 2009, 50, 457; (v) G. Laven and J. Stawinski, Synlett,
2009, 225; (w) M. C. Kohler, T. V. Grimes, X. Wang, T. R. Cundari and
R. A. Stockland Jr., Organometallics, 2009, 28, 1193; (x) Y. Luo and
J. Wu, Organometallics, 2009, 28, 6823; (y) M. Kalek, M. Jezowska and
J. Stawinski, Adv. Synth. Catal., 2009, 351, 3207; (z) N. T. McDougal,
J. Streuff, H. Mukherjee, S. C. Virgil and B. M. Stoltz, Tetrahedron Lett.,
2010, 51, 5550; (aa) X. Zhang, H. Liu, X. Hu, G. Tang, J. Zhu and
Y. Zhao, Org. Lett., 2011, 13, 3478. For selected reviews, see:
(ab) D. Prim, J.-M. Campagne, D. Joseph and B. Andrioletti, Tetrahe-
dron, 2002, 58, 2041; (ac) A. L. Schwan, Chem. Soc. Rev., 2004, 33,
218.
Ethyl (4-methylphenyl)phenylphosphinate (5k).10n Oil, 31P
NMR (CDCl3, 162 MHz): δ = 24.97; 1H NMR (CDCl3,
400 MHz): δ = 7.66 (d, J = 7.2 Hz, 2H), 7.48–7.51 (m, 3H),
7.39–7.45 (m, 1H), 6.96–6.99 (m, 4H), 4.15 (m, 2H), 2.18
(s, 3H), 1.28 (m, 3H).
Acknowledgements
This work was partially supported by the Nippon Chemical
Industrial Co., Ltd, National Natural Science Foundation of
China (20972095), and Science and Technology Commission
of Shanghai Municipality (09JC1407800). Our thanks also go to
the Instrumental Analysis Center of Shanghai Jiao Tong
University.
Notes and references
1 (a) R. Engel, Chem. Rev., 1977, 77, 349; (b) T. Baumgartner and
R. Réau, Chem. Rev., 2006, 106, 4681.
2 (a) K. A. Watson, F. L. Palmieri and J. W. Connell, Macromolecules,
2002, 35, 4968; (b) Z. Jin and B. L. Lucht, J. Am. Chem. Soc., 2005,
127, 5586; (c) Q. Lin, S. Unal, A. R. Fornof, R. S. Armentrout and
T. E. Long, Polymer, 2006, 47, 4085.
3 (a) Y. C. Kim, S. G. Brown, T. K. Harden, J. L. Boyer, G. Dubyak,
B. F. King, G. Burnstock and K. A. Jacobson, J. Med. Chem., 2001, 44,
340; (b) J. J. Shie, J. M. Fang, S. Y. Wang, K. C. Tsai, Y. S. Cheng,
A. S. Yang, S. C. Hsiao, C. Y. Su and C. H. Wong, J. Am. Chem. Soc.,
2007, 129, 11892; (c) T. S. Kumar, S. Y. Zhou, B. V. Joshi,
R. Balasubramanian, T. H. Yang, B. T. Liang and K. A. Jacobson,
J. Med. Chem., 2010, 53, 2562; (d) C. S. Demmer, N. Krogsgaard-Larsen
and L. Bunch, Chem. Rev., 2011, 111, 7981.
4 (a) C. H. Chien, C. K. Chen, F. M. Hsu, C. F. Shu, P. T. Chou and
C. H. Lai, Adv. Funct. Mater., 2009, 19, 560; (b) H. H. Chou and
C. H. Cheng, Adv. Mater., 2010, 22, 2468; (c) F. M. Hsu, C. H. Chien,
C. F. Shu, C. H. Lai, C. C. Hsieh, K. W. Wang and P. T. Chou, Adv.
Funct. Mater., 2009, 19, 2834; (d) D. Kim, S. Salman, V. Coropceanu,
E. Salomon, A. B. Padmaperuma, L. S. Sapochak, A. Kahn and
J. L. Brédas, Chem. Mater., 2010, 22, 247.
5 (a) M. McCarthy and P. J. Guiry, Tetrahedron, 2001, 57, 3809;
(b) W. Tang and X. Zhang, Chem. Rev., 2003, 103, 3029; (c) R. Martin
and S. L. Buchwald, Acc. Chem. Res., 2008, 41, 1461; (d) D. S. Surry
and S. L. Buchwald, Chem. Sci., 2011, 2, 27; (e) H. Fernández-Pérez,
P. Etayo, A. Panossian and A. Vidal-Ferran, Chem. Rev., 2011, 111, 2119.
6 For selected reviews, see: (a) X. Lu, C. Zhang and Z. Xu, Acc. Chem.
Res., 2001, 34, 535; (b) J. L. Methot and W. R. Roush, Adv. Synth.
Catal., 2004, 346, 1035; (c) Y. Wei and M. Shi, Acc. Chem. Res., 2010,
43, 1005.
7 For examples of coupling of aryl halides with secondary phosphines,
their boranes, stannanes, potassium and lithium salts, see: (a) D. J. Ager,
M. B. East, A. Eisenstadt and S. A. Laneman, Chem. Commun., 1997,
2359; (b) D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes,
T. R. Verhoeven and P. J. Reider, Org. Synth., 1999, 76, 6;
(c) J. R. Moncarz, T. J. Brunker, J. C. Jewett, M. Orchowski,
D. S. Glueck, R. D. Sommer, K.-C. Lam, D. Incarvito, T. E. Concolino,
C. Ceccarelli, L. N. Zakharov and A. L. Rheingold, Organometallics,
2003, 22, 3205; (d) H. Shimizu, T. Saito and H. Kumobayashi, Adv.
Synth. Catal., 2003, 345, 185; (e) W.-Y. Lee and L.-C. Liang, Dalton
11 For examples of metal-catalyzed oxidative coupling of alkynes with
secondary phosphonates, see: (a) Y. Gao, G. Wang, L. Chen, P. Xu,
Y. Zhao, Y. Zhou and L.-B. Han, J. Am. Chem. Soc., 2009, 131, 7956.
For metal-catalyzed oxidative coupling of arylboronic acid with second-
ary phosphonates, see: (b) M. Andaloussi, J. Lindh, J. Sävmarker,
P. J. R. Sjöerg and M. Larhed, Chem.–Eur. J., 2009, 15, 13069;
(c) J. Qiao and P. Lam, Synthesis, 2011, 829; (d) R. Zhuang, J. Xu,
S. Cai, G. Tang, M. Fang and Y. Zhao, Org. Lett., 2011, 13, 2110.
12 (a) L.-B. Han, C. Zhang, H. Yazawa and S. Shimada, J. Am. Chem. Soc.,
2004, 126, 5080; (b) M. Niu, H. Fu, Y. Jiang and Y. Zhao, Chem.
Commun., 2007, 272; (c) Q. Xu, R. Shen, Y. Ono, R. Nagahata,
S. Shimada, M. Goto and L.-B. Han, Chem. Commun., 2011, 47, 2333;
(d) A. Fadel, F. Legrand, G. Evano and N. Rabasso, Adv. Synth. Catal.,
3504 | Org. Biomol. Chem., 2012, 10, 3500–3505
This journal is © The Royal Society of Chemistry 2012

View Article Online
2011, 353, 263. For example of addition of secondary phosphines to
alkenes: (e) M. O. Shulyupin, M. A. Kazankova and I. P. Beletskaya,
Org. Lett., 2002, 4, 761.
19 For selected reviews of ligand bite angle effect: (a) P. W. N. M. van
Leeuwen, P. C. J. Kamer, J. N. H. Reek and P. Dierkes, Chem. Rev.,
2000, 100, 2741; (b) M.-N. Birkholzm, Z. Freixa and P. W. N. M. van
Leeuwen, Chem. Soc. Rev., 2009, 38, 1099.
20 For some papers about the decomposition of Ni complex in DMSO and
HMPA: (a) M. F. Semmelhack, P. M. Helquist and L. D. Jones, J. Am.
Chem. Soc., 1971, 93, 5908; (b) M. F. Semmelhack, P. M. Helquist,
L. D. Jones, L. Keller, L. Mendelson, L. S. Ryono, J. G. Smith and
R. D. Stauffer, J. Am. Chem. Soc., 1981, 103, 6460; (c) D. Cai,
J. F. Payack, D. R. Bender, D. L. Hughes, T. R. Verhoeven and
P. J. Reider, J. Org. Chem., 1994, 59, 7180.
21 (a) J. P. Henschke, A. Zanotti-Gerosa, P. Moran, P. Harrison, B. Mullen,
G. Casy and I. C. Lennon, Tetrahedron Lett., 2003, 44, 4379;
(b) H. Shimizu, T. Ishizaki, T. Fujiwara and T. Saito, Tetrahedron: Asym-
metry, 2004, 15, 2169; (c) Y. Suto, R. Tsuji, M. Kanai and M. Shibasaki,
Org. Lett., 2005, 7, 3757; (d) C.-M. Fang, M.-L. Ma, X.-L. Zheng,
Y. Guo, Z.-H. Peng, H. Chen and X.-J. Li, Chin. J. Org. Chem., 2006,
26, 252.
22 (a) C. R. Hauser and D. S. Breslow, Org. Synth., 1941, 21, 51;
(b) R. A. Awl and E. H. Pryde, J. Am. Oil Chem. Soc., 1966, 43, 35;
(c) B. P. Bandgar, S. N. Chavare and S. S. Pandit, J. Chin. Chem. Soc.
(Taipei), 2005, 52, 125.
13 (a) H. Tomori, J. M. Fox and S. L. Buchwald, J. Org. Chem., 2000, 65,
5334; (b) T. Saito, T. Yokozawa, T. Ishizaki, T. Moroi, N. Sayo, T. Miura
and H. Kumobayashi, Adv. Synth. Catal., 2001, 343, 264; (c) J. J. Becker
and M. R. Gagne, Organometallics, 2003, 22, 4984; (d) I. P. Beletskaya,
V. V. Afanasiev, M. A. Kazankova and I. V. Efimova, Org. Lett., 2003, 5,
4309; (e) H. C. Wu, J.-Q. Yu and J. B. Spencer, Org. Lett., 2004, 6,
4675; (f) X. Pu, X. Qi and J. M. Ready, J. Am. Chem. Soc., 2009, 131,
10364; (g) L. Liu, H.-C. Wu and J.-Q. Yu, Chem.–Eur. J., 2011, 17,
10828.
14 (a) K. Matsumura, H. Shimizu, T. Saito and H. Kumobayashi, Adv. Synth.
Catal., 2003, 345, 180; (b) J.-F. Wen, W. Hong, K. Yuan, T. C. W. Mak
and H. N. C. Wong, J. Org. Chem., 2003, 68, 8918.
15 For selected reviews: (a) G. A. Molander and B. Canturk, Angew. Chem.,
Int. Ed., 2009, 48, 9240; (b) D.-G. Yu, B.-J. Li and Z.-J. Shi, Acc. Chem.
Res., 2010, 43, 1486; (c) B. M. Rosen, K. W. Quasdorf, D. A. Wilson,
N. Zhang, A.-M. Resmerita, N. K. Garg and V. Percec, Chem. Rev., 2011,
111, 1346; (d) B.-J. Li, D.-G. Yu, C.-L. Sun and Z.-J. Shi, Chem.–Eur. J.,
2011, 17, 1728.
16 For some examples of C–C bond formation: (a) V. Percec, J.-Y. Bae and
D. H. Hill, J. Org. Chem., 1995, 60, 6895; (b) G.-Q. Lin and R. Hong,
J. Org. Chem., 2001, 66, 2877; (c) V. Percec, G. M. Golding, J. Smidrkal
and O. Weichold, J. Org. Chem., 2004, 69, 3447.
23 (a) D. Tanner, P. Wyatt, F. Johansson, S. K. Bertilsson and
P. G. Andersson, Acta Chem. Scand., 1999, 53, 263; (b) N. Zhao and
D. C. Neckers, J. Org. Chem., 2000, 65, 2145.
17 For some examples of C–N bond formation: (a) C.-Y. Gao and
L.-M. Yang, J. Org. Chem., 2008, 73, 1624; (b) C. Bolm,
J. P. Hildebrand and J. Rudolph, Synthesis, 2000, 911.
18 For some examples of C–B bond formation: (a) D. A. Wilson,
C. J. Wilson, C. Moldoveanu, A.-M. Resmerita, P. Corcoran,
L. M. Hoang, B. M. Rosen and V. Percec, J. Am. Chem. Soc., 2010, 132,
1800; (b) P. Leowanawat, N. Zhang, A.-M. Resmerita, B. M. Rosen and
V. Percec, J. Org. Chem., 2011, 76, 9946.
24 L. Xu, J. Mo, C. Baillie and J. Xiao, J. Organomet. Chem., 2003, 687,
301.
25 A. Jutand and A. Mosleh, J. Org. Chem., 1997, 62, 261.
26 W. Xu, J.-P. Zou and W. Zhang, Tetrahedron Lett., 2010, 51, 2639.
27 N. Furukawa, S. Ogawa, K. Matsumura and H. Fujihara, J. Org. Chem.,
1991, 56, 6341.
28 C. M. Whitaker, K. L. Kott and R. J. McMahon, J. Org. Chem., 1995,
60, 3499.
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Org. Biomol. Chem., 2012, 10, 3500–3505 | 3505