Efficient copper(I)-catalyzed coupling of secondary phosphine oxides with aryl halides

Article abstract of DOI:10.1016/j.tet.2012.10.064

A catalytic system has been developed for the efficient synthesis of tertiary arylphosphine oxides by coupling of readily available secondary phosphine oxides with aryl bromides or iodides in the presence of copper(I) iodide as a catalyst and (S)-α-phenylethylamine as a ligand. The system exhibits high activity in the coupling of secondary diaryl-, alkylaryl- and dialkylphosphine oxides.

Full text of DOI:10.1016/j.tet.2012.10.064

Tetrahedron 69 (2013) 73e81
Contents lists available at SciVerse ScienceDirect
Tetrahedron
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Efficient copper(I)-catalyzed coupling of secondary phosphine oxides
with aryl halides
*
ꢀ
Marek Stankevic , Adam W1odarczyk
Department of Organic Chemistry, Faculty of Chemistry, Marie Curie-Skłodowska University, Gliniana 33, 20-614 Lublin, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 July 2012
Received in revised form 3 October 2012
Accepted 22 October 2012
Available online 30 October 2012
A catalytic system has been developed for the efficient synthesis of tertiary arylphosphine oxides by
coupling of readily available secondary phosphine oxides with aryl bromides or iodides in the presence
of copper(I) iodide as a catalyst and (S)-
in the coupling of secondary diaryl-, alkylaryl- and dialkylphosphine oxides.
Ó 2012 Elsevier Ltd. All rights reserved.
a-phenylethylamine as a ligand. The system exhibits high activity
Keywords:
Coupling reaction
Copper(I) iodide
Secondary phosphine oxides
Tertiary phosphine oxides
Diphosphine dioxides
1. Introduction
metal-catalyzed transformations. However, despite all of the ad-
vantages of palladium catalysts, their use in the cases above is
prohibitively expensive because an effective Hirao coupling gen-
erally requires 5e10 mol % of catalyst. The solution to this problem
could lie in the use of less expensive transition metals possessing
similar activity profiles. A brief look at the literature suggests that
nickel, which is especially suitable as a catalyst for the coupling
of secondary phosphines,7 secondary phosphine-boranes,8 and
secondary phosphine oxides,9 might be regarded as a viable pal-
ladium substitute. Another candidate is copper. This has been
successfully applied in the coupling of secondary phosphites,10 H-
phosphinates,11 and also secondary phosphines, which appear to
couple very efficiently in the presence of copper salts to yield the
corresponding tertiary phosphines (Scheme 2).12
The palladium-catalyzed coupling of secondary phosphites with
sp2 carbon electrophiles described by Hirao and co-workers in
19811 provided a new and powerful method for the synthesis of
aryl or alkenylphosphorus compounds from readily accessible
>P(X)H-type compounds (Scheme 1).
ArBr, Pd(PPh3)4
NEt3
90 oC, 2.5-64 h
34-96%
O
P
EtO
O
P
EtO
H
EtO Aryl
EtO
1
2
Aryl = Ph, p-Tol, o-Tol, p-Cl-C6H4, o-An, p-NO2-C6H4, p-Ac-C6H4,
p-AcNH-C6H4, p-CN-C6H4, p-Br-C6H4, o-Br-C6H4, 1-naphthyl, 3-pyridyl
ArI, CuI, Cs2CO3
Ph
Ph
Ph
Ph
N,N'-dimethyl-ethylenediamine
Scheme 1. Palladium-catalyzed coupling of diethyl phosphite with aryl bromides.
P H
P Aryl
Toluene, 110 oC, 14-24 h
60-91%
Since then, palladium catalysts have become standard tools for
the coupling of other types of phosphorus nucleophiles, such as
secondary phosphites,2 H-phosphinates,3 secondary phosphine
oxides,4 secondary phosphine-boranes,5 and secondary phos-
phines.6 The last of these can be regarded as direct precursors for
tertiary arylphosphines, which are valuable ligands in transition
3
4
Aryl = 1-naphthyl, o-An, o-NH2-C6H4, o-Br-C6H4, o-Ph-C6H4, 3-pyridyl
Scheme 2. Copper-catalyzed coupling of secondary phosphines.
In the case of palladium complexes, reports concerning the use
of copper salts for the coupling of secondary phosphine oxides with
aryl halides are rare. A few examples concerning the coupling of
* Corresponding author. E-mail address: marek.stankevic@poczta.umcs.lublin.pl
ꢀ
(M. Stankevic).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.10.064

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M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
74
diphenylphosphine oxide with simple haloarenes have been pre-
sented by Fu and co-workers,13 and the coupling of three electron-
deficient secondary phosphine oxides with C-chiral 2-(o-bro-
moaryl)oxazolines has been given by Stolz and co-workers.14
In the second step, several bases were tested in the model re-
action (Table 1, entries 12e15). However, all of them were less ef-
fective than potassium carbonate, so all further experiments were
performed in the presence of this base.
The optimization of the ligand/base combination gave us
a chance to take a closer look at the ability of the system to catalyze
the coupling of secondary phosphine oxides with aryl halides. To
provide a broader view of the compatibility of secondary phos-
phine oxides with the coupling reaction we chose diphenylphos-
phine oxide (5a), o-anisylphenylphosphine oxide (5b),
methylphenylphosphine oxide (5c) and tert-butylphenylphosphine
oxide (5d), di-n-hexylphosphine oxide (5e), and di-c-hex-
ylphosphine oxide (5f) as model substrates (Table 2, Scheme 4).
The data presented in Table 2 show that all model secondary
phosphine oxides reacted efficiently with the corresponding aryl
halides and gave tertiary phosphine oxides in good to excellent
yields. Further, diphenylphosphine oxide (5a) afforded good yields
of 6a and 6b in reactions with o-substituted aryl iodides; similarly,
o-anisylphenylphosphine oxide (5b) also reacted either with bulky
aryl iodides (1-iodonaphthalene, o-iodotoluene) or with sterically
non-demanding aryl iodides (2-iodonaphthalene, p-iodotoluene,
m-xylyl iodide) to give the corresponding products in good yields.
The presence of amino or bromo functionalities in the para position
was very well tolerated, and coupling of 5b with methyl o-iodo-
benzoate under the standard reaction conditions also gave the or-
tho-carboxy-functionalized triarylphosphine oxide in 86% yield.
In our previous paper, we described the transformation of
diphenylmethylphosphine oxide into methylphenylphosphine ox-
ide (5c),16 and we have also applied this precursor in coupling re-
actions with aryl iodides. In all cases the reaction led to formation
of the corresponding diarylmethylphosphine oxides 6ken in very
good yields. This two-step transformation can be regarded as
a practical method for exchanging arene groups in arylmethyl-
phosphine oxides. Similarly, the use of bulky phosphine oxide 5d
afforded the corresponding coupling products 6oer in good to
excellent yields.
2. Results and discussion
As part of a research project directed toward the functionali-
zation of the aryl substituents of arylphosphine and arylphospho-
rus acid derivatives through Birch reduction,15 we were interested
in the efficient synthesis of tertiary arylphosphine oxides. We were
pleased to find that treatment of o-anisylphenylphosphine oxide
with m-xylyl iodide in the presence of CuI, rac-1,2-
diaminocyclohexane and K2CO3 afforded the corresponding triar-
ylphosphine oxide in 94% yield.16 This suggested that copper(I) salts
might serve as good substitutes for palladium in coupling reactions
involving secondary phosphine oxides. With this encouraging re-
sult in hand, we performed an optimization of the reaction condi-
tions using 5a and o-iodotoluene as substrates (Table 1, Scheme 3).
Table 1
Optimization of the reaction conditions in coupling of 5a with o-iodotoluene
Nr
Ligand (mol %)
-Proline (20)
2-Picolinic acid (20)
(S)- -Phenylethylamine (20)
Base
Yielda of 6a %
1
2
3
L
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
t-BuOK
DABCO
iPr2NEt
Cs2CO3
K2CO3
44%
80%
87%
77%
29%
29%
63%
35%
71%
77%
74%
30%
20%
15%
53%
44%
a
4
5
TMEDA (10)
DMEDAb (10)
6
7
7
8
Ethylenediamine (10)
2,20-Bipyridine (10)
1,10-Phenanthroline (10)
PPh3 (20)
9
nBu3P (20)
10
11
12
13
14
15
rac-BINAP (10)
(S)-
(S)-
(S)-
(S)-
a
a
a
a
-Phenylethylamine (20)
-Phenylethylamine (20)
-Phenylethylamine (20)
-Phenylethylamine (20)
L-Proline (20)
The coupling of dialkylphosphine oxides 5e and 5f with various
aryl halides was also attempted. In all cases, the coupling product
was formed efficiently; however, in some cases, the use of a two-
fold excess of aryl halide was necessary to keep the yield
high. The starting material was 2-bromopyridine in the case of 2-
pyridylphosphine oxides 6s and 6v and this indicates that aryl
bromides might also find application in coupling reactions with
secondary phosphine oxides.
The entry in bold shows the best reaction conditions.
a
Yields after purification by column chromatography.
DMEDAdN,N0-dimethylethylenediamine.
b
o-Tol-I (1 equiv.), CuI (10 mol%)
O
P
Ph
O
P
Ph
ligand, base (2 equiv.)
PhMe, 110 oC, 24 h
The use of a chiral amine ligand could lead to the formation of
enantiomerically enriched products, however, chiral HPLC analysis
of 6ken showed that in all cases racemates were formed, regard-
Ph
H
Ph
6a
5a
less of the ligand used in the coupling protocol ((S)-
a-phenyleth-
Scheme 3. Optimization of the reaction conditions in coupling of 5a with o-
iodotoluene.
ylamine, -proline or (R)-BINAP).
L
Attempted coupling of phosphine oxides 5b and 5d with p-
bromoiodobenzene afforded the reactive bromo-substituted ter-
tiary arylphosphine oxides 6g and 6q. The more interesting in-
troduction of an aryl fragment possessing a o-bromo functionality,
which might be used the synthesis of symmetrically- or
Previous data12 suggest that toluene is the solvent of choice for
this reaction, so we attempted to find the ligand/base system, which
allows the best substrate conversion. As a first step, a set of amine
and phosphine ligands were tested (Table 1, entries 1e11). When
using K2CO3 as the base, the monochelating (S)-
a
-phenylethyl-
unsymmetrically-substituted
ortho-(diphosphorus-substituted)
amine (Table 1, entry 3) produces 6a with the highest yield. Other
arenes, was also attempted (Scheme 5).
commonly used monoaza-ligands, such as
L
-proline17 (Table 1, entry
However, reaction of 5a with o-dibromobenzene 7a failed to
provide any products under the standard reaction conditions. The
related reaction of 5a with o-bromoiodobenzene 7b provided the
corresponding diphosphine dioxide 8a in 43% yield. These results
can be explained in terms of differences in the reactivity of car-
bonebromide and carboneiodine bonds. The more reactive car-
boneiodine bond enters the reaction with the secondary
phosphine oxide to give the intermediate o-bromophenyl-
substituted tertiary phosphine oxide, which undergoes a second
coupling reaction at the carbonebromine bond. The presence of
1) or 2-picolinic acid18 (Table 1, entry 2) afforded less of the 6a
product. For diamines, DMEDA, which has been shown by Buchwald
and co-workers to be very effective for the coupling of secondary
phosphines with aryl and vinyl halides,12a afforded 6a in only 29%
yield (Table 1, entry 5); TMEDA was found to give 6a in 77% yield, but
this is still less effective than (S)-a-phenylethylamine. Mono- and
diphosphines (Table 1, entries 9e11) could be used to transform 5a
into 6a in relatively yields, but difficulties in separation of the
product from the oxidized ligands made their use inconvenient.

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M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
75
Table 2
Copper-catalyzed coupling of secondary phosphine oxides 5aef with aryl halides
O
O
P
o-An
O
P
o-An
O
P
Ph
OMe
P
Ph
Ph
Ph
Ph
Ph
6b (70%)a
6b (99%)b
6c (82%)
6d (87%)
6a (87%)
O
P
o-An
6e (95%)c
O
P
O
P
o-An
O
P
o-An
Ph
Ph
Ph
Ph
o-An
Br
6f (99%)c
6g (91%)
6h (99%)c
O
P
O
P
Me
O
O
P
Me
COOMe
COOMe
P
Ph
Ph
Ph
Ph
Ph
o-An
o-An
6i (95%)
NH2
6j (99%)
6k (92%)
6l (75%)
O
P
Me
O
P
t-Bu
O
P
Me
O
P
t-Bu
OMe
Ph
Ph
Ph
6m (69%)
6o (91%)
6n (75%)
6p (86%)
O
P
t-Bu
O
P
O
O
P
COOMe
P
N
n-Hex
Ph
n-Hex
Ph
n-Hex
6t (95%)e
n-Hex
6s (78%)c,d
O
t-Bu
6r (91%)
Br
6q (80%)
O
P
O
P
-Hex
6v (91%)c,d
O
P
O
P
c-Hex
COOMe
N
c-Hex
c
-Hex
c-Hex
c-Hex
c-Hex
c
c-Hex
6w (98%)e
O
6u (97%)c,e
6x (82%)
a
b
c
d
e
– 5a and 2-iodoaniline were used. – 5b and iodobenzene were used. – 2 equivalents of aryl halide was used. – 2-bromopyridine was used.
–
triphenylphosphine (20 mol%) was used as ligand.
Scheme 4. Copper-catalyzed coupling of secondary phosphine oxides 5aef with aryl
halides.
Scheme 5. Coupling of 5a with 2-iodobromobenzene.
electron-withdrawing phosphinoyl group in the ortho position
seems likely to facilitate the cleavage of carbonebromine bond in
the second step. The case of o-dibromobenzene is different because
the carbonebromine bond in 7a is not reactive enough to drive the
first step of the reaction. Nevertheless, these results point out that
this system can be used for the synthesis of symmetrical diphos-
phines and their derivatives, and this was checked by coupling of 7b
with a 2 equiv of various secondary phosphine oxides (Scheme 6).
The outcome of the reaction appears to depend on the nature of
the secondary phosphine oxide and, more precisely, on both its
steric and electronic properties. The reaction is driven toward
diphosphine dioxide if the starting phosphine oxide possesses
electron-withdrawing groups at phosphorus. However, in the case

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M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
76
as Attenuated Total Reflection (FTIR ATR) of neat compounds. Thin-
Layer Chromatography (TLC) was performed with precoated silica
gel plates and visualized by UV light or KMnO4 solution. The re-
action mixtures were purified by column chromatography over
silica gel (60e240 mesh).
4.1.1. o-Anisylphenylphosphine oxide (5b). In a flame-dried three-
necked round-bottom flask (500 mL) equipped with a magnetic
stirrer, a reflux condenser, and a dropping funnel was placed THF
(150 mL), magnesium turnings (2.9 g, 0.12 mol) and a piece of io-
dine under inert atmosphere. In a dropping funnel, a solution of o-
bromoanisole (15 mL, 0.12 mol) in THF (50 mL) was placed. After
addition of a small amount of o-bromoanisole solution in THF the
reaction started to reflux gentle in ca. 5 min. Then, the remaining o-
bromoanisole solution in THF was added dropwise to maintain the
gentle reflux. After addition of aryl bromide, the reaction mixture
was refluxed for additional 30 min and then cooled to 0 ꢀC. In an-
other flask, a solution of diethyl phosphite (6.2 mL, 0.048 mol) in
THF (20 mL) was prepared and then added via syringe over 30 min.
After addition of diethyl phosphite, the reaction mixture was
refluxed under inert atmosphere for 3 h. Then, the reaction mixture
was cooled to room temperature and a solution of 10% H2SO4
(50 mL) and water (100 mL) was added. The reaction mixture was
placed in a separatory funnel, the organic phase was removed and
the aqueous phase was extracted with chloroform (3ꢁ50 mL), or-
ganic fractions were collected, dried over MgSO4, and the solvent
was removed under reduced pressure. The residue was crystallized
from toluene yielding 5b (7.6 g, 68%); pale yellow solid; mp
101.0e103.0 ꢀC (lit.29 105e106 ꢀC); Rf (CHCl3/MeOH¼15:1) 0.57;
[found: C, 67.29; H, 5.90. C13H13O2P requires C, 67.24; H, 5.64]; dH
(500 MHz, CDCl3) 3.80 (s, 3H), 6.91e6.95 (m, 1H), 7.10e7.15 (m, 1H),
7.45e7.50 (m, 2H), 7.52e7.58 (m, 2H), 7.72e7.78 (m, 2H), 7.78e7.84
(m, 1H), 8.19 (d, JPeH¼499.4 Hz, 1H); dC (125 MHz, CDCl3) 55.5, 110.7
(d, JPeC¼5.5 Hz), 119.4 (d, JPeC¼101.7 Hz), 121.1 (d, JPeC¼11.8 Hz),
128.5 (d, JPeC¼13.6 Hz), 130.4 (d, JPeC¼11.8 Hz), 132.0 (d,
JPeC¼2.7 Hz), 132.1 (d, JPeC¼104.5 Hz), 133.0 (d, JPeC¼7.3 Hz), 134.4
(d, JPeC¼1.8 Hz), 160.6 (JPeC¼3.6 Hz); dP (202 MHz, CDCl3) 14.35; GC
tR¼14.69 min; GCeMS (EI, 70 eV) m/z¼232 (Mþ) (27), 231 (10), 214
(13), 213 (25), 201 (37), 199 (16), 196 (35), 183 (30), 167 (17), 166
(16), 165 (18), 153 (12), 152 (29), 141 (100), 139 (13), 137 (13), 125
(13), 107 (15), 92 (22), 91 (60); Analytical data are in accordance
with those reported in the literature.30
Scheme 6. Coupling of secondary phosphine oxides 5a,dei with 2-
iodobromobenzene.
of sterically hindered groups, monocoupled dehalogenated prod-
ucts can also be observed (see 5d and 5h).
Secondary phosphine oxides with small aryl groups possessing
electron-donating substituents react sluggishly with 7b whilst
dialkylphosphine oxides form complex reaction mixtures. How-
ever, even if its scope is quite restricted, this method could offer
a convenient access to some symmetrical 1,2-bis(phosphorus-
substituted)benzenes, especially those possessing bulky sub-
stituents in the starting secondary phosphine oxides.
3. Conclusions
In summary, we have presented an efficient method for the
synthesis of tertiary arylphosphine oxides through the coupling of
secondary phosphine oxides with aryl halides by a CuI/(S)-a-
phenylethylamine system, and shown that this methodology could
also find applications in the synthesis of 1,2-bis(phosphorus-
substituted)benzenes.
4. Experimental section
4.1. General
All reactions were performed under an argon atmosphere using
Schlenk techniques. Only dry solvents were used and the glassware
was heated under vacuum prior to use. Solvents for chromatogra-
phy and crystallization were distilled once before the use and the
solvents for extraction were used as received. Toluene was dried
over sodium/benzophenone prior to use. o-Tolyl iodide, o-anisyl
iodide, iodobenzene, 1-iodonaphthalene, p-aminoiodobenzene, 2-
4.2. General procedure for the copper(I)-catalyzed coupling
of secondary phosphine oxides with aryl halides
bromopyridine, 1,2-dibromobenzene,
L-proline, 2-picolinic acid,
(S)-a
-phenylethylamine, TMEDA, DMEDA, ethylenediamine, 2,20-
bipyridine, 1,10-phenanthroline, triphenylphosphine, tri-n-butyl-
phosphine, rac-BINAP, copper(I) iodide, t-BuOK, K2CO3, Cs2CO3,
DABCO, and i-Pr2NEt were commercially available and used as re-
ceived. 2-Iodonaphthalene,19 p-iodotoluene,20 p-bromoiodo-
benzene,21 3,5-dimethyliodobenzene,22 o-bromoiodobenzene,23
methyl o-iodobenzoate,24 2-iodofuran,25 diphenylphosphine ox-
ide (5a),16 methylphenylphosphine oxide (5c),16 tert-butylphenyl-
phosphine oxide (5d),26 di-c-hexylphosphine oxide (5e),27 and di-
n-hexylphosphine oxide (5f)28 were prepared according to the lit-
erature procedures.
The NMR spectra were recorded 500 MHz, 400 MHz or 300 MHz
spectrometers in CDCl3 as a solvent at room temperature unless
otherwise noted. Chemical shifts (d) are reported in parts per mil-
lion relative to residual solvent peak. Mass spectra were recorded in
electron ionization (EI) mode and GC was recorded using following
parameters: pressured97.9 kPa, total flowd19.5 mL/min, column
flowd1.5 mL/min, linear velocityd44.9 cm/s, splitd10, tempera-
ture program (70 ꢀCdhold 3 min, 70e340 ꢀC/12 ꢀC/mindhold
9.5 mindtotal 35 min) and TOF mode for HPLC-HRMS experiments.
IR spectra were recorded on FTIR Nicolet 8700A and all were made
In a flame-dried Schlenk vessel (25 mL) was placed copper io-
dide (0.019 g, 0.1 mmol, 10 mol %) under inert atmosphere. Then,
(S)-a-phenylethylamine (0.024 g, 0.2 mmol, 20 mol %) was added,
followed by aryl halide (1 mmol). After 5 min, toluene (5 mL) was
added followed by addition of secondary phosphine oxide
(1 mmol). In cases where the secondary phosphine oxide was
a liquid, it was dissolved in toluene (1 mL) prior to addition to the
reaction mixture, which contained 4 mL of toluene. After the
mixture was stirred for 5 min, anhydrous potassium carbonate
(0.276 g, 2 mmol) was added and the reaction mixture was stirred
at 110 ꢀC for 24 h under argon atmosphere. Then, the mixture was
allowed to cool to room temperature and was filtered through
a short plug of Celite under reduced pressure. Celite was washed
three times with DCM (15 mL each) and the filtrate was evaporated
under reduced pressure. The residue was purified by flash chro-
matography using CHCl3/MeOH (15:1 v/v) as eluent.
4.2.1. Diphenyl(o-tolyl)phosphine oxide (6a). Prepared using the
general procedure from diphenylphosphine oxide (5a) (0.202 g,
1 mmol) and o-iodotoluene (0.127 mL, 1 mmol): yield 0.254 g

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M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
77
(87%); white solid; mp 121.5e122.9 ꢀC (lit.31 121e123 ꢀC); Rf (CHCl3/
MeOH¼15:1) 0.68; [found: C, 78.35; H, 5.95. C19H17OP requires C,
78.07; H, 5.86]; nmax (ATR) 3491, 3445, 3061, 2925, 1590, 1433, 1311,
1281, 1178, 1118, 1102, 764, 703, 694; dH (500 MHz, CDCl3) 2.45 (s,
3H, Me), 7.00e7.05 (m, 1H), 7.10e7.15 (m, 1H), 7.26e7.30 (m, 1H),
7.39e7.44 (m, 1H) 7.45e7.49 (m, 4H) 7.52e7.57 (m, 2H) 7.62e7.68
(m, 4H); dC (125 MHz, CDCl3) 21.6 (d, JPeC¼5.4 Hz), 125.1 (d,
JPeC¼12.7 Hz), 128.5 (d, JPeC¼12.7 Hz), 130.7 (d, JPeC¼103.5 Hz),
131.7 (d, JPeC¼2.7 Hz),131.8 (d, JPeC¼10.0 Hz),132.0 (d, JPeC¼2.7 Hz),
132.6 (d, JPeC¼102.6 Hz), 133.4 (d, JPeC¼12.4 Hz), 143.2 (d,
JPeC¼8.2 Hz); dP (202 MHz, CDCl3) 31.82; GC tR¼21.34 min; GCeMS
(EI, 70 eV) m/z¼292 (Mþ) (21), 291 (62), 278 (34), 277 (100), 201
(15), 199 (26), 183 (19), 165 (12), 152 (18); HRMS [MþH]þ: calcd for
C19H18OP: 293.1090. Found: 293.1086; Analytical data are in ac-
cordance with those reported in the literature.31
(m, 4H), 7.65e7.70 (m, 1H), 7.72e7.82 (m, 3H), 7.85e7.89 (m, 3H),
8.34e8.39 (m, 1H); dC (125 MHz, CDCl3) 55.2, 111.3 (d, JPeC¼6.3 Hz),
120.2 (d, JPeC¼103.5 Hz), 120.9 (d, JPeC¼11.8 Hz), 126.6, 127.0 (d,
JPeC¼10.9 Hz), 127.6 (d, JPeC¼11.8 Hz), 127.8 (d, JPeC¼17.2 Hz), 128.1
(d, JPeC¼12.7 Hz), 128.9, 130.2 (d, JPeC¼107.2 Hz), 131.5 (d,
JPeC¼2.7 Hz), 131.7 (d, JPeC¼10.9 Hz), 132.3 (d, JPeC¼13.6 Hz), 133.2
(d, JPeC¼107.1 Hz), 133.6 (d, JPeC¼9.1 Hz), 134.3 (d, JPeC¼1.8 Hz),
134.5 (d, JPeC¼2.6 Hz), 135.0 (d, JPeC¼7.2 Hz), 160.9 (d, JPeC¼3.6 Hz);
dP (202 MHz, CDCl3) 27.24; GC tR¼29.22 min; GCeMS (EI, 70 eV) m/
z¼358 (Mþ) (85), 357 (23), 341 (16), 340 (28), 339 (11), 339 (11), 327
(27), 267 (49), 250 (12), 251 (12), 249 (65), 234 (14), 233 (17), 218
(20), 217 (100), 215 (14), 203 (13), 202 (44), 201 (16), 200 (13), 199
(68),183 (10),165 (10),152 (28),142 (26),141 (73),139 (17),128 (26),
127 (45), 126 (18), 115 (19), 91 (30), 77 (54), 51 (28), 47 (17); HRMS
[MþH]þ: calcd for C23H20O2P: 359.1195. Found: 359.1206.
4.2.2. o-Anisyldiphenylphosphine oxide (6b). Prepared using the
general procedure from o-anisylphenylphosphine oxide (5b)
(0.232 g, 1 mmol) and o-iodoanisole (0.130 mL, 1 mmol): yield
0.305 g (99%); pale yellow solid; mp 164.2e166.6 ꢀC (lit.32
165e166 ꢀC); Rf (CHCl3/MeOH¼15:1) 0.38; [found: C, 74.40; H,
5.40. C19H17O2P requires C, 74.02; H, 5.56]; nmax (ATR) 3049, 3015,
2988, 2948, 2842, 1589, 1577, 1480, 1435, 1280, 1249, 1174, 1117,
4.2.5. o-Anisylphenyl(p-tolyl)phosphine oxide (6e). Prepared using
the general procedure from o-anisylphenylphosphine oxide (5b)
(0.232 g, 1 mmol) and p-iodotoluene (0.436 g, 2 mmol): yield
0.306 g (95%); pale brown thick oil; Rf (CHCl3/MeOH¼15:1) 0.58;
[found: C, 74.39; H, 5.93. C20H19O2P requires C, 74.32; H, 5.94]; nmax
(ATR) 3056, 3019, 2938, 2837, 2212, 1588, 1574, 1476, 1432, 1273,
1245, 1175, 1116, 1102, 1073, 1017, 800, 757, 716, 693; dH (500 MHz,
CDCl3) 2.39 (s, 3H), 3.56 (s, 3H), 6.88e6.93 (m, 1H), 7.03e7.10 (m,
1H), 7.21e7.26 (m, 2H), 7.38e7.44 (m, 2H), 7.46e7.55 (m, 2H),
7.56e7.63 (m, 2H), 7.66e7.72 (m, 2H), 7.73e7.78 (m, 1H); dC
(125 MHz, CDCl3) 21.5, 55.2, 111.3 (d, JPeC¼6.3 Hz), 120.4 (d,
JPeC¼103.5 Hz), 120.8 (d, JPeC¼11.8 Hz), 128.0 (d, JPeC¼11.8 Hz),
128.8 (d, JPeC¼12.7 Hz), 129.6 (d, JPeC¼109.9 Hz), 131.2 (d,
JPeC¼2.7 Hz),131.7 (d, JPeC¼9.9 Hz),131.8 (d, JPeC¼10.0 Hz),133.5 (d,
JPeC¼108.1 Hz), 134.1 (d, JPeC¼2.7 Hz), 134.9 (d, JPeC¼7.3 Hz), 141.8
(d, JPeC¼2.7 Hz), 160.8 (d, JPeC¼3.6 Hz); dP (202 MHz, CDCl3) 27.37;
GC tR¼22.74 min; GCeMS (EI, 70 eV) m/z¼322 (Mþ) (100), 321 (41),
305 (20), 304 (50), 303 (16), 293 (19), 292 (12), 291 (58), 232 (12),
231 (87), 229 (24), 218 (11), 217 (82), 215 (39), 214 (20), 213 (92),
212 (15), 201 (15), 200 (13), 199 (88), 197 (17), 183 (29), 181 (13), 168
(11),167 (14),166 (26),165 (48),153 (19),152 (57),151 (10),141 (10),
139 (27), 137 (13), 128 (11), 115 (19), 109 (19), 107 (13), 105 (69), 95
(10), 92 (19), 91 (86), 89 (14), 79 (10), 78 (17), 77 (85), 65 (52), 64
(12), 63 (20), 51 (47), 47 (32), 39 (24); HRMS [MþH]þ: calcd for
C20H20O2P: 323.1195. Found: 323.1204.
1072, 1013, 752, 693; dH (500 MHz, CDCl3)
(m, 1H), 7.03e7.18 (m, 1H), 7.37e7.43 (m, 4H), 7.45e7.54 (m, 3H),
7.66e7.72 (m, 4H), 7.73e7.79 (m, 1H); dC (125 MHz, CDCl3) 55.1,
d 3.53 (s, 3H), 6.87e6.91
d
111.3 (d, JPeC¼6.4 Hz), 120.1 (d, JPeC¼104.5 Hz), 120.8 (d,
JPeC¼11.8 Hz), 128.0 (d, JPeC¼12.7 Hz), 131.3 (d, JPeC¼3.6 Hz), 131.7
(d, JPeC¼10.9 Hz), 133.1 (d, JPeC¼108.1 Hz), 134.2 (d, JPeC¼1.8 Hz),
134.8 (d, JPeC¼7.3 Hz), 160.7 (d, JPeC¼2.7 Hz); dP (121.5 MHz, CDCl3)
d
27.65; GC tR¼21.67 min; GCeMS (EI, 70 eV) m/z¼308 (Mþ) (49),
307 (27), 291 (12), 290 (31), 289 (11), 279 (15), 277 (36), 229 (12),
218 (12), 217 (87), 201 (23), 200 (14), 199 (100), 183 (24), 153 (13),
152 (47), 139 (15), 115 (14), 91 (35); Analytical data are in accor-
dance with those reported in the literature.33
4.2.3. o-Anisyl(1-naphthyl)phenylphosphine oxide (6c). Prepared
using the general procedure from o-anisylphenylphosphine oxide
(5b) (0.232 g, 1 mmol) and 1-iodonaphthalene (0.146 mL, 1 mmol):
yield 0.294 g (82%); pale yellow solid; mp 196.2e197.7 ꢀC; Rf 0.45
(CHCl3/MeOH¼15:1); [found: C, 77.35; H, 5.09. C23H19O2P requires
C, 77.08; H, 5.34]; nmax (ATR) 3069, 2960, 2926, 2851, 1588, 1476,
1458, 1432, 1272, 1238, 1180, 1109, 1074, 1015, 800, 771, 746, 693; dH
(500 MHz, CDCl3) 3.47 (s, 3H), 6.90e6.94 (m, 1H), 7.06e7.11 (m, 1H),
7.38e7.57 (m, 8H), 7.71e7.77 (m, 2H), 7.77e7.82 (m, 1H), 7.86e7.90
(m, 1H), 7.97e8.01 (m, 1H), 8.56e8.60 (m, 1H); dC (125 MHz, CDCl3)
55.3, 111.6 (d, JPeC¼6.4 Hz), 120.9 (d, JPeC¼104.5 Hz), 121.1 (d,
JPeC¼11.8 Hz), 124.2 (d, JPeC¼14.5 Hz), 126.1, 127.0, 127.4 (d,
JPeC¼6.4 Hz),128.1 (d, JPeC¼12.7 Hz),128.6,129.1 (d, JPeC¼109.0 Hz),
131.4 (d, JPeC¼2.7 Hz),132.0 (d, JPeC¼10.0 Hz),132.6 (d, JPeC¼2.7 Hz),
133.0 (d, JPeC¼11.8 Hz), 133.5 (d, JPeC¼107.2 Hz), 133.6 (d,
JPeC¼9.1 Hz), 133.7 (d, JPeC¼9.1 Hz), 134.2 (d, JPeC¼1.8 Hz), 134.8 (d,
JPeC¼7.3 Hz), 161.0 (d, JPeC¼2.7 Hz); dP (202 MHz, CDCl3) 30.48; GC
tR¼29.09 min; GCeMS (EI, 70 eV) m/z¼358 (Mþ) (45), 357 (100), 341
(16), 328 (17), 327 (72), 250 (11), 249 (58), 217 (25), 202 (27), 199
(21), 173 (13), 152 (13), 141 (27), 127 (18), 126 (10), 101 (11), 91 (19).
4.2.6. o-Anisylphenyl(o-tolyl)phosphine oxide (6f). Prepared using
the general procedure from o-anisylphenylphosphine oxide (5b)
(0.232 g, 1 mmol) and o-iodotoluene (0.127 mL, 1 mmol): yield
0.319 g (99%); pale brown-yellow thick oil; Rf (CHCl3/MeOH¼15:1)
0.69; [found: C, 74.35; H, 5.80. C20H19O2P requires C, 74.32; H, 5.94];
nmax (ATR) 3057, 3001, 2927, 2847, 1578, 1574, 1477, 1431, 1275, 1247,
1178, 1134, 1107, 1083, 1011, 804, 748, 712, 693; dH (500 MHz, CDCl3)
2.41 (s, 3H), 3.50 (s, 3H), 6.88e6.91 (m, 1H), 7.04e7.08 (m, 1H),
7.08e7.13 (m, 1H), 7.14e7.23 (m, 2H), 7.33e7.37 (m, 1H), 7.37e7.42
(m, 2H), 7.45e7.53 (m, 2H), 7.67e7.73 (m, 2H), 7.75e7.80 (m, 1H); dC
(75 MHz, CDCl3)
d
21.3 (d, JPeC¼4.6 Hz), 55.2, 111.3 (d, JPeC¼6.3 Hz),
120.6 (d, JPeC¼102.6 Hz), 121.0 (d, JPeC¼11.8 Hz), 124.8 (d,
JPeC¼13.5 Hz), 128.0 (d, JPeC¼12.4 Hz), 130.8 (d, JPeC¼106.3 Hz),
131.2 (d, JPeC¼2.9 Hz), 131.4 (d, JPeC¼4.9 Hz), 131.5 (d, JPeC¼2.9 Hz),
131.8 (d, JPeC¼10.4 Hz), 132.9 (d, JPeC¼13.5 Hz), 133.3 (d,
JPeC¼106.6 Hz), 134.0 (d, JPeC¼2.0 Hz), 134.6 (d, JPeC¼7.2 Hz), 142.6
4.2.4. o-Anisyl(2-naphthyl)phenylphosphine oxide (6d). Prepared
using the general procedure from o-anisylphenylphosphine oxide
(5b) (0.232 g, 1 mmol) and 2-iodonaphthalene (0.254 g, 1 mmol):
yield 0.211 g (59%); pale brown solid; mp 132.0e133.0 ꢀC (lit.34
139e142 ꢀC); Rf (CHCl3/MeOH¼15:1) 0.47; [found: C, 77.01; H,
5.22. C23H19O2P requires C, 77.08; H, 5.34]; nmax (ATR) 3054, 2935,
2836, 2212,1588,1574,1476,1432,1273,1245,1175,1134,1109,1087,
1016, 907, 800, 746, 727, 714, 693; dH (500 MHz, CDCl3) 3.55 (s, 3H),
6.91e6.95 (m, 1H), 7.06e7.11 (m, 1H), 7.41e7.46 (m, 2H), 7.49e7.60
(d, JPeC¼8.9 Hz),160.6 (d, JPeC¼3.5 Hz); dP (202 MHz, CDCl3)
d 29.93;
GC tR¼21.33 min; GCeMS (EI, 70 eV) m/z¼322 (Mþ) (3), 292 (20),
291 (100), 212 (15), 166 (11), 165 (19), 152 (10), 91 (10), 77 (10);
HRMS [MþH]þ: calcd for C20H20O2P: 323.1195. Found 323.1184.
4.2.7. o-Anisyl(p-bromophenyl)phenylphosphine oxide (6g). Prepared
using the general procedure from o-anisylphenylphosphine oxide
(5b) (0.232 g, 1 mmol) and p-bromoiodobenzene (0.283 g, 1 mmol):

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M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
78
yield 0.352 g (91%); pale brown thick oil; Rf (CHCl3/MeOH¼15:1)
0.55; [found: C, 58.80; H, 4.32. C19H16BrO2P requires C, 58.94; H,
4.16]; nmax (ATR) 3057, 2965, 2837, 1588, 1574, 1476, 1461, 1432, 1382,
1274, 1244, 1176, 1115, 1067, 1009, 816, 800, 738, 714, 693; dH
(500 MHz, CDCl3) 3.57 (s, 3H), 6.90e6.94 (m, 1H), 7.07e7.11 (m, 1H),
7.41e7.45 (m, 2H), 7.49e7.55 (m, 2H), 7.55e7.61 (m, 4H), 7.65e7.70
(m, 2H), 7.76e7.82 (m, 1H); dC (125 MHz, CDCl3) 55.2, 111.3 (d,
JPeC¼6.4 Hz), 119.6 (d, JPeC¼104.5 Hz), 121.0 (d, JPeC¼11.8 Hz), 126.4
(d, JPeC¼2.7 Hz),128.2 (d, JPeC¼12.7 Hz), 131.3 (d, JPeC¼13.6 Hz), 131.6
(d, JPeC¼2.7 Hz), 131.6 (d, JPeC¼10.0 Hz), 132.4 (d, JPeC¼108.1 Hz),
132.6 (d, JPeC¼108.1 Hz), 133.4 (d, JPeC¼10.9 Hz), 134.5 (d,
JPeC¼2.7 Hz), 134.9 (d, JPeC¼7.3 Hz), 160.6 (d, JPeC¼3.6 Hz); dP
(202 MHz, CDCl3) 26.61; GC tR¼19.31 min; GCeMS (EI, 70 eV) m/
z¼388 (24), 387 (Mþ) (15), 386 (24), 385 (10), 370 (14), 368 (14), 357
(18), 355 (14), 297 (21), 295 (23), 279 (23), 277 (21), 229 (9), 218 (13),
217 (100), 215 (10), 201 (14), 200 (10), 199 (66),183 (22), 171 (13), 170
(12), 168 (11), 165 (10), 153 (12), 152 (45), 151 (12), 139 (22), 137 (9),
115 (10), 107 (12), 92 (11), 91 (33).
phenylphosphine oxide (5b) (0.232 g, 1 mmol) and methyl
o-iodobenzoate (0.147 mL, 1 mmol): yield 0.315 g (86%); light
brown oil; Rf (CHCl3/MeOH¼15:1) 0.61; [found: C, 68.66; H, 5.00.
C21H19O4P requires C, 68.85; H, 5.21; N, 4.33]; nmax (ATR) 3060,
2948, 2837, 1726, 1588, 1574, 1477, 1431, 1274, 1253, 1179, 1120,
1078, 1016, 800, 748, 710, 694; dH (500 MHz, CDCl3) 3.34 (s, 3H),
3.44 (s, 3H), 6.81e6.85 (m, 1H), 7.00e7.04 (m, 1H), 7.32e7.37 (m,
2H), 7.38e7.44 (m, 3H), 7.45e7.54 (m, 2H), 7.68e7.81 (m, 4H); dC
(125 MHz, CDCl3) 51.6, 54.9, 111.0 (d, JPeC¼7.3 Hz), 120.9 (d,
JPeC¼107.2 Hz), 120.6 (d, JPeC¼11.8 Hz), 127.7 (d, JPeC¼11.8 Hz),
129.5 (d, JPeC¼8.2 Hz), 130.2 (d, JPeC¼11.8 Hz), 130.9 (d,
JPeC¼2.7 Hz), 131.0 (d, JPeC¼2.7 Hz), 131.3 (d, JPeC¼10.9 Hz), 132.7
(d, JPeC¼103.5 Hz), 133.5 (d, JPeC¼109.9 Hz), 133.6 (d,
JPeC¼12.7 Hz), 134.1 (d, JPeC¼6.4 Hz), 135.4 (d, JPeC¼6.4 Hz), 159.8
(d, JPeC¼2.7 Hz), 167.9 (d, JPeC¼3.6 Hz); dP (202 MHz, CDCl3) 28.00;
GC tR¼24.69 min; GCeMS (EI, 70 eV) m/z¼366 (Mþ) (2), 350 (29),
332 (12), 306 (31), 302 (12), 288 (12), 242 (15), 226 (12), 216 (27),
198 (36), 165 (12), 152 (30), 139 (10), 92 (14), 91 (100), 77 (33), 51
(12); HRMS [MþH]þ: calcd for C21H20O4P 367.1094. Found
367.1110.
4.2.8. o-Anisyl(3,5-dimethylphenyl)phenylphosphine oxide (6h).
Prepared using the general procedure from o-anisylphenylphos-
phine oxide (5b) (0.232 g,1 mmol) and 1-iodo-3,5-dimethylbenzene
4.2.11. ((o-Methoxycarbonyl)phenyl)methylphenylphosphine oxide
(6k). Prepared using the general procedure from methyl-
phenylphosphine oxide (5c) (0.140 g, 1 mmol) and methyl o-iodo-
benzoate (0.147 mL, 1 mmol): yield 0.252 g (92%); colorless thick
oil; Rf (CHCl3/MeOH¼15:1) 0.51; [found: C, 65.90; H, 5.66.
C15H15O3P requires C, 65.69; H, 5.51]; nmax (ATR) 3058, 2951, 1721,
1588, 1568, 1435, 1277, 1257, 1157, 1116, 1063, 880, 743, 694; dH
(500 MHz, CDCl3) 2.24 (d, JPeH¼14.2 Hz, 3H), 3.56 (s, 3H), 7.39e7.44
(m, 2H), 7.45e7.50 (m, 1H), 7.58e7.64 (m, 3H), 7.69e7.73 (m, 1H),
7.87e7.91 (m, 1H), 8.35e8.40 (m, 1H); dC (125 MHz, CDCl3) 16.3 (d,
JPeC¼77.2 Hz), 52.2, 128.2 (d, JPeC¼12.7 Hz), 129.9 (d, JPeC¼10.0 Hz),
130.2 (d, JPeC¼8.2 Hz), 131.2 (d, JPeC¼2.7 Hz), 131.6 (d, JPeC¼3.6 Hz),
131.7 (d, JPeC¼10.9 Hz), 133.6 (d, JPeC¼3.6 Hz), 134.0 (d,
JPeC¼90.8 Hz), 134.4 (d, JPeC¼8.2 Hz), 134.6 (d, JPeC¼107.2 Hz), 167.1
(d, JPeC¼2.7 Hz); dP (202 MHz, CDCl3) 32.81; GC tR¼15.19 min;
GCeMS (EI, 70 eV) m/z¼273 (5), 260 (16), 259 (100), 243 (13), 241
(9), 227 (20), 215 (11), 199 (13), 197 (17), 183 (7), 181 (25), 152 (20),
151 (10), 139 (15), 91 (16).
(0.464 g,
2 mmol): yield 0.352 g (99%); white solid; mp
208.0e209.0 ꢀC; Rf (CHCl3/MeOH¼15:1) 0.42; nmax (ATR) 3092, 3053,
3021, 3006, 2919, 2841,1588,1571,1475,1433,1280,1248,1192,1165,
1109,1013, 859, 799, 760, 715, 695; dH (500 MHz, CDCl3) 2.30 (s, 6H),
3.57 (s, 3H), 6.90e6.93 (m, 1H), 7.03e7.05 (m, 1H), 7.12 (m, 1H), 7.32
(m, 2H), 7.39e7.44 (m, 2H), 7.47e7.54 (m, 2H), 7.64e7.73 (m, 3H); dC
(125 MHz, CDCl3) 21.3, 55.2, 111.4 (d, JPeC¼6.3 Hz), 120.5 (d,
JPeC¼102.6 Hz),120.8 (d, JPeC¼10.9 Hz),128.0 (d, JPeC¼11.8 Hz),129.3
(d, JPeC¼10.9 Hz), 131.2 (d, JPeC¼2.7 Hz), 131.7 (d, JPeC¼9.9 Hz), 132.6
(d, JPeC¼107.2 Hz), 133.2 (d, JPeC¼2.7 Hz), 133.4 (d, JPeC¼106.3 Hz),
134.1 (d, JPeC¼2.7 Hz), 134.9 (d, JPeC¼7.2 Hz), 137.6 (d, JPeC¼12.7 Hz),
160.9 (d, JPeC¼2.7 Hz); dP (202 MHz, CDCl3) 27.73; GC tR¼19.31 min;
GCeMS (EI, 70 eV) m/z¼336 (Mþ) (100), 335 (40), 319 (19), 318 (47),
317 (18), 307 (13), 305 (38), 246 (13), 245 (76), 229 (37), 228 (10), 227
(61), 218 (12), 217 (86), 215 (10), 213 (16), 212 (26), 201 (19), 200 (14),
199 (88), 183 (22), 180 (12), 179 (13), 178 (10), 167 (11), 166 (17), 165
(42), 153 (16), 152 (41), 139 (23), 120 (12), 119 (46), 115 (13), 109 (10),
105 (36), 103 (15), 92 (13), 91 (52); HRMS [MþH]þ: calcd for
C21H22O2P: 337.1352. Found 337.1348. Analytical data are in accor-
dance with those reported in the literature.16
4.2.12. Methyl(2-naphthyl)phenylphosphine oxide (6l). Prepared
using the general procedure from methylphenylphosphine oxide
(5c) (0.140 g, 1 mmol) and 2-iodonaphthalene (0.254 g, 1 mmol):
yield 0.200 g (75%); pale yellow solid; mp 144.0e146.0 ꢀC (lit.35
146e147 ꢀC); Rf (EtOAc/MeOH¼20:1) 0.69; [found: C, 76.40; H,
5.50. C17H15OP requires C, 76.68; H, 5.68]; nmax (ATR) 3053, 2921,
2852, 1589, 1435, 1295, 1171, 1112, 1085, 882, 817, 704, 693; dH
(500 MHz, CDCl3) 2.12 (d, JPeH¼13.2 Hz, 3H), 7.46e7.51 (m, 2H),
7.52e7.56 (m, 1H), 7.57e7.61 (m, 2H), 7.62e7.67 (m, 1H), 7.75e7.80
(m, 2H), 7.86e7.90 (m,1H), 7.90e7.95 (m, 2H), 8.37e8.41 (m,1H); dC
(125 MHz, CDCl3) 16.5 (d, JPeC¼73.6 Hz), 125.5 (d, JPeC¼10.9 Hz),
120.0, 127.8, 128.1, 128.5 (d, JPeC¼11.8 Hz), 128.7 (d, JPeC¼11.8 Hz),
128.8, 130.5 (d, JPeC¼10.0 Hz), 131.0 (d, JPeC¼101.7 Hz), 131.8 (d,
JPeC¼2.7 Hz), 132.3 (d, JPeC¼9.1 Hz), 132.5 (d, JPeC¼12.7 Hz), 134.1
(d, JPeC¼100.8 Hz), 134.6 (d, JPeC¼2.7 Hz); dP (202 MHz, CDCl3)
4.2.9. (p-Aminophenyl)(o-anisyl)phenylphophine oxide (6i). Prepared
using the general procedure from o-anisylphenylphosphine oxide
(5b) (0.232 g, 1 mmol) and p-iodoaniline (0.219 g, 1 mmol): yield
0.307
g
(95%); brown solid; mp 219.0e222.0 ꢀC; Rf (CHCl3/
MeOH¼15:1) 0.46; [found: C, 70.80; H, 5.79; N, 4.00. C19H18NO2P
requires C, 70.58; H, 5.61; N, 4.33]; nmax (ATR) 3331, 3207, 3072, 2928,
2849, 1635, 1596, 1506, 1476, 1430, 1272, 1245, 1150, 1115, 1101, 1017,
801, 755, 692; dH (500 MHz, CDCl3) 3.56 (s, 3H), 4.07 (br s, 2H),
6.63e6.67 (m, 2H) 6.82e6.92 (m, 1H), 6.99e7.08 (m, 1H), 7.37e7.42
(m, 2H), 7.42e7.47 (m, 3H), 7.47e7.53 (m, 1H), 7.65e7.71 (m, 2H),
7.68e7.79 (m, 1H); dC (125 MHz, CDCl3) 55.2, 111.3 (d, JPeC¼6.4 Hz),
114.0 (d, JPeC¼12.7 Hz), 120.4 (d, JPeC¼116.3 Hz), 121.0 (d,
JPeC¼103.5 Hz), 120.7 (d, JPeC¼10.9 Hz), 127.9 (d, JPeC¼11.8 Hz), 131.1
(d, JPeC¼2.7 Hz),131.7 (d, JPeC¼10.0 Hz), 133.5 (d, JPeC¼10.9 Hz), 134.2
(d, JPeC¼108.1 Hz),133.9 (d, JPeC¼1.8 Hz),134.9 (d, JPeC¼7.3 Hz),149.5
(d, JPeC¼2.7 Hz),160.8 (d, JPeC¼2.7 Hz); dP (202 MHz, CDCl3) 27.51; GC
tR¼29.46 min; GCeMS (EI, 70 eV) m/z¼323 (Mþ) (11), 305 (9), 292
(18), 236 (26), 214 (21), 199 (13), 167 (10), 152 (7),107 (12), 106 (100),
93 (12), 91 (11); HRMS [MþH]þ: calcd for C19H19NO2P: 324.1148.
Found 324.1126.
d
30.90; GC tR¼16.90 min; GCeMS (EI, 70 eV) m/z¼266 (Mþ) (51),
265 (100), 251 (35), 233 (6), 207 (5), 202 (9), 173 (7), 128 (9), 127
(27), 126 (9), 115 (8), 91 (6). Analytical data are in accordance with
those reported in the literature.36
4.2.13. o-Anisylmethylphenylphosphine oxide (6m). Prepared using
the general procedure from methylphenylphosphine oxide (5c)
(0.140 g, 1 mmol) and o-iodoanisole (0.130 mL, 1 mmol): yield
0.170 g (69%); white solid; mp 131.0e133.0 ꢀC (lit.37 129e130 ꢀC); Rf
(CHCl3/MeOH¼20:1) 0.33; [found: C, 68.45; H, 6.00. C14H15O2P
requires C, 68.29; H, 6.14]; nmax (ATR) 3048, 3004, 2940, 2838, 1590,
4.2.10. o-Anisyl((o-methoxycarbonyl)phenyl)phenylphosphine oxide
(6j). Prepared using the general procedure from o-anisyl-

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79
1578, 1478, 1462, 1433, 1273, 1239, 1167, 1117, 1076, 1020, 879, 864,
770, 756, 699; dH (500 MHz, CDCl3) 2.09 (d, JPeH¼14.2 Hz, 3H), 3.74
(s, 3H), 6.87e6.92 (m, 1H), 7.09e7.14 (m, 1H), 7.40e7.45 (m, 2H),
7.46e7.49 (m, 1H), 7.49e7.54 (m, 1H), 7.72e7.78 (m, 2H), 7.95e8.00
(m, 1H); dC (125 MHz, CDCl3) 16.1 (d, JPeC¼74.5 Hz), 55.3, 110.8 (d,
JPeC¼6.4 Hz), 121.0 (d, JPeC¼10.9 Hz), 128.2 (d, JPeC¼12.7 Hz), 130.2
(d, JPeC¼10.0 Hz),131.2 (d, JPeC¼2.7 Hz),133.8 (d, JPeC¼1.8 Hz),133.9
(d, JPeC¼6.4 Hz), 135.0 (d, JPeC¼104.4 Hz), 159.8 (d, JPeC¼4.5 Hz); dP
(202 MHz, CDCl3) 28.38; GC tR¼14.64 min; GCeMS (EI, 70 eV)
m/z¼246 (M) (55), 245 (51), 229 (24), 228 (37), 217 (28), 216 (15),
215 (100), 213 (18), 199 (33), 167 (17), 155 (69), 153 (12), 152 (33),
140 (15), 139 (37), 137 (12), 125 (19), 121 (10), 115 (12), 109 (11), 107
(12), 95 (11), 92 (20), 91 (85). Analytical data are in accordance with
those reported in the literature.38
128 (55), 127 (33), 126 (10); HRMS [MþH]þ: calcd for C20H22OP:
309.1403. Found 309.1405.
4.2.17. (p-Bromophenyl)-tert-butylphenylphosphine oxide (6q).
Prepared using the general procedure from tert-butylphenylphos-
phine oxide (5d) (0.182 g, 1 mmol) and p-bromoiodobenzene
(0.283 g,
1 mmol): yield 0.270 g (80%); olive solid; mp
126.8e128.7 ꢀC; Rf (CHCl3/MeOH¼15:1) 0.77; [found: C, 56.97; H,
5.33. C16H18BrOP requires C, 56.99; H, 5.38]; nmax (ATR) 3060, 2957,
2864, 1576, 1472, 1433, 1381, 1359, 1166, 1108, 1069, 1006, 813, 732,
712, 693; dH (300 MHz, CDCl3) 1.23 (d, JPeH¼15.0 Hz, 9H), 7.43e7.57
(m, 3H), 7.58e7.65 (m, 2H), 7.77e7.85 (m, 2H), 7.87e7.96 (m, 2H); dC
(75 MHz, CDCl3) 25.1, 33.9 (d, JPeC¼71.4 Hz), 126.6 (d, JPeC¼3.5 Hz),
128.3 (d, JPeC¼10.9 Hz), 131.5 (d, JPeC¼10.9 Hz), 131.6 (d,
JPeC¼2.3 Hz), 132.0 (d, JPeC¼8.1 Hz), 133.6 (d, JPeC¼8.6 Hz); dP
(121.5 MHz, CDCl3) 38.77; GC tR¼18.73 min; GCeMS (EI, 70 eV)
m/z¼336 (Mþ) (0.2), 282 (11), 281 (93), 281 (30), 280 (100), 278
(16), 201 (50), 154 (42), 152 (15), 125 (25); HRMS [MþH]þ: calcd for
C16H19BrOP: 337.0351. Found 337.0339.
4.2.14. Methylphenyl(o-tolyl)phosphine oxide (6n). Prepared using
the general procedure from methylphenylphosphine oxide (5c)
(0.140 g, 1 mmol) and o-iodotoluene (0.127 mL, 1 mmol): yield
0.173 g (75%); white solid; mp 130.5e131.1 ꢀC (lit.39 134 ꢀC); Rf
(CHCl3/MeOH¼15:1) 0.67; [found: C, 73.13; H, 6.42. C14H15OP re-
quires C, 73.03; H, 6.57]; nmax (ATR) 3055, 2980, 2917, 1592, 1452,
1436, 1299, 1166, 1135, 1110, 1029, 879, 739, 694; dH (500 MHz,
CDCl3) 2.04 (d, JPeH¼13.2 Hz, 3H), 2.38 (s, 3H), 7.21e7.25 (m, 1H),
7.28e7.33 (m, 1H), 7.42e7.48 (m, 3H), 7.49e7.54 (m, 1H), 7.63e7.71
(m, 3H); dC (125 MHz, CDCl3) 17.2 (d, JPeC¼73.6 Hz), 21.3 (d,
JPeC¼4.5 Hz), 125.5 (d, JPeC¼11.8 Hz), 128.6 (d, JPeC¼11.8 Hz), 130.3
(d, JPeC¼10.0 Hz), 131.4 (d, JPeC¼11.8 Hz), 131.5 (d, JPeC¼2.7 Hz),
131.8 (d, JPeC¼10.0 Hz), 132.0 (d, JPeC¼2.7 Hz), 134.7 (d,
JPeC¼99.9 Hz), 142.05 (d, JPeC¼9.1 Hz); dP (202 MHz, CDCl3) 31.62;
GC tR¼13.83 min; GCeMS (EI, 70 eV) m/z¼230 (Mþ) (26), 229 (100),
215 (5), 165 (14), 91 (15). Analytical data are in accordance with
those reported in the literature.40
4.2.18. tert-Butyl((o-methoxycarbonyl)phenyl)phenylphosphine ox-
ide (6r). Prepared using the general procedure from tert-butyl-
phenylphosphine oxide (5d) (0.182 g, 1 mmol) and methyl o-
iodobenzoate (0.147 mL, 1 mmol): yield 0.171 g (54%); pale yellow
thick oil; Rf (CHCl3/MeOH¼15:1) 0.54; [found: C, 68.35; H, 6.95.
C18H21O3P requires C, 68.34; H, 6.69]; nmax (ATR) 3056, 2962, 2867,
1733,1475, 1458, 1430, 1394, 1366,1292, 1253, 1170,1117, 1105, 1067,
812, 756, 717, 701; dH (500 MHz, CDCl3) 1.31 (d, JPeH¼14.8 Hz, 9H),
3.69 (s, 3H), 7.41e7.57 (m, 6H), 7.75e7.80 (m, 2H), 7.92e7.99 (m,
1H); dC (125 MHz, CDCl3) 25.7, 34.7 (d, JPeC¼69.9 Hz), 52.3, 128.0 (d,
JPeC¼11.8 Hz), 128.7 (d, JPeC¼10.9 Hz), 129.3 (d, JPeC¼8.2 Hz), 129.8
(d, JPeC¼86.3 Hz), 131.1 (d, JPeC¼3.6 Hz), 131.1 (d, JPeC¼2.7 Hz), 131.4
(d, JPeC¼9.1 Hz), 131. 5 (d, JPeC¼8.2 Hz), 139.3 (d, JPeC¼5.45 Hz),
169.6 (d, JPeC¼3.6 Hz); dP (202 MHz, CDCl3) 39.89; GC
tR¼18.64 min; GCeMS (EI, 70 eV) m/z¼316 (Mþ) (1), 260 (16), 259
(100), 245 (64), 227 (30), 199 (14), 167 (18), 152 (26); HRMS
[MþH]þ: calcd for C18H22O3P: 317.1301. Found: 317.1290.
4.2.15. tert-Butyldiphenylphosphine oxide (6o). Prepared using the
general procedure from tert-butylphenylphosphine oxide (5d)
(0.182 g, 1 mmol) and iodobenzene (0.112 mL, 1 mmol): yield
0.235 g (91%); white solid; mp 124.2e126.0 ꢀC (lit.41 127e129 ꢀC); Rf
(CHCl3/MeOH¼15:1) 0.49; [found: C, 74.40; H, 7.41. C16H19OP re-
quires C, 76.68; H, 5.68]; nmax (ATR) 3095, 2963, 2086, 1475, 1436,
1394, 1365, 1213, 1163, 1111, 1095, 813, 744, 719, 699; dH (500 MHz,
CDCl3) 1.19 (d, JPeH¼14.8 Hz, 9H), 7.38e7.48 (m, 6H), 7.88e7.94 (m,
4H); dC (125 MHz, CDCl3) 25.0, 33.7 (d, JPeC¼69.9 Hz), 128.0 (d,
JPeC¼10.9 Hz), 130.9 (d, JPeC¼89.92 Hz), 131.2 (d, JPeC¼2.7 Hz), 131.9
(d, JPeC¼8.2 Hz); dP (202 MHz, CDCl3) 38.48; GC tR¼16.52 min;
GCeMS (EI, 70 eV) m/z¼258 (Mþ) (0.25), 203 (13), 202 (100), 201
(24), 155 (32), 125 (11); HRMS [MþH]þ: calcd for C16H20OP
259.1246. Analytical data are in accordance with those reported in
the literature.41
4.2.19. Di(n-hexyl)-2-pyridylphosphine oxide (6s). Prepared using
the general procedure from di-n-hexylphosphine oxide (5e)
(0.218 g, 1 mmol) and 2-bromopyridine (0.096 mL, 1 mmol): yield
0.180 g (61%); colorless oil; Rf (CHCl3/MeOH¼20:1) 0.83; [found: C,
69.30; H, 10.26; N, 4.50. C17H30NOP requires C, 69.12; H, 10.24; N,
4.74]; nmax (ATR) 3046, 2954, 2925, 2857, 1575, 1455, 1425, 1378,
1180,1137,1084, 990, 755; dH (500 MHz, CDCl3) 0.83 (t, JHeH¼6.6 Hz,
6H), 1.17e1.27 (m, 9H), 1.28e1.42 (m, 7H), 1.95e2.09 (m, 4H),
7.34e7.44 (m, 1H), 7.80e7.87 (m, 1H), 8.07e8.16 (m, 1H), 8.68e8.75
(m, 1H); dC (125 MHz, CDCl3) 13.9, 21.2, 22.2, 28.3 (d, JPeC¼68.1 Hz),
30.4 (d, JPeC¼14.5 Hz), 31.1, 124.9 (d, JPeC¼1.8 Hz), 127.8 (d,
JPeC¼17.3 Hz), 135.8 (d, JPeC¼8.2 Hz), 149.8 (d, JPeC¼18.2 Hz), 156.6
(d, JPeC¼118.1 Hz); dP (202 MHz, CDCl3) 42.20; GC tR¼14.69 min;
GCeMS (EI, 70 eV) m/z¼295 (Mþ) (1), 280 (4), 266 (17), 238 (15),
211 (26), 210 (92), 196 (8), 168 (14), 162 (12), 148 (81), 141 (18), 135
(28), 134 (48), 127 (15), 126 (92), 120 (14), 110 (10), 106 (29), 93
(100), 80 (14).
4.2.16. tert-Butyl(2-naphthyl)phenylphosphine oxide (6p). Prepared
using the general procedure from tert-butylphenylphosphine oxide
(5d) (0.182 g, 1 mmol) and 2-iodonaphthalene (0.254 g, 1 mmol):
yield 0.265 g (86%); purple solid; mp 152.8e154.8 ꢀC; Rf (CHCl3/
MeOH¼15:1) 0.83; [found: C, 77.99; H, 6.99. C20H21OP requires C,
77.90; H, 6.86]; nmax (ATR) 3051, 2960, 2900, 2864, 1586, 1474,
1435, 1362, 1164, 1134, 1103, 1080, 1009, 854, 828, 812, 745, 710,
695; dH (400 MHz, CDCl3) 1.36 (d, JPeH¼14.9 Hz, 9H), 7.21e7.27 (m,
3H), 7.35e7.41 (m, 2H), 7.87e7.97 (m, 4H), 8.02e8.09 (m, 2H),
8.59e8.64 (m, 1H); dC (75 MHz, CDCl3) 25.3, 34.2 (d, JPeC¼70.7 Hz),
126.8 (d, JPeC¼12.4 Hz), 126.9, 127.9 (d, JPeC¼91.7 Hz), 128.0 (d,
JPeC¼11.5 Hz), 128.2, 128.47, 128.49 (d, JPeC¼11.5 Hz), 128.6 (d,
JPeC¼12.1 Hz), 129.0, 130.5 (d, JPeC¼91.7 Hz), 131.8 (d, JPeC¼2.9 Hz),
132.1 (d, JPeC¼10.1 Hz), 132.2 (d, JPeC¼8.3 Hz), 132.5 (d,
JPeC¼12.1 Hz), 134.5 (d, JPeC¼7.2 Hz), 134.5 (d, JPeC¼2.0 Hz); dP
(162 MHz, CDCl3) 41.64; GC tR¼21.41 min; GCeMS (EI, 70 eV)
m/z¼308 (Mþ) (6), 253 (17), 252 (100); 251 (51), 205 (32), 204 (10),
4.2.20. 2-Furyl-di(n-hexyl)phosphine oxide (6t). Prepared using the
general procedure from di-n-hexylphosphine oxide (5e) (0.218 g,
1 mmol) and 2-iodofurane (0.096 mL, 1 mmol): yield 0.270 g (95%);
colorless oil; Rf (CHCl3/MeOH¼20:1) 0.60; [found: C, 67.40; H,
10.50. C16H29O2P requires C, 67.58; H, 10.28]; nmax (ATR) 3114, 2954,
2926, 2857, 1555, 1463, 1403, 1367, 1189, 1161, 1125, 1003, 909, 749,
719, 695; dH (500 MHz, CDCl3) 0.86 (t, JHeH¼6.9 Hz, 6H), 1.20e1.31
(m, 8H), 1.32e1.41 (m, 4H), 1.42e1.54 (m, 2H), 1.56e1.68 (m, 2H),
1.85e2.01 (m, 4H), 6.48e6.52 (m, 1H), 7.11e7.14 (m, 1H), 7.64e7.67
(m, 1H); dC (125 MHz, CDCl3) 14.0, 21.2 (d, JPeC¼3.6 Hz), 22.4, 29.5

ꢀ
M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
80
(d, JPeC¼72.7 Hz), 30.5 (d, JPeC¼14.5 Hz), 31.2, 110.7 (d, JPeC¼7.3 Hz),
121.2 (d, JPeC¼15.4 Hz), 147.1 (d, JPeC¼6.4 Hz); dP (162 MHz, CDCl3)
34.60; GC tR¼13.54 min; GCeMS (EI, 70 eV) m/z¼284 (Mþ) (28),
255 (39), 241 (52), 227 (49), 213 (13), 200 (11), 199 (26), 185 (31),
182 (12), 172 (13), 171 (39), 158 (13), 157 (44), 144 (68), 143 (18), 131
(14), 130 (100), 129 (12), 117 (13), 116 (20), 115 (87), 99 (10), 83 (14),
82 (10), 81 (93).
requires C, 68.94; H, 8.39]; nmax (ATR) 3059, 2919, 2848, 1715, 1587,
1568, 1448, 1428, 1296, 1264, 1159, 1111, 1059, 961, 883, 740, 715,
696; dH (500 MHz, CDCl3) 1.09e1.37 (m, 10H), 1.60e1.71 (m, 6H),
1.80e1.88 (m, 2H), 2.05e2.14 (m, 2H), 2.29e2.40 (m, 2H), 3.93 (s,
3H), 7.52e7.56 (m, 1H), 7.62e7.66 (m, 1H), 7.88e7.94 (m, 1H),
8.18e8.25 (m, 1H); dC (125 MHz, CDCl3) 25.7, 26.3 (d, JPeC¼3.6 Hz),
26.5 (d, JPeC¼34.5 Hz), 26.4 (d, JPeC¼3.6 Hz), 26.5 (d, JPeC¼8.2 Hz),
37.1 (d, JPeC¼68.1 Hz), 52.6, 130.0 (d, JPeC¼7.3 Hz), 130.6 (d,
JPeC¼2.7 Hz),131.6 (d, JPeC¼10.0 Hz),135.0 (d, JPeC¼7.3 Hz),168.0 (d,
JPeC¼1.8 Hz); dP (202 MHz, CDCl3) 49.87; GC tR¼20.86 min; GCeMS
(EI, 70 eV) m/z¼348 (Mþ) (0.5), 289 (27), 265 (44), 252 (14), 251
(100), 183 (23), 169 (20), 153 (14), 151 (47), 83 (11), 77 (13), 55 (67),
47 (10), 41 (42); HRMS [MþH]þ: calcd for C20H30O3P: 349.1927.
Found: 349.1911.
4.2.21. Di(c-hexyl)phenylphosphine oxide (6u). Prepared using the
general procedure from di-c-hexylphosphine oxide (5f) (0.214 g,
1 mmol) and iodobenzene (0.224 mL, 2 mmol): yield 0.281 g (97%);
white solid; mp 154.0e154.9 ꢀC (lit.42, 157.5 ꢀC); Rf (CHCl3/
MeOH¼20:1) 0.38; [found: C, 74.35; H, 9.45. C18H27OP requires C,
74.45; H, 9.37]; nmax (ATR) 3051, 2927, 2851, 1436, 1208, 1163, 1112,
1002, 889, 851, 743, 697; dH (400 MHz, CDCl3) 1.07e1.36 (m, 10H),
1.57e1.70 (m, 4H), 1.70e1.78 (m, 2H), 1.78e1.85 (m, 2H), 1.98e2.09
(m, 4H), 7.43e7.54 (m, 3H), 7.61e7.68 (m, 2H); dC (75 MHz, CDCl3)
24.6 (d, JPeC¼3.5 Hz), 25.5 (d, JPeC¼2.0 Hz), 25.8 (d, JPeC¼1.4 Hz),
26.3 (d, JPeC¼8.0 Hz), 26.5 (d, JPeC¼8.6 Hz), 35.1 (d, JPeC¼67.2 Hz),
128.2 (d, JPeC¼10.1 Hz), 129.9 (d, JPeC¼85.6 Hz), 131.2 (d,
JPeC¼3.2 Hz),131.4 (d, JPeC¼7.8 Hz); dP (121.5 MHz, CDCl3) 45.52; GC
tR¼19.56 min; GCeMS (EI, 70 eV) m/z¼290 (Mþ) (7), 289 (6), 235
(21), 209 (21), 208 (100), 207 (16),193 (5),167 (6),154 (10),153 (30),
127 (43), 126 (44), 125 (49), 83 (21), 81 (14).
4.2.25. Phenyl-di-o-tolylphosphine oxide (6y). Prepared using the
general procedure from di-o-tolylphosphine oxide (5h) (0.460 g,
2 mmol) and o-bromoiodobenzene (0.128 mL, 1 mmol): yield
0.064 g (21%); pale brown waxy solid; Rf (CHCl3/MeOH¼15:1) 0.71;
[found: C, 78.60; H, 6.49. C20H19OP requires C, 78.41; H, 6.25]; dH
(500 MHz, CDCl3) 2.52 (s, 6H), 7.01e7.06 (m, 2H), 7.12e7.17 (m, 2H),
7.29e7.33 (m, 2H), 7.41e7.45 (m, 2H), 7.46e7.50 (m, 2H), 7.54e7.59
(m, 1H), 7.59e7.64 (m, 2H); dC (125 MHz, CDCl3) 21.8 (d,
JPeC¼4.5 Hz), 125.3 (d, JPeC¼12.7 Hz), 128.5 (d, JPeC¼12.7 Hz), 130.8
(d, JPeC¼101.7 Hz), 131.7 (d, JPeC¼2.7 Hz), 131.8 (d, JPeC¼2.7 Hz),
131.9 (d, JPeC¼10.9 Hz), 132.2 (d, JPeC¼10.0 Hz), 132.7 (d,
JPeC¼102.6 Hz), 132.9 (d, JPeC¼12.7 Hz), 143.4 (d, JPeC¼8.2 Hz); dP
(202 MHz, CDCl3) 39.40; GC tR¼16.16 min; GCeMS (EI, 70 eV)
m/z¼306 (Mþ) (6), 305 (20), 292 (21), 291 (100), 213 (18), 166 (18),
165 (37), 152 (8), 109 (6), 91 (18).
4.2.22. Di(c-hexyl)-2-pyridylphosphine oxide (6v). Prepared using
the general procedure from di-c-hexylphosphine oxide (5f)
(0.214 g, 1 mmol) and 2-bromopyridine (0.192 mL, 2 mmol): yield
0.285 g (98%); colorless oil; Rf (CHCl3/MeOH¼20:1) 0.38; [found: C,
70.22; H, 9.12; N, 5.00. C17H26NOP requires C, 70.08; H, 8.99; N,
4.81]; nmax (ATR) 3052, 2954, 2925, 2857, 1575, 1455, 1425, 1181,
1137, 1084, 990, 755, 721, 695; dH (500 MHz, CDCl3) 1.03e1.31 (m,
8H), 1.33e1.44 (m, 2H), 1.44e1.54 (m, 2H), 1.57e1.72 (m, 4H),
1.72e1.83 (m, 2H), 1.97e2.09 (m, 2H), 2.12e2.24 (m, 2H), 7.28e7.35
(m,1H), 7.72e7.79 (m,1H), 7.99e8.05 (m,1H), 8.66e8.72 (m,1H); dC
(125 MHz, CDCl3) 24.7 (d, JPeC¼2.7 Hz), 25.3 (d, JPeC¼3.6 Hz), 25.8,
26.2 (d, JPeC¼12.4 Hz), 26.3 (d, JPeC¼12.6 Hz), 34.8 (d, JPeC¼66.3 Hz),
124.7 (d, JPeC¼2.7 Hz), 129.2 (d, JPeC¼16.4 Hz), 135.5 (d,
JPeC¼8.2 Hz), 149.4 (d, JPeC¼17.3 Hz), 155.6 (d, JPeC¼110.8 Hz); dP
(202 MHz, CDCl3) 44.88; GC tR¼19.38 min; GCeMS (EI, 70 eV)
m/z¼236 (4), 209 (59), 208 (100), 161 (36), 160 (15), 127 (52), 126
(97), 109 (17), 93 (17).
4.2.26. 1,2-Bis(diphenylphosphinoyl)benzene (8a). Prepared using
the general procedure from diphenylphosphine oxide (5a) (0.404 g,
2 mmol) and o-bromoiodobenzene (0.128 mL, 1 mmol): yield
0.339 g (71%); colorless oil; Rf (CHCl3/MeOH¼15:1) 0.37; [found: C,
75.39; H, 5.15. C30H24O2P2 requires C, 75.31; H, 5.06]; nmax (ATR)
3054, 2963, 1589, 1483, 1435, 1195, 1115, 1070, 741, 719, 689; dH
(500 MHz, CDCl3) 7.24e7.29 (m, 8H), 7.36e7.40 (m, 4H), 7.43e7.49
(m, 8H), 7.62e7.66 (m, 2H), 7.93e8.00 (m, 2H); dC (125 MHz, CDCl3)
127.8e127.9 (m), 130.9e131.2 (m), 131.4, 131.9e132.1 (m), 133.1 (d,
JPeC¼108.1 Hz), 135.8e136.0 (m); dP (202 MHz, CDCl3) 31.43. Ana-
lytical data are in accordance with those reported in the literature.43
4.2.23. 2-Furyl-di(c-hexyl)phosphine oxide (6w). Prepared using
the general procedure from di-c-hexylphosphine oxide (5f)
(0.214 g, 1 mmol) and 2-iodofurane (0.096 mL, 1 mmol): yield
0.274 g (98%); white solid; Rf (CHCl3/MeOH¼20:1) 0.40; [found: C,
68.45; H, 8.95. C16H25O2P requires C, 68.55; H, 8.99]; nmax (ATR)
2928, 2853, 1555, 1448, 1210, 1160, 1125, 1004, 889, 851, 744; dH
(400 MHz, CDCl3) 0.90e1.17 (m, 10H), 1.54e1.63 (m, 2H), 1.63e1.72
(m, 2H), 1.72e1.87 (m, 4H), 1.94e2.07 (m, 4H), 6.47e6.50 (m, 1H),
7.11e7.15 (m, 1H), 7.63e7.67 (m, 1H); dC (75 MHz, CDCl3) 24.4 (d,
JPeC¼3.2 Hz), 25.1 (d, JPeC¼2.9 Hz), 25.8 (d, JPeC¼1.7 Hz), 26.2 (d,
JPeC¼7.8 Hz), 26.4 (d, JPeC¼8.3 Hz), 35.5 (d, JPeC¼71.3 Hz), 110.5 (d,
JPeC¼7.2 Hz), 122.8 (d, JPeC¼13.8 Hz), 147.0 (d, JPeC¼112.6 Hz), 147.1
(d, JPeC¼5.7 Hz); dP (162 MHz, CDCl3) 41.37; GC tR¼17.84 min;
GCeMS (EI, 70 eV) m/z¼280 (Mþ) (22), 251 (10), 225 (27), 199 (18),
198 (63), 197 (16), 170 (41), 169 (15), 156 (11), 143 (22), 142 (15), 133
(12), 1332 (12), 130 (23), 117 (30), 116 (59), 115 (100), 104 (9), 95 (8),
88 (15), 83 (57), 81 (42).
4.2.27. 1,2-Bis(di-p-tolylphosphinoyl)benzene (8b). Prepared using
the general procedure from di-p-tolylphosphine oxide (5g) (0.460 g,
2 mmol) and o-bromoiodobenzene (0.128 mL,1 mmol): yield 0.075 g
(14%); colorless oil; Rf (CHCl3/MeOH¼15:1) 0.48; [found: C, 76.22; H,
5.88. C34H32O2P2 requires C, 76.39; H, 6.03]; nmax (ATR) 3021, 2962,
2921, 1601, 1500, 1450, 1398, 1185, 1113, 1098, 1020, 909, 803, 742; dH
(500 MHz, CDCl3) 2.32 (s,12H), 7.01e7.08 (m, 8H), 7.28e7.37 (m, 8H),
7.56e7.64 (m, 2H), 7.91e8.02 (m, 2H); dC (125 MHz, CDCl3) 21.3,
128.3e128.5 (m), 130.1 (d, JPeC¼109.9 Hz), 130.7 (d, JPeC¼10.0 Hz),
130.8 (d, JPeC¼9.1 Hz),132.0e132.2 (m),135.8 (d, JPeC¼10.0 Hz), 135.9
(d, JPeC¼10.9 Hz), 136.7 (dd, JPeC¼8.2 Hz, JPeC¼98.1 Hz), 141.4 (d,
JPeC¼1.8 Hz); dP (202 MHz, CDCl3) 31.42.
4.2.28. 1,2-Bis(di-o-tolylphosphinoyl)benzene (8c). Prepared using
the general procedure from di-o-tolylphosphine oxide (5h)
(0.460 g, 2 mmol) and o-bromoiodobenzene (0.128 mL, 1 mmol):
yield 0.390 g (73%); pale yellow thick oil; Rf (CHCl3/MeOH¼15:1)
0.65; [found: C, 76.60; H, 6.00. C34H32O2P2 requires C, 76.39; H,
6.03]; nmax (ATR) 3057, 2959, 2917, 1618, 1592, 1567, 1451, 1434,
1285, 1203, 1157, 1130, 1109, 1086, 1027, 806, 756, 722, 694; dH
(500 MHz, CDCl3) 2.37 (br s, 12H), 6.82e7.13 (br m, 12H), 7.15e7.31
(br m, 6H), 7.61e7.68 (m, 2H); dC (125 MHz, CDCl3) 21.9 (d,
JPeC¼1.8 Hz), 124.3 (d, JPeC¼12.7 Hz), 129.9e130.3 (br m), 131.0 (d,
4.2.24. Di-c-hexyl(o-methoxycarbonylphenyl)phosphine oxide (6x).
Prepared using the general procedure from di-c-hexylphosphine
oxide (5f) (0.214 g, 1 mmol) and methyl o-iodobenzoate (0.147 mL,
1 mmol): yield 0.285 g (82%); pale yellow solid; mp 149.0e151.0 ꢀC;
Rf (CHCl3/MeOH¼15:1) 0.43; [found: C, 69.12; H, 8.50. C20H29O3P

ꢀ
M. Stankevic, A. Włodarczyk / Tetrahedron 69 (2013) 73e81
81
9. (a) Wen, J.-F.; Hong, W.; Yuan, K.; Mak, T. C. W.; Wong, H. N. C. J. Org. Chem.
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Muller, G.; Solans, X.; Font-Bardia, M. Tetrahedron: Asymmetry 2004, 15,
1477e1486.
JPeC¼7.3 Hz), 131.4, 133.6e134.3 (br m), 135.3e135.9 (br m), 142.9
(d, JPeC¼7.3 Hz); dP (202 MHz, CDCl3) 37.51.
10. (a) Evano, G.; Tadiparthi, K.; Couty, F. Chem. Commun. 2011,179e181; (b) Zhuang,
R.; Xu, J.; Cai, Z.; Tang, G.; Fang, M.; Zhao, Y. Org. Lett. 2011, 13, 2110e2113.
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Allen, D.; Venkataraman, D. J. Org. Chem. 2003, 68, 4590e4593; (c) Tani, K.;
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5020e5022; (b) Jiang, D.; Jiang, Q.; Fu, H.; Jiang, Y.; Zhao, Y. Synthesis 2008,
3473e3477.
4.2.29. 1,2-Bis(di-p-anisylphosphinoyl)benzene (8d). Prepared using
the general procedure from di-p-anisylphosphine oxide (5i)
(0.524 g, 2 mmol) and o-bromoiodobenzene (0.128 mL, 1 mmol):
yield 0.156 g (26%); pale brown thick oil; Rf (CHCl3/MeOH¼15:1)
0.44; [found: C, 68.44; H, 5.74. C34H32O6P2 requires C, 68.22; H,
5.39]; nmax (ATR) 2962, 2838, 1595, 1569, 1502, 1460, 1440, 1292,
1252, 1176, 1115, 1025, 909, 825, 800, 742; dH (500 MHz, CDCl3) 3.80
(s, 12H), 6.72e6.78 (m, 8H), 7.32e7.40 (m, 8H), 7.58e7.64 (m, 2H),
7.95e8.04 (m, 2H); dC (125 MHz, CDCl3) 55.1, 113.1e113.3 (m), 124.8
(d, JPeC¼114.4 Hz), 130.7e130.9 (m), 133.8e134.1 (m), 135.8 (dd,
JPeC¼10.0 Hz, JPeC¼10.9 Hz), 136.9 (dd, JPeC¼8.2 Hz, JPeC¼99.0 Hz),
161.8; dP (202 MHz, CDCl3) 30.79.
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14. McDougal, N. T.; Streuff, J.; Mukherjee, H.; Virgil, S. C.; Stolz, B. M. Tetrahedron
Lett. 2010, 51, 5550e5554.
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15. (a) Stankevic, M.; Pietrusiewicz, K. M. Tetrahedron Lett. 2009, 50, 7093e7096;
ꢀ
ꢁ
ꢀ
(b) Stankevic, M.; Jaklinska, M.; Pietrusiewicz, K. M. J. Org. Chem. 2012, 77,
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1991e2000; (c) Stankevic, M.; Jaklinska, M.; Wojcik, K.; Pietrusiewicz, K. M. Eur.
J. Org. Chem. 2012, 2521e2534.
16. Stankevic, M.; W1odarczyk, A.; Jaklinska, M.; Parcheta, R.; Pietrusiewicz, K. M.
Tetrahedron 2011, 67, 8671e8678.
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Acknowledgements
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Authors are grateful to Dr. Duncan Carmichael for his guidance
during the preparation of the manuscript.
19. Eaborn, C.; Golborn, P.; Spillett, R. E.; Taylor, R. J. Chem. Soc. B 1968, 1112e1123.
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Supplementary data
21. Banerjee, M.; Shukla, R.; Rathore, R. J. Am. Chem. Soc. 2009, 131, 1780e1786.
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