Ytterbium-catalyzed dual intermolecular hydrophosphination: Synthesis of bis(phosphinyl)dienes and bis(alkenyl)phosphine oxides

Article abstract of DOI:10.1016/j.tet.2005.12.049

Dual intermolecular hydrophosphination of conjugated diynes with 2 equiv of diphenylphosphine was catalyzed by ytterbium complexes, Yb(η²- Ph₂CNPh)(hmpa)₃ (1) and Yb[N(SiMe₃) ₂]₃(hmpa)

Full text of DOI:10.1016/j.tet.2005.12.049

Tetrahedron 62 (2006) 2511–2519
Ytterbium-catalyzed dual intermolecular hydrophosphination:
synthesis of bis(phosphinyl)dienes and
bis(alkenyl)phosphine oxides
*
Kimihiro Komeyama, Daisuke Kobayashi, Yuta Yamamoto,
*
Katsuomi Takehira and Ken Takaki
Department of Chemistry and Chemical Engineering, Graduate School of Engineering, Hiroshima University, Kagamiyama,
Higashi-Hiroshima 739-8527, Japan
Received 19 November 2005; revised 17 December 2005; accepted 21 December 2005
Available online 18 January 2006
Abstract—Dual intermolecular hydrophosphination of conjugated diynes with 2 equiv of diphenylphosphine was catalyzed by ytterbium
complexes, Yb(h2-Ph2CNPh)(hmpa)3 (1) and Yb[N(SiMe3)2]3(hmpa)2 (2), to give the corresponding 1,4-bis(diphenylphosphinyl)buta-1,3-
dienes in high yields after oxidative work-up. Distribution of the four possible stereoisomers sharply depended on substituents of the
substrates. (Z,Z)-Isomers were predominantly obtained from the disubstituted diynes, together with minor (Z,E)-isomers. On the other hand,
the reaction of the terminal diynes provided major (E,Z) and minor (E,E)-butadienes. 1,4-Di-tert-butylbuta-1,3-diyne was exclusively
converted to an allenic compound. Moreover, the dual hydrophosphination using phenyphosphine was also performed with 1 and 2. Thus, the
reaction of 2 equiv of aromatic alkynes with PhPH2 and subsequent oxidation gave bis(alkenyl)phosphine oxides in preference of the
(Z,Z)-stereoisomers.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
the active species generated in situ were ytterbium
phosphides, Yb(PPh2)2 and Yb(PPh2)3, which exhibited
similar regio- and stereoselectivity irrespective of their
valence state.5 Based on this work, we intended to
develop a simple method for the synthesis of potentially
useful phosphorus compounds 3–5. Diphenylphosphinyl-
a,b-Unsaturated phosphorus compounds are useful building
blocks in organic synthesis.1 Of their synthetic methods,
addition reaction of (RO)2P(O)H and R2P(O)H to alkynes
through oxidative addition of groups 9 and 10 catalysts to
P–H bond has been recognized as the most promising and
atom-economical process.2 When this methodology was
applied to the reaction of R2PH, instead of pentavalent
phosphorus, harsh conditions were necessary to promote the
reaction, because of strong affinity of the late transition
metals with the trivalent phosphines.3 On the other hand,
interaction between hard lanthanide metals and the soft
phosphines could be so weak, and thus efficient intra-
molecular hydrophosphination of alkynyl and alkenylpho-
sphines has been explored with lanthanocenes.4
dienes
3
have been already prepared by the
Y[N(SiMe3)2]3-catalyzed dimerization of terminal
alkynes, followed by hydrophosphination of the resulting
enynes with Ph2PH in one-pot.6 Compound 4 would be
synthesized with dual hydrophosphination of conjugated
diynes with 2 equiv of Ph2PH. However, two preliminary
examples revealed that 4 was formed from primary
alkyldiyne, but in contrast, tertiary alkyldiyne gave an
allenic product.5 Bis(alkeny)phosphines and their oxide 5
would be also prepared using PhPH2, though it has been
never used in the present system. To confirm these
possibilities, we investigated the dual intermolecular
hydrophosphination leading to 4 and 5.
Previously, we reported that a divalent ytterbium–imine
complex, Yb(h2-Ph2CNPh)(hmpa)3 (1), and a trivalent
silylamide complex, Yb[N(SiMe3)2]3(hmpa)2 (2), served
as highly effective precatalysts for intermolecular hydro-
phosphination of alkynes with diphenylphosphine and that
1
O
1
1
R
R
R
O
PPh
2
P
Ph P
Ph P
2
2
2
2
Ph
R
R
2
O
O
R
Keywords: Rare-earth catalysts; Dual hydrophosphination; Diynes.
*
3
4
5
Corresponding authors. Tel.: C81 824 24 7738; fax: C81 824 24 5494;
e-mail: kkome@hiroshima-u.ac.jp
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.12.049

2512
K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
2. Results and discussion
Aromatic terminal diyne 6i was exclusively polymerized
with both 1 and 2, because of its higher reactivity (run 16).
When hexadeca-7,9-diyne (6a) was treated with 2 equiv of
Ph2PH in the presence of 1 (10 mol%) in THF at room
temperature for 1 h, 7,10-bis(diphenylphosphinyl)hexa-
deca-7,9-diene (4a) was obtained in 80% total yield as a
mixture of two stereoisomers (61:39) after oxidation with
H2O2 (Table 1, run 1).7 The major product showed one
olefinic signal at 7.74 ppm with 34.8 Hz of trans-3JP–H in 1H
NMR and one signal at 29.53 ppm in 31P NMR. On the other
hand, two olefinic signals at 6.83 (cis-3JP–HZ20.6 Hz) and
7.13 ppm (trans-3JP–HZ35.0 Hz) in 1H NMR and two
signals at 28.18 and 33.58 ppm in 31P NMR were observed
for the minor. Therefore, the major product was definitely
assigned to the (Z,Z)-isomer, and the minor to the (Z,E)-
isomer. The stereoselectivity was increased a little with
decreasing temperature (run 2). The reaction was also
conducted with the silylamide 2 effectively (run 3). Two
cyclohexyl substituents in 6c did not change the reaction
mode, though its reactivity was somewhat decreased (run 5).
Arylalkyldiynes 6d and 6e gave the (Z,Z) and (Z,E)-dienes
4d and 4e; in the latter substrate, a small amount of the
(E,Z)-isomer was contaminated in the mixture (runs 6–9).
1,4-Diphenylbuta-1,3-diene (6f) was so reactive that no
phosphinylated product 4f was obtained with 1, other than
polymers even at K78 8C (run 10). In the absence of Ph2PH,
6f was recovered unchanged by the treatment with 1 at room
temperature. Use of milder precatalyst 2 afforded (E,E)-4f in
low yield (run 11). The reaction of terminal diynes 6g and
6h gave the expected products 4g and 4h, but their
stereochemistry was drastically altered, (E,Z) and (E,E)-
isomers being major and minor, respectively (runs 12–15).
The behavior of di-tert-butyldiyne 6j seems to be very
different from that of others. Thus, the reaction with 1
at K35 8C gave bis(diphenylphosphinyl)allene 7 and
(Z,Z)-diene 4j in 71 and 12% yields, respectively (Eq. 1).
When the reaction was performed at room temperature with
1 and 2, the allene 7 was exclusively obtained in high yields.
i) 1 or 2 (10 mol%)
THF
t
t
+
Bu
Bu
2 Ph PH
2
ii) H O
2
2
6j
t
t
Bu
Bu
Ph (O)P
P(O)Ph
2
·
t
+
Bu
P(O)Ph
2
2
t
Bu
P(O)Ph
2
(
Z,Z)-4j
7
12%
0%
0%
71%
89%
80%
with 1 –35 °C
rt
with 2
rt
(1)
Then, single hydrophosphination of unsymmetrical diynes
6d and 6g was carried out using equimolar amounts of
Ph2PH to learn the reaction process (Eq. 2). Apparently, the
first reaction in 6d took place at the a-alkyne carbon
attached to the Ph group, with high selectivity for anti-
addition, to yield (Z)-8d. This result contrasts well with the
regio- and stereoselectivity observed for simple aromatic
alkynes, in which syn-addition of Ph2P occurred at the
b-alkyne carbon to the aryl substituents, giving rise to
Table 1. Dual hydrophosphination of conjugated diynes with diphenylphosphine
i) 1 or 2 (10 mol%)
THF, 1 h
1
2
+
R
R
2 Ph PH
2
ii) H O
2
2
6
1
1
R
R
Ph (O)P
Ph (O)P
2
2
2
2
P(O)Ph
R
P(O)Ph
R
2
2
1
1
+
+
+
Ph (O)P
Ph (O)P
2
R
R
2
2
2
R
P(O)Ph
R
P(O)Ph
2
2
(Z,Z)-4
R1
(Z,E)-4
(E,Z)-4
(E,E)-4
Run
6
R2
Precatalyst Temperature (8C)
4
Total yield (%)a Ratio of isomers
(Z,Z):(Z,E):(E,Z):(E,E)
1
2
3
4
5
6
7
8
6a
nHex
nHex
1
1
2
1
1
1
2
1
2
1
2
1
2
1
rt
4a
80
82
82
92
74
98
95
85
65
0
28
80
89
89
72
0
61:39:—:0
K15
K15
K15
K15
K15
K15
K15
K15
K78
K78
K78b
K78b
K78b
K78b
K78
74:26:—:0
61:39:—:0
67:33:—:0
86:14:—:0
73:27:0:0
72:28:0:0
73:19:8:0
74:18:8:0
6b
6c
6d
nBu
c-C6H11
Ph
nBu
c-C6H11
4b
4c
4d
nHex
6e
6f
4-MeOPh
nHex
Ph
4e
4f
9
10
11
12
13
14
15
16
Ph
H
Polymerization
0:0:—:100
0:0:61:39
6g
6h
6i
nHex
nBu
Ph
4g
4h
4i
6:0:75:19
H
16:0:64:20
7:0:61:32
Polymerization
2
1 or 2
H
a NMR yield.
b K78 8C for 1 h then room temperature for 2 h.

K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
2513
(E)-products.5 In the reaction of the terminal diyne 6g,
enyne compound (Z)-8g was formed as a single isomer
through anti-addition to the terminal position.
repeated anti-addition of the Yb–phosphide complex could
produce (Z,Z)-4, which is the case of the internal diynes
6a–6e. In general, the overall stereoselectivity would be
rationalized by the isomerization of the intermediate B
formed by the second addition, which proceeds through
allenic species C (Scheme 2). In the case of the terminal
diynes 6g and 6h, B (R1ZH) changes readily to other
dienylytterbium D to avoid the steric repulsion between
Ph2P and Yb in the structure of B, giving rise to (E,Z)-4g
and 4h as major products. Moreover, it is likely that all four
stereoisomeric dienylytterbiums such as B and D are
interconvertible via C, but the equilibrium would not be
attained completely, because of the rapid protonation of the
intermediates with Ph2PH. Therefore, stereoselectivity of
the present reaction would be a reflection of both kinetic and
thermodynamic factors.
i) 1 or 2 (10 mol%)
THF, –78 ˚C, 30 min
1
n
+
Ph PH
2
R
Hex
ii) H O
2
2
6d, 6g
1
R
Ph (O)P
2
(2)
+
1
Ph (O)P
2
R
n
n
Hex
Hex
1
8d: R = Ph with 1 (
Z
Z
Z
) 85%
) 89%
) 94%
(
(
(
E
E
E
) 8%
) 0%
) 0%
1
8g: R = H with 1 (
with 2 (
Combining these results with the reaction mechanism for
the hydrophosphination of simple alkynes,5 the process of
the present system would be accounted for as follows
(Scheme 1). At first, bis or tris(diphenylphosphino)ytter-
bium species, [Yb]-PPh2, was generated in situ from the
precatalysts 1 or 2 as previously proved. anti-Addition of
the phosphide complex to the diyne 6 gave the intermediate
A, which was readily protonated with Ph2PH to yield the
enyne compound 8 and regenerate the active phosphide
species. The enyne 8 reacted further with the phosphide in a
manner similar to the first cycle to yield the diene 4 via
dienylytterbium B.
Formation of the allene 7 from di-tert-butyldiyne 6j
substantiates the scenario described above. In this case,
two tertiary substituents caused severe steric crowding in
the form of a dienylytterbium species, and thus the allenic C
should be the most stable intermediate, giving rise to 7
exclusively at room temperature. However, when the
reaction was carried out at lower temperature, the (Z,Z)-
diene 4j derived from B was included as a minor product.
Thus, 4j and 7 could be kinetic and thermodynamic
products, respectively.
Next, we studied the dual hydrophosphination with
phenylphosphine for the synthesis of bis(alkenyl)pho-
sphines and their oxides 5. The reaction of 1-phenylprop-
1-yne (9a) (2 equiv) with PhPH2 using the imine complex 1
(10 mol%) was slower than that with Ph2PH, and required
heating (Table 2, runs 1 and 2). After oxidative work-up
with H2O2, three isomers of bis(b-methylstyryl)phenylpho-
sphine oxide (5a) were formed in 43% total yield (run 2).7
The silylamide precatalyst 2 gave better yield, which was
further increased to 64% yield, though still non-selective, by
addition of 20 mol% of aniline (runs 3 and 4). The reaction
using equimolar amounts of the alkyne 9a and PhPH2 gave
an intractable mixture, in which bis(1-methyl-2-phenyl-
ethyl)phenylphosphine oxide, a reduced product of 5a, was
mainly detected. In the reaction of phenylacetylene (9b), the
aniline additive showed a significant effect for improvement
of the selectivity as well as total yield of 5b (run 5 vs 6).
Thus, the (Z,Z)- and (Z,E)-isomers were obtained in 80 and
20% yields, respectively. Similarly, various aromatic
alkynes 9c–9f were converted to the expected products
5c–5f in high yields (runs 7–10).
1 or 2
Ph PH
2
1
[Yb] PPh
2
R
H
PPh
2
Ph P
2
1
2
2
R
R
H
R
4
6
1
R
H
Ph PH
Ph P
2
2
8
2
R
Ph PH
2
1
1
R
[Yb]
R
H
PPh
2
Ph P
Ph P
2
2
2
[Yb]
R
2
R
A
B
Scheme 1.
Unfortunately, this method was not applicable to the
reaction of aliphatic alkynes, which resulted in recovery
of the starting materials or exclusive consumption of PhPH2
under various conditions. Moreover, the reaction of
diphenylacetylene (9g) gave cyclic phosphine oxide 10
Regiochemistry was independent of the substituents of the
diyne 6, that is, two Ph2P were introduced to the 1- and
4-position of the butadiyne moiety, whereas stereochem-
istry was significantly variable. As proposed in Scheme 1,
1
PPh Ph P
R
2
2
1
PPh
R
PPh
2
2
2
1
Ph P
R
R
2
2
2
[Yb]
R
PPh
[Yb]
[Yb]
R
2
B
D
C
Scheme 2.

2514
K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
Table 2. Dual hydrophosphination of alkynes with phenylphosphine
i) 1 or 2 (10 mol%)
PhNH (20 mol%)
2
1
2
+
2 R
R
PhPH
2
THF, 4 h
9
ii) H O
2
2
1
2
2
2
R
R
P
R
P
R
P
O
O
O
+
+
1
1
1
R
R
R
Ph
Ph
Ph
1
2
1
2
2
R
R
R
R
R
(
Z,Z)-5
(
Z,E)-5
(
E,E)-5
Run
9
R1
Ph
R2
Precatalyst Temperature (8C)
5
Total yield (%)a Ratio of isomers
(Z,Z):(Z,E):(E,E)
1
2
3
4
5
6
7
8
9
10
9a
Me
1b
1b
2b
2
rtc
Reflux
Reflux
Reflux
rt
rt
rt
rt
rt
rt
5a
7
43
100:0:0
37:37:26
46:34:20
36:34:30
48:52:0
80:20:0
82:18:0
89:11:0
78:22:0
81:19:0
59
64
75
9b
Ph
H
2b
2
5b
Quant
Quant
97
9c
9d
9e
9f
4-MeOPh
4-MePh
4-CIPh
H
H
H
H
2
2
2
2
5c
5d
5e
5f
89
89
4-BrPh
a NMR yield.
b In the absence of PhNH2.
c Reaction period is 15 h.
unexpectedly in low yields, together with small amounts of
trans-stilbene (Eq. 3).8
afford the (Z,Z)-isomers. The high (Z)-selectivity may be
caused by a radical mechanism instead of the process
proposed in Scheme 3.9 However, this possibility was
completely ruled out. Thus, the reaction of 2 equiv of
1-decene with PhPH2 did not occur with 2, but in contrast,
addition product 11 was quantitatively formed under radical
conditions (Eq. 4). Alternatively, the (Z)-selectivity would
be attributed to the amine additive, which has been known to
change the activity of the lanthanide catalysts and product
selectivity in various reactions as a proton source and
ligand.6,10 In fact, aliphatic amines like amylamine
decreased the yield and selectivity in contrast to aniline.
However, the reason for the difference between the reaction
with PhPH2 and Ph2PH is still unclear at present.
Ph
Ph
i) 1 or 2 (10 mol%)
+
PhPH
2
Ph
Ph
2
P(O)Ph
Ph
THF, reflux, 24 h
ii) H O
Ph
9g
2
2
10 26% with 1
32% with 2
(3)
The present reaction would proceed in a mechanism
analogous to that with diphenylphosphine as shown in
Scheme 3. Addition of phenylphosphinoytterbium, [Yb]-
PHPh, to aromatic alkyne 9, followed by intramolecular
proton transfer would yield alkenylphosphide species F,
which reacts further with the second molecule of 9 to give
bis(alkenyl)phosphine 5 through the intermediate G.
i) 2 or AIBN (10 mol%)
n
n
+
Oct
PhPH
2
2
PhP(O)( C
H )
10 21 2
THF, reflux, 24 h
ii) H O
11
2
2
no reaction with 2
2
2
[Yb]
Ar
R
H
R
P
[Yb] PHPh
quantitative with AIBN
2
Ar
R
(4)
PH
Ar
[Yb]
9
Ph
Ph
E
F
2
2
R
R
P
In summary, dual intermolecular hydrophosphination of
conjugated diynes with 2 equiv of Ph2PH has been achieved
using ytterbium (II) and (III) precatalysts 1 and 2 to give
bis(diphenylphosphinyl)dienes 4 in high yields. Addition
reaction of the active species, Yb–phosphide, was found to
proceed in an anti-fashion, but the resulting intermediates
could isomerize via an allenic species. Thus, the stereo-
chemistry of the products 4 was determined both kinetically
and thermodynamically, depending on their substituents.
Moreover, bis(alkenyl)phosphine oxides 5 were effectively
obtained from 2 equiv of aromatic alkynes and PhPH2 by
the dual reaction in the presence of an aniline additive.
9
P
Ar
[Yb]
Ar
Ar
Ar
Ph
Ph
2
2
R
R
G
5'
Scheme 3.
The regiochemistry was in agreement with that observed for
the reaction with Ph2PH, whereas the stereochemistry was
reversed. Since isomerization of the intermediates and
products is less likely in the present system, anti-addition of
the phosphide species would take place preferentially to

K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
2515
3. Experimental
JZ35.0 Hz); 13C NMR (CDCl3) d 13.9, 22.3, 28.6, 29.3
(d, JZ3.7 Hz), 31.2, 35.7 (d, JZ12.3 Hz), 128.5 (d, JZ
8.3 Hz), 131.7 (d, JZ2.5 Hz), 131.8 (d, JZ10.7 Hz), 133.2
(d, JZ101.7 Hz), 137.6 (d, JZ86.2 Hz), 140.9 (dd, JZ
10.3, 3.7 Hz); 31P NMR (CDCl3) d 29.53. Anal. Calcd for
C40H48O2P2: C, 77.15; H, 7.77. Found: C, 77.03; H, 7.74.
(Z,E)-Isomer: yellow oil; IR (neat) 1178 cmK1; MS
3.1. General
1H, 13C, and 31P NMR spectra were recorded at 396, 99, and
160 MHz, respectively. IR spectra were taken on an FT-IR
spectrophotometer. Mass spectra (EI) were obtained at
70 eV on a GC–MS apparatus. MALDI-TOF mass spectra
were acquired using 1,8,9-trihydroxyanthracene as the
matrix. Microanalyses were performed at our analytical
laboratory. Melting points are uncorrected. All reactions
were carried out under argon. THF was distilled from
sodium/benzophenone ketyl immediately prior to use.
HMPA was distilled from CaH2 and stored over molecular
sieves. The Yb-imine precatalyst 1 was generated in situ
from Yb metal, Ph2CZNPh, and HMPA (6 equiv) in THF
as previously reported.5 The silylamide precatalyst 2 was
also generated by treatment of Yb[N(SiMe3)2]3(thf)211 with
HMPA (2 equiv) in THF. Symmetrical diynes 6a–6c and
6f,12 unsymmetrical diynes 6d and 6e,13 and terminal diynes
6g–6i14 were prepared according to the literature methods.
All other materials were commercially available and were
used after drying and distillation.
1
(MALDI) m/z 621.17 (MCK1); H NMR (CDCl3) d 0.81
(3H, t, JZ7.0 Hz), 0.84 (3H, t, JZ7.0 Hz), 1.09–1.37 (16H,
m), 2.21 (2H, dt, JZ13.8, 6.9 Hz), 2.50 (2H, dt, JZ16.1,
7.7 Hz), 6.83 (1H, dd, JZ20.6, 11.8 Hz), 7.13 (1H, ddd, JZ
35.0, 11.8, 1.2 Hz), 7.27–7.53 (20H, m); 13C NMR (CDCl3)
d 13.9, 14.0, 22.4, 22.5, 28.7, 29.3, 29.5 (d, JZ4.1 Hz), 30.5
(d, JZ1.7 Hz), 31.3, 31.4, 36.4 (d, JZ1.7 Hz), 36.5 (d, JZ
1.6 Hz), 128.3 (d, JZ11.4 Hz), 128.5 (d, JZ12.3 Hz),
131.1 (d, JZ101.7 Hz), 131.5 (d, JZ9.8 Hz), 131.62 (d, JZ
10.7 Hz), 131.63 (d, JZ10.1 Hz), 131.8 (d, JZ9.0 Hz),
132.7 (d, JZ101.7 Hz), 136.7 (dd, JZ19.7, 5.7 Hz), 136.9
(dd, JZ14.0, 9.8 Hz), 140.1 (dd, JZ96.0, 2.1 Hz), 140.9
(d, JZ86.1 Hz); 31P NMR (CDCl3) d 28.18, 33.58.
3.2.2. 5,8-Bis(diphenyphophinyl)dodeca-5,7-diene (4b).
(Z,Z)-Isomer: white solid; mp 162–163 8C; IR (KBr)
1
1180 cmK1; MS (MALDI) m/z 564.81 (MCK2); H NMR
(CDCl3) d 0.56 (6H, t, JZ6.9 Hz), 0.85–0.92 (8H, m), 1.92
(4H, dt, JZ13.5, 6.7 Hz), 7.44–7.55 (12H, m), 7.64–7.69
(8H, m), 7.76 (2H, d, JZ34.8 Hz); 13C NMR (CDCl3) d
13.4, 21.9, 31.2, 35.3 (d, JZ12.3 Hz), 128.4 (d, JZ
12.3 Hz), 131.72, (d, JZ9.8 Hz), 131.73, 133.1 (d, JZ
100.9 Hz), 137.5 (dd, JZ88.2, 2.1 Hz), 140.8 (dd, JZ9.8,
4.1 Hz); 31P NMR (CDCl3) d 29.57. Anal. Calcd for
C36H40O2P2: C, 76.31; H, 7.12. Found: C, 76.51; H, 7.08.
(Z,E)-Isomer: yellow oil; IR (neat) 1182 cmK1; MS
3.2. Dual hydrophosphination of the conjugated diynes 6
with diphenylphosphine
Ph2PH (2.0 mmol) was added to a solution of 1 or 2
(0.1 mmol) in THF (1 mL) and the mixture was stirred for
30 min at room temperature. After cooling the mixture to
the appropriate temperature indicated in Table 1, diyne 6
(1.0 mmol) was added to the solution and stirring was
continued for 1 h at this temperature. In the case of terminal
diynes, the mixture was stirred for 1 h at K78 8C, and then
for 2 h at room temperature to ensure the completion of the
reaction. The reaction was quenched with H2O (1 mL) and
HCl solution (1 M, 1 mL), and the mixture was oxidized
with H2O2 (30%, 1 mL) at 0 8C. Dimethyl terephthalate was
added to the mixture as an internal standard. The reaction
mixture was extracted with CHCl3, washed with brine, dried
over MgSO4, and concentrated in vacuo. The product yield
1
(MALDI) m/z 564.86 (MCK2); H NMR (CDCl3) d 0.74
(3H, t, JZ7.2 Hz), 0.83 (3H, t, JZ7.1 Hz), 1.14–1.37 (8H,
m), 2.21 (2H, dt, JZ13.7, 6.6 Hz), 2.53 (2H, dt, JZ15.4,
7.6 Hz), 6.81 (1H, dd, JZ20.6, 11.4 Hz), 7.13 (1H, dd, JZ
35.0, 11.4 Hz), 7.34–7.50 (20H, m); 13C NMR (CDCl3) d
13.5, 13.6, 22.1, 22.7, 27.2 (d, JZ9.0 Hz), 31.6 (d, JZ
4.1 Hz), 32.6, 36.1 (d, JZ10.6 Hz), 128.3 (d, JZ12.3 Hz),
128.4 (d, JZ12.3 Hz), 131.1 (d, JZ102.5 Hz), 131.4 (d, JZ
9.8 Hz), 131.61 (d, JZ9.8 Hz), 131.62 (d, JZ9.8 Hz),
131.7 (d, JZ9.8 Hz), 132.6 (d, JZ101.7 Hz), 136.5 (dd, JZ
19.7, 6.5 Hz), 136.8 (dd, JZ14.7, 9.8 Hz), 140.0 (dd, JZ
96.8, 2.1 Hz), 140.9 (d, JZ87.6 Hz); 31P NMR (CDCl3) d
28.25, 33.71.
1
and ratio were determined by H and 31P NMR spectra of
the crude mixture. Analytically pure compounds 4 were
isolated by column chromatography on silica gel with
chloroform–acetone eluent.
For determination of the stereochemistry of the products,
the coupling constants between the olefinic protons
and Ph2P(O) in 1H NMR are informative; trans-3JP–H
(ca. 35 Hz), cis-3JP–H (ca. 19 Hz), and 2JP–H (ca. 22 Hz). In
addition, 31P NMR signals of the olefinic (Z)-Ph2P(O)
always appear in higher field than those of the (E).9 For
examples, (alkyl)[P(O)]C]CHR appears at ca. 29 (Z) and
33 ppm (E), (aryl)[P(O)]C]CHR at ca. 26 (Z) and 31 ppm
(E), (H)[P(O)]C]CHR at ca. 22 (Z) and 25 ppm (E).
3.2.3. 1,4-Bis(diphenylphosphinyl)-1,4-dicyclohexylbuta-
1,3-diene (4c). (Z,Z)-Isomer: white solid; mp 238–239 8C;
IR (KBr) 1174 cmK1; MS (MALDI) m/z 616.76 (MCK2);
1H NMR (CDCl3) d 0.68–0.74 (10H, m), 1.25–1.43 (10H,
m), 2.00 (2H, quin, JZ11.5 Hz), 7.43–7.55 (14H, m), 7.63–
7.67 (8H, m); 13C NMR (CDCl3) d 25.4, 26.3, 33.0 (d, JZ
10.6 Hz), 44.2 (d, JZ10.6 Hz), 128.3 (d, JZ12.3 Hz),
131.56, (d, JZ9.8 Hz), 131.57, 133.4 (d, JZ100.9 Hz),
138.2 (dd, JZ10.7, 4.1 Hz), 143.0 (dd, JZ87.0, 2.4 Hz);
31P NMR (CDCl3) d 29.61. Anal. Calcd for C40H44O2P2: C,
77.65; H, 7.17. Found: C, 77.77; H, 7.21. (Z,E)-Isomer:
isolated as a mixture with (Z,Z)-isomer; MS (MALDI) m/z
617.46 (MCK1); 1H NMR (CDCl3) (clearly assignable
peaks) d 6.69 (1H, dd, JZ22.1, 11.7 Hz); 13C NMR (CDCl3)
d 25.80, 25.83, 26.6, 26.9, 32.3 (d, JZ3.3 Hz), 33.9 (d, JZ
4.1 Hz), 40.1 (d, JZ9.0 Hz), 42.0 (d, JZ11.5 Hz), 128.2
3.2.1. 7,10-Bis(diphenylphosphinyl)hexadeca-7,9-diene
(4a). (Z,Z)-Isomer: white solid; mp 137–140 8C; IR (KBr)
1180 cmK1; MS (MALDI) m/z 619.99 (MCK2); MS m/z
622 (MC), 551 (MCKC5H11), 421 (MCKPh2PO), 201
1
(Ph2POC); H NMR (CDCl3) d 0.75 (6H, t, JZ7.2 Hz),
0.83–0.97 (12H, m), 1.00–1.09 (4H, m), 1.86–1.97 (4H, m),
7.45–7.55 (12H, m), 7.64–7.69 (8H, m), 7.76 (2H, d,

2516
K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
(d, JZ11.5 Hz), 128.5 (d, JZ12.3 Hz), 131.4 (d, JZ
2.4 Hz), 131.5 (d, JZ42.7 Hz), 131.64 (d, JZ9.8 Hz),
131.65 (d, JZ2.4 Hz), 131.9 (d, JZ9.8 Hz), 132.9 (d, JZ
101.7 Hz), 135.1 (dd, JZ20.9, 5.3 Hz), 136.9 (dd, JZ15.6,
9.8 Hz), 144.0 (dd, JZ93.5, 1.6 Hz), 145.1 (d, JZ86.1,
1.6 Hz); 31P NMR (CDCl3) d 29.92, 35.16.
NMR (CDCl3) d 128.1 (d, JZ30.4 Hz), 128.2 (d, JZ
2.4 Hz), 128.3 (d, JZ2.4 Hz), 129.5 (d, JZ2.4 Hz), 130.7
(d, JZ104.2 Hz), 131.78 (d, JZ9.0 Hz), 131.82 (d, JZ
7.4 Hz), 134.1 (d, JZ4.5 Hz), 137.9 (d, JZ14.4 Hz), 142.8
(dd, JZ94.3, 1.4 Hz); 31P NMR (CDCl3) d 29.97. Anal.
Calcd for C40H32O2P2: C, 79.20; H, 5.32. Found: C, 79.13;
H, 5.02.
3.2.4. 1,4-Bis(diphenylphosphinyl)-1-phenyldeca-1,3-
diene (4d). (Z,Z)-Isomer: white solid; mp 124–126 8C; IR
(KBr) 1180 cmK1; MS (MALDI) m/z 613.77 (MCK1); 1H
NMR (CDCl3) d 0.77 (3H, t, JZ7.4 Hz), 0.87–1.00 (6H, m),
1.07 (2H, quint, JZ7.1 Hz), 1.95–2.00 (2H, m), 6.69 (2H, d,
JZ7.0 Hz), 6.94 (2H, t, JZ7.4 Hz), 7.01 (1H, t, JZ7.3 Hz),
7.32–7.68 (20H, m), 7.82 (1H, dd, JZ35.5, 11.0 Hz), 7.89
(1H, dd, JZ33.9, 11.0 Hz); 13C NMR (CDCl3) (clearly
assignable peaks) d 13.9, 22.2, 28.6, 29.1 (d, JZ4.1 Hz),
31.1, 35.6 (d, JZ11.5 Hz), 132.8 (d, JZ101.7 Hz), 133.5
(d, JZ102.5 Hz), 138.5 (dd, JZ90.2, 2.1 Hz), 139.5 (d, JZ
9.8 Hz), 140.3 (dd, JZ87.4, 2.0 Hz); 31P NMR (CDCl3) d
26.13, 29.43. Anal. Calcd for C40H40O2P2: C, 78.16; H,
6.56. Found: C, 78.03; H, 6.68. (Z,E)-Isomer: colorless oil;
IR (neat) 1182 cmK1; MS (MALDI) m/z 613.04 (MCK1);
1H NMR (CDCl3) d 0.80 (3H, t, JZ7.3 Hz), 1.09–1.45 (8H,
m), 2.54 (2H, dd, JZ16.0, 8.0 Hz), 6.99–7.01 (2H, m),
7.07–7.18 (4H, m), 7.27–7.53 (21H, m); 13C NMR (CDCl3)
(clearly assignable peaks) d 13.9, 22.4, 27.5 (d, JZ9.0 Hz),
29.2, 30.4, 31.2, 136.5 (dd, JZ14.8, 9.1 Hz), 139.9 (dd, JZ
9.9, 1.7 Hz), 141.8 (dd, JZ88.6, 1.6 Hz), 143.0 (dd, JZ
95.2, 1.7 Hz); 31P NMR (CDCl3) d 25.52, 33.38.
3.2.7. 1,4-Bis(diphenylphosphinyl)deca-1,3-diene (4g).
(Z,Z)-Isomer: white solid; mp 174–176 8C; IR (KBr) 1195,
1
1176 cmK1; MS (MALDI) m/z 536.73 (MCK2); H NMR
(CDCl3) d 0.76 (3H, t, JZ7.1 Hz), 0.91–1.14 (8H, m), 1.98–
2.05 (2H, m), 6.12 (1H, dd, JZ24.6, 12.3 Hz), 7.45–7.53
(12H, m), 7.64–7.74 (8H, m), 8.15 (1H, dd, JZ34.8,
12.3 Hz), 8.27 (1H, dt, JZ37.4, 12.3 Hz); 13C NMR
(CDCl3) d 13.8, 22.2, 28.6, 29.2 (d, JZ4.1 Hz), 31.0, 35.7
(d, JZ11.5 Hz), 124.0 (dd, JZ96.8, 1.6 Hz), 124.4 (d, JZ
6.6 Hz), 128.5 (d, JZ7.6 Hz) 130.9 (d, JZ9.8 Hz), 131.6
(d, JZ2.4 Hz), 131.7 (d, JZ9.8 Hz), 131.8 (d, JZ3.3 Hz),
132.5 (d, JZ102.6 Hz), 133.8 (d, JZ105.0 Hz), 140.9 (dd,
JZ10.2, 4.5 Hz), 141.0 (dd, JZ84.5, 2.1 Hz), 144.7 (dd,
JZ9.4, 2.9 Hz); 31P NMR (CDCl3) d 22.32, 30.73. Anal.
Calcd for C34H36O2P2: C, 75.82; H, 6.74. Found: C, 75.46;
H, 6.71. (E,Z)-Isomer: colorless oil; IR (neat) 1182 cmK1
;
1
MS (MALDI) m/z 538.13 (MC); H NMR (CDCl3) d 0.81
(3H, t, JZ7.1 Hz), 1.05–1.24 (6H, m), 1.32 (2H, quin, JZ
7.5 Hz), 2.20 (2H, dt, JZ12.7, 7.5 Hz), 6.33 (1H, t, JZ
16.7 Hz), 6.91 (1H, dd, JZ34.9, 11.4 Hz), 7.16 (1H, td, JZ
16.7, 11.4 Hz), 7.37–7.43 (8H, m), 7.48–7.55 (12H, m); 13C
NMR (CDCl3) d 13.9, 22.3, 28.7, 29.4 (d, JZ3.3 Hz), 31.2,
35.9 (d, JZ9.8 Hz), 128.4 (d, JZ12.3 Hz), 128.5, (d, JZ
11.5 Hz), 128.6 (br d, JZ103.3 Hz) 131.3 (d, JZ97.6 Hz),
131.4 (d, JZ9.8 Hz), 131.5 (d, JZ9.9 Hz), 131.8 (d, JZ
6.5 Hz), 132.4 (d, JZ102.6 Hz), 141.5 (dd, JZ22.5,
5.6 Hz), 142.7 (br d, JZ86.1 Hz), 143.0 (dd, JZ9.5,
6.2 Hz); 31P NMR (CDCl3) d 26.31, 28.25. Anal. Calcd
for C34H36O2P2: C, 75.82; H, 6.74. Found: C, 75.64; H,
6.53. (E,E)-Isomer: white solid; mp 212–214 8C; IR (KBr)
3.2.5. 1,4-Bis(diphenylphosphinyl)-1-(4-methoxyphe-
nyl)deca-1,3-diene (4e). (Z,Z)-Isomer: white solid; mp
113–115 8C; IR (KBr) 1178 cmK1; MS (MALDI) m/z
1
643.88 (MCK1); H NMR (CDCl3) d 0.77 (3H, t, JZ
7.2 Hz), 0.79–1.12 (8H, m), 1.91–2.00 (2H, m), 3.67 (3H, s),
6.48 (2H, d, JZ8.2 Hz), 6.59 (2H, d, JZ8.2 Hz), 7.35–7.68
(20H, m), 7.78 (1H, dd, JZ35.3, 12.1 Hz), 7.83 (1H, dd, JZ
34.5, 12.1 Hz); 13C NMR (CDCl3) d 14.0, 22.3, 28.7, 29.2
(d, JZ3.3 Hz), 31.2, 35.7 (d, JZ10.7 Hz), 55.1, 113.1,
128.3 (d, JZ12.3 Hz), 128.5 (d, JZ11.5 Hz), 129.9 (d, JZ
4.9 Hz), 131.5 (d, JZ2.4 Hz), 131.6 (d, JZ9.8 Hz), 131.7
(d, JZ9.8 Hz), 131.8 (d, JZ2.4 Hz), 132.1 (d, JZ10.7 Hz),
133.0 (d, JZ101.7 Hz), 133.7 (d, JZ102.5 Hz), 138.0 (dd,
JZ90.7, 2.1 Hz), 140.0 (dd, JZ87.4, 2.1 Hz), 140.4 (dd,
JZ8.6, 4.5 Hz), 140.9 (dd, JZ9.4, 5.3 Hz), 158.8; 31P NMR
(CDCl3) d 26.18, 29.41. Anal. Calcd for C41H42O3P2: C,
76.38; H, 6.57. Found: C, 75.96; H, 6.52. (Z,E)-Isomer:
isolated as a mixture of (Z,E) and (E,Z)-isomer (65:35):
1
1186 cmK1; MS (MALDI) m/z 537.94 (MCK1); H NMR
(CDCl3) d 0.78 (3H, t, JZ7.2 Hz), 0.96–1.17 (8H, m), 2.32–
2.40 (2H, m), 6.53 (1H, dd, JZ22.6, 17.0 Hz), 6.84 (1H, dd,
JZ19.3, 11.2 Hz), 7.37 (1H, td, JZ17.0, 11.2 Hz), 7.46–
7.57 (13H, m), 7.65–7.72 (7H, m); 13C NMR (CDCl3) d
13.9, 22.4, 28.9 (d, JZ9.8 Hz), 29.3, 30.6, 31.2, 128.5 (d,
JZ11.5 Hz), 128.6 (d, JZ12.3 Hz), 129.5 (d, JZ100.9 Hz)
131.2 (d, JZ102.5 Hz), 131.3 (d, JZ9.9 Hz), 131.9 (d, JZ
9.9 Hz), 132.0 (d, JZ2.4 Hz), 132.4 (d, JZ67.3 Hz), 139.5
(dd, JZ20.5, 10.7 Hz), 140.5 (dd, JZ18.4, 3.7 Hz), 142.6
(br d, JZ91.9 Hz); 31P NMR (CDCl3) d 23.77, 31.68.
1
yellow oil; MS (MALDI) m/z 643.88 (MCK1); H NMR
(CDCl3) d 0.81 (3H, t, JZ7.1 Hz), 0.99–1.39 (8H, m), 2.49–
2.57 (2H, m), 3.72 (3H, s), 6.65 (2H, d, JZ8.7 Hz), 6.93
(2H, d, JZ8.7 Hz), 7.07 (1H, dd, JZ20.4, 11.7 Hz), 7.28–
7.57 (21H, m); 31P NMR (CDCl3) d 25.69, 33.58. (E,Z)-
Isomer: 1H NMR (CDCl3) (clearly assignable peaks) d 0.77
(3H, t, JZ7.4 Hz), 2.06–2.11 (2H, m), 3.75 (3H, s), 6.81
(2H, d, JZ8.7 Hz), 7.22 (2H, d, JZ8.9 Hz); 31P NMR
(CDCl3) d 28.33, 31.37.
3.2.8. 1,4-Bis(diphenylphosphinyl)octa-1,3-diene (4h).
(Z,Z)-Isomer: isolated as a mixture of (Z,Z) and (E,E)-
isomer (52:48); white solid; IR (KBr) 1178 cmK1; MS
1
(MALDI) m/z 509.78 (MCK1); H NMR (CDCl3) d 0.60
(3H, t, JZ7.2 Hz), 0.94–1.10 (4H, m), 1.97–2.04 (2H, m),
6.12 (1H, dd, JZ25.3, 12.4 Hz), 7.44–7.73 (20H, m), 8.14
(1H, dd, JZ34.6, 12.4 Hz), 8.26 (1H, dt, JZ37.8, 12.4 Hz);
31P NMR (CDCl3) d 22.41, 30.82. (E,Z)-Isomer: isolated as
a mixture of (E,Z) and (E,E)-isomer (57:43); white solid;
3.2.6. (E,E)-1,4-Bis(diphenylphosphinyl)-1,4-diphenyl-
buta-1,3-diene (4f). White solid; mp 267–270 8C; IR
(KBr) 1182 cmK1; MS (MALDI) m/z 605.67 (MCK1);
1H NMR (CDCl3) d 6.76 (2H, d, JZ16.9 Hz), 7.04–7.16
(10H, m), 7.27–7.43 (12H, m), 7.53–7.58 (8H, m); 13C
1
MS (MALDI) m/z 510.25 (MC); H NMR (CDCl3) d 0.71
(3H, t, JZ7.2 Hz), 1.05–1.32 (4H, m), 2.16–2.23 (2H, m),
6.31 (1H, t, JZ17.3 Hz), 6.89 (1H, dd, JZ34.8, 11.1 Hz),
7.11 (1H, td, JZ17.3, 11.1 Hz), 7.34–7.54 (16H, m),

K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
2517
1
7.63–7.70 (4H, m); 31P NMR (CDCl3) d 26.71, 28.41. Anal.
Calcd for C32H32O2P2: C, 75.28; H, 6.32. Found: C, 75.43;
H, 6.30. (E,E)-Isomer: 1H NMR (CDCl3) (clearly assignable
peaks) d 0.66 (3H, t, JZ7.2 Hz), 2.32–2.39 (2H, m), 6.53
(1H, dd, JZ22.4, 16.8 Hz), 6.83 (1H, dd, JZ19.5, 11.2 Hz),
7.36 (1H, td, JZ16.8, 11.2 Hz); 31P NMR (CDCl3) d 23.71,
31.70.
white solid; MS (EI) m/z 330 (MC); H NMR (CDCl3) d
6.22 (1H, dd, JZ19.0, 13.9 Hz), 6.41 (1H, dd, JZ22.9,
17.4 Hz), 7.11–7.54 (13H, m), 7.68–7.79 (4H, m); 13C NMR
(CDCl3) d 120.3 (d, JZ105.0 Hz), 122.5 (d, JZ100.1 Hz),
127.3, 127.8, 128.3, 128.5 (d, JZ9.0 Hz), 129.2, 129.6,
129.8 (d, JZ1.6 Hz), 130.4 (d, JZ9.8 Hz), 131.3 (d, JZ
3.3 Hz), 133.5 (d, JZ107.5 Hz), 134.9 (d, JZ7.4 Hz),
135.1 (d, JZ18.0 Hz), 146.0 (d, JZ3.3 Hz), 148.9; 31P
NMR (CDCl3) d 17.56.
3.2.9. (Z,Z)-3,6-Bis(diphenylphosphinyl)-2,2,7,7-tetra-
methylocta-3,5-diene (4j). White solid; IR (Nujol)
1
1188 cmK1; MS (EI) m/z 566 (MC); H NMR (CDCl3) d
3.3.3. Bis(4-methoxystyryl)phenylphosphine oxide (5c).
(Z,Z)-Isomer: IR (neat) 1180 cmK1; MS (EI) m/z 390 (MC);
1H NMR (CDCl3) d 3.76 (6H, s), 5.92 (2H, dd, JZ19.5,
14.0 Hz), 6.75–6.79 (4H, m), 7.17 (2H, dd, JZ40.5,
14.0 Hz), 7.26–7.34 (3H, m), 7.70–7.76 (6H, m); 13C
NMR (CDCl3) d 55.2, 113.4, 121.1 (d, JZ100.9 Hz),
128.07 (d, JZ18.9 Hz), 128.09, 130.8 (d, JZ9.8 Hz), 131.0
(d, JZ3.3 Hz), 132.1 (d, JZ1.6 Hz), 134.3 (d, JZ
106.6 Hz), 147.5 (d, JZ1.6 Hz), 160.4; 31P NMR (CDCl3)
d 15.91. Anal. Calcd for C24H23O3P: C, 73.83; H, 5.94.
Found: C, 73.43; H, 5.98. (Z,E)-Isomer: MS (EI) m/z 390
0.85 (18H, s), 7.35–7.53 (14H, m), 7.68 (4H, tm, JZ
8.8 Hz), 7.90 (4H, tm, JZ8.8 Hz); 13C NMR (CDCl3)
(clearly assignable peaks) d 29.7, 36.7. Anal. Calcd for
C36H40O2P2: C, 76.31; H, 7.11. Found: C, 76.80; H, 7.47.
3.3. Dual hydrophosphination of aromatic alkynes 9 with
phenylphosphine
The reaction was carried out in a manner similar to that of
the diynes 6 described above, using the aromatic alkynes 9
(2.0 mmol), PhPH2 (1.0 mmol), and 1 or 2 (0.1 mmol) in
THF (1 mL). In the reaction with aniline, this additive and
PhPH2 were successively added to a solution of 1 or 2, and
the mixture was stirred for 30 min at room temperature.
(MC); H NMR (CDCl3) d 3.72 (3H, s), 3.80 (3H, s), 6.04
1
(1H, dd, JZ19.4, 13.8 Hz), 6.30 (1H, dd, JZ22.6, 17.2 Hz),
6.74–6.85 (4H, m), 7.29–7.48 (7H, m), 7.64–7.80 (4H, m);
13C NMR (CDCl3) d 55.2, 55.3, 113.4, 114.1, 117.8 (d, JZ
107.5 Hz), 119.7 (d, JZ100.9 Hz), 127.9 (d, JZ7.4 Hz),
128.2, 128.4 (d, JZ12.3 Hz), 129.1, 130.6 (d, JZ9.8 Hz),
131.3 (d, JZ2.4 Hz), 132.0, 134.2 (d, JZ107.5 Hz), 145.5
(d, JZ4.2 Hz), 148.4, 160.5, 160.9; 31P NMR (CDCl3) d
18.57.
3.3.1. Bis(b-methylstyryl)phenylphosphine oxide (5a).
(Z,Z)-Isomer: IR (Nujol) 1178 cmK1; MS (EI) m/z 358
(MC); 1H NMR (CDCl3) d 1.96 (6H, dd, JZ12.2, 1.5 Hz),
7.03 (2H, dd, JZ37.0, 1.5 Hz), 7.17–7.19 (6H, m), 7.28–
7.40 (7H, m), 7.66–7.71 (2H, m); 13C NMR (CDCl3) d 23.9
(d, JZ13.1 Hz), 127.3, 127.9, 128.1, 128.4 (d, JZ50.9 Hz),
129.5 (d, JZ1.6 Hz), 131.1 (d, JZ3.2 Hz), 131.5 (d, JZ
9.0 Hz), 132.5 (d, JZ99.9 Hz), 136.0 (d, JZ6.5 Hz), 144.6
(d, JZ6.5 Hz); 31P NMR (CDCl3) d 27.52. Anal. Calcd for
C24H23OP: C, 80.43; H, 6.47. Found: C, 80.29; H, 6.51.
3.3.4. Bis(4-methylstyryl)phenylphosphine oxide (5d).
(Z,Z)-Isomer: white solid; mp 98–99 8C; IR (KBr)
1
1178 cmK1; MS (EI) m/z 358 (MC); H NMR (CDCl3) d
2.29 (6H, s), 6.00 (2H, dd, JZ19.8, 14.0 Hz), 7.04–7.32
(10H, m), 7.61–7.72 (5H, m); 13C NMR (CDCl3) d 21.3,
122.8 (d, JZ100.9 Hz), 127.9 (d, JZ11.5 Hz), 128.7, 130.2
(d, JZ1.6 Hz), 130.8 (d, JZ9.8 Hz), 130.9 (d, JZ3.3 Hz),
132.5 (d, JZ7.4 Hz), 134.2 (d, JZ107.5 Hz), 139.4, 147.9
(d, JZ1.6 Hz); 31P NMR (CDCl3) d 15.29. Anal. Calcd for
C24H23OP: C, 80.43; H, 6.47. Found: C, 80.21; H, 6.43.
1
(Z,E)-Isomer: MS (EI) m/z 358 (MC); H NMR (CDCl3) d
1.75 (3H, dd, JZ14.0, 1.0 Hz), 2.09 (3H, dd, JZ12.0,
1.2 Hz), 7.05–7.49 (15H, m), 7.66–7.71 (2H, m); 13C NMR
(CDCl3) d 14.4 (d, JZ11.4 Hz), 23.8 (d, JZ12.3 Hz),
127.3, 127.5, 127.9 (d, JZ12.6 Hz), 128.1, 128.2 (d, JZ
11.5 Hz), 128.8 (d, JZ90.9 Hz), 129.2, 129.5 (d, JZ
1.6 Hz), 131.0 (d, JZ81.1 Hz), 131.1 (d, JZ3.3 Hz), 131.3
(d, JZ21.5 Hz), 132.0 (d, JZ84.4 Hz), 135.8 (d, JZ
5.7 Hz), 136.0 (d, JZ18.9 Hz), 141.3 (d, JZ9.8 Hz), 145.4
(d, JZ7.3 Hz); 31P NMR (CDCl3) d 29.81. (E,E)-Isomer:
1
(Z,E)-Isomer: MS (EI) m/z 358 (MC); H NMR (CDCl3) d
2.24 (3H, s), 2.33 (3H, s), 6.14 (1H, dd, JZ19.0, 14.0 Hz),
6.35 (1H, dd, JZ22.8, 17.2 Hz), 6.92–7.79 (15H, m): 13C
NMR (CDCl3) d 21.2, 21.3, 119.3 (d, JZ105.8 Hz), 121.5
(d, JZ100.1 Hz), 127.4, 128.4 (d, JZ12.3 Hz), 128.7,
129.3, 130.1, 130.6 (d, JZ9.8 Hz), 131.3 (d, JZ3.3 Hz),
132.4 (d, JZ7.4 Hz), 132.7 (d, JZ18.9 Hz), 134.0 (d, JZ
107.5 Hz), 139.5, 139.9, 145.9 (d, JZ3.3 Hz), 148.9; 31P
NMR (CDCl3) d 18.09.
1
MS (EI) m/z 358 (MC); H NMR (CDCl3) d 2.17 (6H, dd,
JZ13.2, 1.2 Hz), 7.25–7.57 (15H, m), 7.80–7.85 (2H, m);
13C NMR (CDCl3) d 15.0 (d, JZ9.8 Hz), 128.3, 128.4,
128.68, 128.71 (d, JZ29.5 Hz), 129.4, 129.6 (d, JZ
41.7 Hz), 131.4 (d, JZ92.6 Hz), 132.0 (d, JZ9.8 Hz),
135.9 (d, JZ18.0 Hz), 142.4 (d, JZ10.6 Hz); 31P NMR
(CDCl3) d 38.40.
3.3.5. Bis(4-chlorostyryl)phenylphosphine oxide (5e).
(Z,Z)-Isomer: white solid; mp 111–112 8C; IR (CHCl3)
1
1175 cmK1; MS (EI) m/z 398 (MC); H NMR (CDCl3) d
3.3.2. Bis(styryl)phenylphosphine oxide (5b). (Z,Z)-Iso-
mer: white solid; mp 78–80 8C; IR (KBr) 1178 cmK1; MS
6.09 (2H, dd, JZ19.6, 14.0 Hz), 7.15–7.39 (9H, m), 7.64–
7.68 (6H, m); 13C NMR (CDCl3) d 124.4 (d, JZ100.0 Hz),
128.1, 128.3, 130.7 (d, JZ9.8 Hz), 131.39, 131.44 (d, JZ
3.2 Hz), 133.2 (d, JZ106.5 Hz), 133.5 (d, JZ8.2 Hz),
135.3, 147.0; 31P NMR (CDCl3) d 14.78. Anal. Calcd for
C22H17Cl2OP: C, 66.18; H, 4.29. Found: C, 66.12; H, 4.01.
(Z,E)-Isomer: white solid; mp 150–151 8C; IR (CHCl3)
1
(EI) m/z 330 (MC); H NMR (CDCl3) d 6.07 (2H, dd, JZ
19.5, 14.0 Hz), 7.18–7.32 (11H, m), 7.65–7.72 (6H, m); 13C
NMR (CDCl3) d 123.9 (d, JZ100.0 Hz), 127.8, 128.0,
129.1, 130.0, 130.7 (d, JZ9.8 Hz), 131.0 (d, JZ2.5 Hz),
133.7 (d, JZ107.5 Hz), 135.2 (d, JZ7.4 Hz), 148.0; 31P
NMR (CDCl3) d 15.03. Anal. Calcd for C22H19OP: C,
79.98; H, 5.80. Found: C, 79.87; H, 5.81. (Z,E)-Isomer:
1
1180 cmK1; MS (EI) m/z 398 (MC); H NMR (CDCl3) d
6.25 (1H, dd, JZ19.1, 13.8 Hz), 6.40 (1H, dd, JZ22.7,

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K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
17.1 Hz), 7.20–7.50 (11H, m), 7.64–7.77 (4H, m); 31P NMR
(CDCl3) d 17.21. Anal. Calcd for C22H17Cl2OP: C, 66.18;
H, 4.29. Found: C, 66.19; H, 4.16.
1H NMR (CDCl3) d 0.86 (3H, t, JZ7.1 Hz), 1.15–1.27 (8H,
m), 1.97–2.00 (2H, m), 6.47 (1H, dd, JZ18.7, 13.2 Hz),
6.53 (1H, ddt, JZ35.8, 13.2, 2.4 Hz), 7.43–7.53 (6H, m),
7.76–7.81 (4H, m); 13C NMR (CDCl3) d 14.0, 19.6, 22.4,
27.7, 28.4, 31.2, 77.3 (d, JZ12.3 Hz), 104.8, 128.3 (d, JZ
12.3 Hz), 128.4 (d, JZ1.6 Hz), 131.26 (d, JZ9.8 Hz),
131.30 (d, JZ99.3 Hz), 131.6 (d, JZ3.5 Hz), 133.0 (d, JZ
105.8 Hz); 31P NMR (CDCl3) d 21.46. Anal. Calcd for
C22H25OP: C, 78.55; H, 7.49. Found: C, 78.60; H, 7.58.
3.3.6. Bis(4-bromostyryl)phenylphosphine oxide (5f).
(Z,Z)-Isomer: white solid; mp 117–118 8C; IR (CHCl3)
1
1180 cmK1; MS (EI) m/z 486 (MC); H NMR (CDCl3) d
6.10 (2H, dd, JZ19.7, 14.0 Hz), 7.20 (2H, dd, JZ40.1,
14.0 Hz), 7.27–7.39 (7H, m), 7.58–7.68 (6H, m); 13C NMR
(CDCl3) d 123.8, 124.6 (d, JZ99.2 Hz), 128.2 (d, JZ
12.3 Hz), 130.7 (d, JZ9.8 Hz), 131.2, 131.5 (d, JZ2.5 Hz),
131.6 (d, JZ1.2 Hz), 133.2 (d, JZ107.3 Hz), 134.0 (d, JZ
7.4 Hz), 147.1; 31P NMR (CDCl3) d 12.14. Anal. Calcd for
C22H17Br2OP: C, 54.13; H, 3.51. Found: C, 54.18; H, 3.51.
(Z,E)-Isomer: white solid; MS (EI) m/z 486 (MC); 1H NMR
(CDCl3) d 6.25 (1H, dd, JZ19.1, 14.0 Hz), 6.40 (1H, dd,
JZ23.0, 17.4 Hz), 7.19–7.76 (15H, m); 13C NMR (CDCl3)
d 121.0 (d, JZ104.9 Hz), 123.4 (d, JZ99.2 Hz), 124.1,
128.7 (d, JZ12.2 Hz), 128.9, 129.1, 130.5 (d, JZ10.7 Hz),
131.2, 131.6, 131.8, 132.0, 133.1 (d, JZ112.0 Hz), 133.98,
134.03 (d, JZ25.4 Hz), 145.1 (d, JZ3.3 Hz), 147.8; 31P
NMR (CDCl3) d 14.61.
3.3.10. 1,2,3,4,5-Pentaphenyl-1-phosphacyclopent-2-ene
1-oxide (10). Isolated as a single isomer with unknown
stereochemistry; white solid; mp 295–297 8C; IR (KBr)
1215 cmK1; MS (MALDI) m/z 482.60 (MC); 1H NMR
(CDCl3) d 3.98 (1H, dd, JZ10.1, 8.2 Hz), 4.96 (1H, dd, JZ
27.3, 8.2 Hz), 7.01–7.39 (23H, m), 7.67–7.72 (2H, m); 13C
NMR (CDCl3) d 51.0 (d, JZ69.7 Hz), 59.7 (d, JZ7.3 Hz),
126.7, 127.0, 127.4, 127.7, 128.1, 128.27, 128.34, 128.40 (d,
JZ10.6 Hz), 128.85, 128.90, 129.7, 130.8 (d, JZ7.5 Hz),
131.5 (d, JZ9.8 Hz), 131.6 (d, JZ2.4 Hz), 133.1 (d, JZ
119.6 Hz), 133.7 (d, JZ1.0 Hz), 133.9, 134.0, 136.1 (d, JZ
92.6 Hz), 136.6 (d, JZ15.5 Hz), 137.2, 157.9 (d,
JZ25.4 Hz); 31P NMR (CDCl3) d 52.06. Anal. Calcd for
C34H27OP: C, 84.63; H, 5.64. Found: C, 84.44; H, 5.68.
3.3.7. 3,6-Bis(diphenylphosphinyl)-2,2,7,7-tetramethy-
locta-3,4-diene (7). White solid; mp 202–204 8C; IR
(KBr) 1203, 1186 cmK1; MS (MALDI) m/z 564.01
(MCK2); MS m/z 566 (MC), 509 (MCKtBu), 452
(MCK2tBu), 365 (MCKPh2PO), 308 (365-tBuC), 201
3.3.11. Di(decyl)phenylphosphine oxide (11). White solid;
mp 56–57 8C; IR (KBr) 1165 cmK1; MS (EI) m/z 406 (MC);
1H NMR (CDCl3) d 0.86 (6H, t, JZ6.7 Hz), 1.21–2.17
(36H, m), 7.47–7.52 (3H, m), 7.66–7.71 (2H, m); 13C NMR
(CDCl3) d 14.1, 21.4 (d, JZ4.1 Hz), 22.7, 29.1, 29.3, 29.4,
29.5 30.0 (d, JZ68.1 Hz), 31.0 (d, JZ13.8 Hz), 31.9, 128.6
(d, JZ11.4 Hz), 130.4 (d, JZ8.2 Hz), 131.4 (d, JZ3.2 Hz),
132.3 (d, JZ91.8 Hz); 31P NMR (CDCl3) d 40.72. Anal.
Calcd for C26H47OP: C, 76.80; H, 11.65. Found: C, 76.84;
H, 11.65.
1
(Ph2POC); H NMR (CDCl3) d 1.16 (9H, s), 1.33 (9H, s),
2.81 (1H, ddd, JZ7.7, 5.9, 4.3 Hz), 5.30 (1H, ddd, JZ16.7,
11.6, 7.7 Hz), 6.94–7.76 (20H, m); 13C NMR (CDCl3) d
29.8 (d, JZ5.7 Hz), 29.9 (d, JZ4.1 Hz), 37.5 (d, JZ
6.6 Hz), 37.8 (d, JZ5.7 Hz), 45.3 (dd, JZ70.6, 4.9 Hz),
90.6 (d, JZ13.9 Hz), 107.8 (d, JZ96.8 Hz), 127.9 (d, JZ
11.5 Hz), 128.1 (d, JZ100.9 Hz), 128.7, 130.2 (d, JZ
1.6 Hz), 130.8 (d, JZ9.8 Hz), 130.9 (d, JZ12.3 Hz), 128.3
(d, JZ11.5 Hz), 128.4 (d, JZ11.5 Hz), 130.0 (d, JZ
9.1 Hz), 130.5 (d, JZ8.2 Hz), 130.7 (d, JZ2.5 Hz), 131.1
(d, JZ3.3 Hz), 131.4 (d, JZ2.5 Hz), 131.5 (d, JZ3.3 Hz),
131.6 (d, JZ9.0 Hz), 132.0 (d, JZ10.7 Hz), 132.9 (d, JZ
100.9 Hz), 134.0 (d, JZ96.0 Hz), 135.6 (d, JZ95.2 Hz),
137.8 (d, JZ108.3 Hz), 207.1 (d, JZ26.3 Hz); 31P NMR
(CDCl3) d 28.78 (d, JZ5.9 Hz), 31.68 (d, JZ5.9 Hz). Anal.
Calcd for C36H40O2P2: C, 76.31; H, 7.11. Found: C, 76.53;
H, 7.11.
References and notes
1. For a review, see: Minami, T.; Okauchi, T. In Katritzky, A. K.,
Taylor, R. J. K., Eds.; Comprehensive Organic Functional
Group Transformations II; Elsevier: Oxford, 2005; Vol. 2,
Chapter 2.16, pp 853–907.
2. (a) Han, L.-B.; Tanaka, M. J. Am. Chem. Soc. 1996, 118,
1571–1572. (b) Reichwein, J. F.; Patel, M. C.; Pagenkopf,
B. L. Org. Lett. 2001, 3, 4303–4306. (c) Deprele, S.;
Montchamp, J.-L. J. Am. Chem. Soc. 2002, 124, 9386–9387.
For a recent example, see: Han, L.-B.; Zhang, C.; Yazawa, H.;
Shimada, S. J. Am. Chem. Soc. 2004, 126, 5080–5081 and
references therein.
3.3.8. 1-Diphenylphosphinyl-1-phenyldec-1-en-3-yne
(8d). Isolated as a mixture of (Z) and (E)-isomer (91:9);
yellow oil; IR (neat) 1190 cmK1; MS (EI) m/z 412 (MC); 1H
NMR (CDCl3) d (Z)-isomer: 0.84 (3H, t, JZ6.9 Hz), 1.14–
1.56 (8H, m), 2.53–2.61 (2H, m), 6.52 (1H, d, JZ36.2 Hz),
6.87 (2H, d, JZ7.0 Hz), 7.15–7.57 (9H, m), 7.70–7.86 (4H,
m); (E)-isomer: 6.22 (d, JZ18.1 Hz); 13C NMR (CDCl3) d
(Z)-isomer: 14.0, 22.4, 28.7, 29.4 (d, JZ3.2 Hz), 31.5, 34.9
(d, JZ8.2 Hz), 86.7 (d, JZ10.6 Hz), 99.8 (d, JZ1.6 Hz),
120.8 (d, JZ6.5 Hz), 127.9, 128.3 (d, JZ12.3 Hz), 128.5,
131.3, 131.73, 131.76 (d, JZ10.7 Hz), 131.8, 132.5 (d, JZ
103.4 Hz), 146.8 (d, JZ90.5 Hz); 31P NMR (CDCl3) d (Z)-
isomer: 27.76, (E)-isomer: 31.77. Anal. Calcd for
C28H29OP: C, 81.53; H, 7.09. Found: C, 81.56; H, 7.22.
3. (a) Ohmiya, H.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int.
Ed. 2005, 44, 2368–2370. (b) Kazankova, M. A.; Efimova,
I. V.; Kochetkov, A. N.; Afanas’ev, V. V.; Beletskaya, I. P.;
Dixneul, P. H. Synlett 2001, 497–500. This method was,
however, applicable to olefin hydrophosphination, see: (c)
Shulyupin, M. O.; Kazankova, M. A.; Beletskaya, I. P. Org.
Lett. 2002, 4, 761–763. (d) Kazankova, M. A.; Shulyupin,
M. O.; Beletskaya, I. P. Synlett 2003, 2155–2158.
4. (a) Douglass, M. R.; Marks, T. J. J. Am. Chem. Soc. 2000, 122,
1824–1825. (b) Douglass, M. R.; Stern, C. L.; Marks, T. J.
J. Am. Chem. Soc. 2001, 123, 10221–10238. (c) Douglass,
3.3.9. (Z)-1-Diphenylphosphinyldec-1-en-3-yne (8g).
Yellow oil; IR (neat) 1188 cmK1; MS (EI) m/z 336 (MC);

K. Komeyama et al. / Tetrahedron 62 (2006) 2511–2519
2519
M. R.; Ogasawara, M.; Hong, S.; Metz, M. V.; Marks, T. J.
Organometallics 2002, 21, 283–292.
9. Mitchell, T. N.; Heesche, K. J. Organomet. Chem. 1991, 409,
163–170.
5. (a) Takaki, K.; Takeda, M.; Koshoji, G.; Shishido, T.;
Takehira, K. Tetrahedron Lett. 2001, 42, 6357–6360. (b)
Takaki, K.; Koshoji, G.; Komeyama, K.; Takeda, M.;
Shishido, T.; Kitani, A.; Takehira, K. J. Org. Chem. 2003, 68,
6554–6565.
10. (a) Komeyama, K.; Takehira, K.; Takaki, K. Synthesis
2004, 1062–1066. (b) Komeyama, K.; Sasayama, D.;
Kawabata, T.; Takehira, K.; Takaki, K. Chem. Commun.
2005, 634–636.
11. Bradley, D. C.; Ghotra, J. S.; Hart, F. A. J. Chem. Soc., Dalton
Trans. 1973, 1021–1023.
6. Komeyama, K.; Kawabata, T.; Takehira, K.; Takaki, K. J. Org.
Chem. 2005, 70, 7260–7266.
12. Sonogashira, K. In Trost, B. M., Fleming, I., Eds.;
Comprehensive Organic Synthesis; Pergamon: Oxford, 1991;
Vol. 3, Chapters 2.4 and 2.5, pp 521–561.
7. The original phosphine products were isolable, but oxidized
partially during the work-up and purification. Thus, they were
isolated and characterized as phosphine oxides.
8. Although the mechanism leading to 10 is unknown at present,
it may be formed by cyclization of (Z)-phosphinoalkenylyt-
terbium species, (Z)-isomer corresponding to G depicted in
Scheme 3.
13. Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763–2766.
14. (a) Dabdoub, M. J.; Dabdoub, V. B. Tetrahedron 1995, 51,
9839–9850. (b) Dabdoub, M. J.; Baroni, A. C. M.; Lenardao,
E. L.; Gianeti, T. R.; Hurtado, G. R. Tetrahedron 2001, 57,
4271–4276.