Hypervalent iodine in synthesis. 52. Palladium-catalyzed arylation of O,O-dialkyl phosphites with diaryliodonium salts: A convenient method for synthesis of arylphosphonates

Article abstract of DOI:10.1081/SCC-100106038

Palladium-catalyzed coupling reaction of diaryliodonium salts with O,O-dialkyl phosphites gave arylphosphonates in good yields.

Full text of DOI:10.1081/SCC-100106038

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HYPERVALENT IODINE IN SYNTHESIS. 52. PALLADIUM-
CATALYZED ARYLATION OF O,O-DIALKYL PHOSPHITES
WITH DIARYLIODONIUM SALTS: A CONVENIENT
METHOD FOR SYNTHESIS OF ARYLPHOSPHONATES
Tao Zhou a & Zhen-Chu Chen b
a Department of Chemistry , Zhejiang University (Xi-Xi Campus) , Hangzhou, 310028, P.
R. China
b Department of Chemistry , Zhejiang University (Xi-Xi Campus) , Hangzhou, 310028, P.
R. China
Published online: 20 Aug 2006.
To cite this article: Tao Zhou & Zhen-Chu Chen (2001) HYPERVALENT IODINE IN SYNTHESIS. 52. PALLADIUM- CATALYZED
ARYLATION OF O,O-DIALKYL PHOSPHITES WITH DIARYLIODONIUM SALTS: A CONVENIENT METHOD FOR SYNTHESIS OF
ARYLPHOSPHONATES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 31:21, 3289-3294, DOI: 10.1081/SCC-100106038
To link to this article: http://dx.doi.org/10.1081/SCC-100106038
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SYNTHETIC COMMUNICATIONS, 31(21), 3289–3294 (2001)
HYPERVALENT IODINE IN
SYNTHESIS. 52. PALLADIUM-
CATALYZED ARYLATION OF
O,O-DIALKYL PHOSPHITES
WITH DIARYLIODONIUM
SALTS: A CONVENIENT
METHOD FOR SYNTHESIS
OF ARYLPHOSPHONATES
Tao Zhou andZhen-Chu Chen *
Department of Chemistry, Zhejiang
University (Xi-Xi Campus), Hangzhou,
310028, P. R. China
ABSTRACT
Palladium-catalyzed coupling reaction of diaryliodonium salts
with O,O-dialkyl phosphites gave arylphosphonates in good
yields.
The synthesis of arylphosphonates as precursors of phosphorous het-
erocycles or phosphorus analogs of heterocyclic compounds1 is of consider-
able interest. A number of methods have been described for synthesis of
arylphosphonates. For example, substitution of aryl halides with trialkyl
*Corresponding author.
3289
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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ZHOU AND CHEN
phosphites in the presence of nickle2 or copper3 catalyst; coupling of aryl
halides or triflates with dialkyl phosphites in the presence of palladium
catalyst,4 the reaction of diaryliodonium salts with trialkyl phosphites;5
the quenching of aryllithium derivatives with diethyl chlorophosphate;6
the anodic7 or chemical oxidation8 of a mixture of arenes and tri- or dialkyl
phosphites; the photoactivated substitution of halogenoanilines with diethyl
phosphite;9 the reaction of Grignard reagent with diethyl cyanophospho-
nate.10 However, most of these methods have certain disadvantages, such as
the use of excess phosphites, harsh reaction conditions or low yield.
Therefore, there is still a need to develop an efficient method for the
synthesis of arylphosphonates.
In our previous reports dealing with synthetic applications of hyper-
valent iodine compounds,11 it has been shown that diaryliodonium salts
are high reactive substances in many palladium-catalyzed arylating reac-
tions. In our continuing studies on the palladium-catalyzed arylation, we
have explored the palladium-catalyzed arylation to carbon-phosphorus
bond forming reaction. Here we report the results which are summarized
in Scheme 1 and Table 1. The products were characterized by IR, 1H-NMR
and comparison with literature value.
Scheme 1.
We have found that in the presence of K2CO3 the palladium-catalyzed
arylation of O,O-dialkyl phosphites with diaryliodonium salts takes
place smoothly and reaches completion within 2–3 h at 90ꢀC in DMF. We
examined the effect of a variety of catalysts for the reaction of diphenylio-
donium salt with O,O-dipropyl phosphite in the presence of potassium
carbonate. As can be seen in Table 1 (Entries 1, 2, 3, 4), tetrakis(triphenyl-
phosphine) palladium was found to be the most effective catalyst for the
reaction. In the absence of palladium catalyst, the reaction can hardly pro-
ceed (Entry 5), so palladium catalyst is essential for this reaction. Several
diaryliodonium salts containing various substituents such as methyl, chloro,
methoxy and nitro groups, were successfully arylated with O,O-dialkyl
phosphites.

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HYPERVALENT IODINE IN SYNTHESIS. 52
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Table 1. Palladium-Catalyzed Coupling of Diaryliodonium Salts and Dialkyl-
phosphites
Entry
Catalyst
Product
Yield (%)a
1
2
3
4
5
6
7
8
Pd(PPh3)4
PdCl2(PPh3)2
PdCl2
Pd(OAc)2
/
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
PhP(O)(OPr-n)2 3a
3a
3a
3a
3a
98
74
70
66
trace
92
98
91
86
86
89
82
78
82
72
83
PhP(O)(OEt)2 3b
PhP(O)(OPr-i)2 3c
PhP(O)(OBu-n)2 3d
p-TolP(O)(OEt)2 3e
p-TolP(O)(OPr-n)2 3f
p-TolP(O)(OPr-i)2 3g
p-TolP(O)(OBu-n)2 3h
p-ClC6H4P(O)(OPr-i)2 3i
p-ClC6H4P(O)(OPr-n)2 3j
m-NO2C6H4P(O)(OEt)2 3k
p-CH3OC6H4P(O)(OEt)2 3l
9
10Pd(PPh
)
3 4
11
12
13
14
15
16
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
aIsolated yields based on diaryliodonium salts.
We previously reported a method of preparing arylphosphonates
by the reaction of diaryliodonium salts with dialkyl phosphite salts.12 But
present method is more convenient. There is no need to use strong base and
the reaction time is shorter.
In summary, we provide an effective synthesis for arylphosphonates by
palladium-catalyzed arylation of O,O-dialkyl phosphites with diarylio-
donium salts. It has some advantages over others such as mild reaction
conditions, simple procedure and good yields. It also extends the palladium-
catalyzed arylation to carbon-heteroatom bond forming reaction with
diaryliodonium salts.
EXPERIMENTAL
1H NMR spectra were recorded on PMK-60spectrometer using CCl
4
as the solvent with TMS as an internal standard. IR spectra were determined
on PE-683 Infrared spectrophotometer.
Typical procedure for preparation of dialkyl arylphosphonate: A mix-
ture of Ph2IþBF4À (360mg, 1 mmol), K 2CO3 (166 mg, 1.2 mmol), Pd (PPh3)4

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ZHOU AND CHEN
(60 mg, 0.05 mmol), DMF (6 mL) and dialkyl phosphonate (0.2 mL,
1.2 mmol) was stirred at 90ꢀC for 2 h under nitrogen atmosphere, then
diluted with saturated aqueous NH4Cl (20mL) and extracted with ether
(15 mL Â 3). The combined organic layer was washed with brine and dried
over anhydrous Na2SO4. After the removal of the solvent in vacuum, the
residue was isolated by TLC with c-hexane-EtOAc (2 : 1) as developer to
give pure dipropyl phenylphosphonate (3a) 235 mg, 98% yield.
Spectroscopic Data for the Product
Dipropyl phenylphosphonate 3a: oil, bp 115ꢀC/2 Torr (lit13 bp
106–108ꢀC/1 Torr), 1H NMR, dH 0.9 (t, 6H), 1.6 (m, 4H), 3.9 (m, 4H),
7.6 (m, 3H), 7.9 (m, 2H). IR (film), nmax 1255 (P¼O), 1030 (P-O-C),
980cm À1 (Ar-P).
Diethyl phenylphosphonate 3b: oil, bp 112ꢀC/2 Torr (lit2 bp
96–98ꢀC/0.2 Torr), H NMR, dH 1.28 (t, 6H), 4.13 (m, 4H), 7.7 (m, 3H),
1
8.1 (m, 2H). IR (film), nmax 1250, 1030, 965 cmÀ1
.
Diisopropyl phenylphosphonate 3c: oil, bp 131ꢀC/2 Torr (lit2 bp
1
96–97ꢀC/0.1 Torr), H NMR, dH 1.25 (m, 12H), 4.6 (m, 2H), 7.5 (m, 3H),
7.8 (m, 2H). IR (film), nmax 1250, 1010, 980 cmÀ1
.
Dibutyl phenylphosphonate 3d: oil, 154ꢀC/2 Torr (lit14 166ꢀC/
3.8 Torr), 1H NMR, dH 0.85 (t, 6H), 1.5 (m, 8H), 3.95 (m, 4H), 7.5 (m, 3H),
7.85 (m, 2H). IR (film), nmax 1250, 1025, 970 cmÀ1
.
Diethyl p-tolylphosphonate 3e: oil, 179ꢀC/2 Torr (lit2 bp 118–119ꢀC/
0.05 Torr), 1H NMR, dH 1.23 (t, 6H), 2.33 (s, 3H), 4.1 (m, 4H), 7.3 (m, 2H),
7.7 (m, 2H). IR (film), nmax 1250, 1030, 970 cmÀ1
.
Dipropyl p-tolylphosphonate 3f: oil, 120ꢀC/2 Torr (lit13 bp 110–112ꢀC/
1
1 Torr), H NMR, dH 0.88 (t, 6H), 1.55 (m, 4H), 2.35 (s, 3H), 3.9 (m, 4H),
7.3 (m, 2H), 7.72 (m, 2H). IR (film), nmax 1250, 1050, 990 cmÀ1
.
Diisopropyl p-tolylphosphonate 3g: oil, 118ꢀC/2 Torr (lit13
98–100ꢀC/1 Torr), H NMR, dH 1.25 (m, 12H), 2.35 (s, 3H), 4.6 (m, 2H),
1
7.25 (m, 2H), 7.7 (m, 2H). IR (film), nmax 1250, 1010, 980 cmÀ1
.
Dibutyl p-tolylphosphonate 3h: oil, 164ꢀC/2 Torr (lit15 148ꢀC/
1
0.7 Torr), H NMR, dH 0.88 (t, 6H), 1.4 (m, 8H), 2.37 (s, 3H), 4.0 (m, 4H),
7.35 (m, 2H), 7.75 (m, 2H). IR (film), nmax 1250, 1010, 970 cmÀ1
.
Diisopropyl p-chlorophenylphosphonate 3i: oil, 145ꢀC/2 Torr (lit16 oil,
bp was not reported) 1H NMR, dH 1.25 (m, 12H), 4.6 (m, 2H), 7.25–7.9 (m,
4H). IR (film), nmax 1250, 1020, 980 cmÀ1
.
Dipropyl p-chlorophenylphosphonate 3j: oil, 142ꢀC/2 Torr (lit17
148.5ꢀC/3 Torr), 1H NMR, dH 0.9 (t, 6H), 1.6 (m, 4H), 3.9 (m, 4H),
7.22–7.9 (m, 4H). IR (film), nmax 1250, 1020, 980 cmÀ1
.

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HYPERVALENT IODINE IN SYNTHESIS. 52
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Diethyl m-nitrophenylphosphonate 3k: oil, 168ꢀC/2 Torr (lit18
133–137ꢀC/0.2 Torr), H NMR, dH 1.23 (t, 6H), 4.1 (m, 4H), 7.3–8.0(m,
1
4H). IR (film), nmax 1250, 1010, 980 cmÀ1
.
Diethyl p-methoxyphenylphosphonate 3l: oil, 173ꢀC/2 Torr (lit2 bp
168–169ꢀC/1.5 Torr), H NMR, dH 1.2 (t, 6H), 3.9 (m, 4H), 3.7 (s, 3H),
1
7.25–7.8 (m, 4H). IR (film), nmax 1250, 1020, 960 cmÀ1
.
ACKNOWLEDGMENT
We are grateful for the financial support from the National Science
Foundation of China. (Project 29472036)
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Received in the USA January 10, 2001

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