Copper (II)-catalyzed regio- and stereoselective addition of H/P(O)R 2 to alkynes

Article abstract of DOI:10.1016/j.tet.2014.02.037

Cu(acac)₂ is the new universal catalyst for β-E regio- and stereoselective syn-addition of the H-P(O)-bond of diphenylphosphine oxide, H-phosphinates, dialkylphosphites to various alkynes in the synthesis of P(O)-containing alkenes. Without additives and ligands Cu(II)-compounds showed better results than CuI or Ni(acac)₂. The catalytic system developed is tolerant to typical organic functional groups present in the alkynes and to the nature of different substituents in the H-P(O)-compounds.

Full text of DOI:10.1016/j.tet.2014.02.037

Tetrahedron 70 (2014) 2556e2562
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Tetrahedron
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Copper (II)-catalyzed regio- and stereoselective addition of H/P(O)R2
to alkynes
*
Inna G. Trostyanskaya, Irina P. Beletskaya
Department of Chemistry, Moscow State University, Leninskie Gory, 119991 Moscow, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Cu(acac)2 is the new universal catalyst for b-E regio- and stereoselective syn-addition of the HeP(O)-
Received 6 December 2013
Received in revised form 6 February 2014
Accepted 17 February 2014
Available online 22 February 2014
bond of diphenylphosphine oxide, H-phosphinates, dialkylphosphites to various alkynes in the synthesis
of P(O)-containing alkenes. Without additives and ligands Cu(II)-compounds showed better results than
CuI or Ni(acac)2. The catalytic system developed is tolerant to typical organic functional groups present in
the alkynes and to the nature of different substituents in the HeP(O)-compounds.
Ó 2014 Elsevier Ltd. All rights reserved.
Keywords:
Hydrophosphinylation
Hydrophosphonylation
Hydrophosphorylation
Alkynes
Copper(II)-catalyst
syn-Addition
1. Introduction
Transition metal catalyzed addition of the HeP(O) bond to the
triple bond of terminal and internal alkynes is intensively studied
a
,
b
-Unsaturated tetra co-ordinated organophosphorus com-
using palladium, rhodium and to a lesser extent nickel based cat-
pounds are a useful class of intermediates that undergo many
synthetic organic transformations. They are commonly used as
building blocks in the preparation of carbocyclic and heterocyclic
compounds,1 as Michael acceptors, 1,3-dipolarophiles and pre-
alysts11 and even hexacarbonylmolybdenum(0).12
They allow to develop efficient and selective methods for the
synthesis of a- and b-alkenylphosphorus derivates (Markovnikov
and anti-Markovnikov isomers).11e13 (Scheme 1).
cursors in the synthesis of allenes,2 -ketophosphonates,3 some of
g
which are biologically active,4 in the preparation of ligands for
homogeneous catalysis and in asymmetric synthesis.5 Alkenyl-
phosphine oxides, phosphonates, and phosphinates serve as in-
termediates for the synthesis of herbicides,6 in polymer science
as additives or flame-retardants.7 Many compounds with useful
biological and pharmacological properties contain an alkenyl-P(V)
fragment,8 and besides there compounds serve as precursor
of many other biologically or pharmacologically active
compounds.9a,10,11
The addition reactions of element-hydrogen bonds to triple
bonds present the most efficient and atom-economical pathway to
alkenyl derivatives of the corresponding elements, many of which
present interest as building blocks or biologically active
compounds.9e11
Scheme 1. Possible products in a P(O)eH bond addition reaction to alkynes.
One of the main trends in modern catalysis is the replacement of
costly palladium and rhodium catalysts for more cheap and easily
accessible copper and nickel compounds. Following this trend we
decided to test the ligandless copper, both Cu(I) and Cu(II), and
nickel salts as catalysts in the addition of various HeP derivatives,
H-phosphine oxides, H-phosphinates, H-phosphonates, to alkynes.
We started with the most widely studied substrate Ph2P(O)H,
for which both the conditions for obtaining the
a-isomer (Mar-
kovnikov’s adduct)14b,15e17 and the
b-E-isomer using Pd, Rh, Ni
catalysts11i,12,14a,15,18 and CuI in DMSO with ethylenediamine as li-
gand are known.13
* Corresponding author. Tel.: þ7 495 9393618; fax: þ7 499 135 5328; e-mail
address: beletska@org.chem.msu.ru (I.P. Beletskaya).
0040-4020/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.02.037

I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
2557
2. Results and discussion
electronic and coordination properties, the reaction proceeded
with quantitative yield and high regio- and stereoselectivity, al-
though the yield of alkenylphosphinate (3ca) synthesized from
dimethylpropargyl amine (1c) was slightly lower.
From these data one can safely conclude that the addition of
Ph2P(O)H to aromatic and aliphatic alkynes proceeds as syn-
As a model reaction, we studied the addition of Ph2P(O)H to
phenylacetylene in different solvents (THF, DMF, MeCN, i-PrOH,
dioxane, ethanol etc.) using Ni and Cu salts as catalysts (Table 1).
The reaction did not go without catalyst at 50e100 ꢀC (entry 1).
Table 1
Ni- and Cu-catalyzed addition of diphenylphosphine oxide to phenylacetylene
Ph
cat(5mol%),
solvent, h
Ph
P(O)Ph2
+
Ph2P(O)H
Ph
+
P(O)Ph2
E
Z
Entry
Catalyst
Solvent
THF, DMF, CH3CN
Toluene, THF, CH3CN, i-PrOH, dioxane
Temp, (ꢀC)
Time, (h)
Conversion, (%)
Ratio of isomers, E/Z, (%)a,b
1
2
3
None
NiCI2, NiBr2
Ni(acac)2
90e100
100
100
50
50
8
<10
<50
65
d
60e70/40e30
85/15
THF
EtOH
60
80/20
DMF
82
85/15
CH3CN
90
90/10
4
CuI
i-AmOH/ethylene glycol 10/1
CH3CN
75e80
8
7
100
80
100
100
DMF
7
6
100
100
100c
100
100
100
DMF/THF 3/1
DMF/THF 3/1
DMF/THF 3/1
None
DMSO
Toluene
DMF
CH3CN
DMF/THF 3/1
5
CuSO4
70e75
70e75
70e75
70e75
70e75
70e75
70e75
70e75
24
8
40
1.5
2
20
23
6
Mixture of compounds
100
75
6
7
8
9
10
11
12
Cu(OAc)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
78
c
d
c
d
100
100
100d
98
98
100
a
0.5 mmol Ph2P(O)H, 0.5 mmol phenylacetylene, 0.25 mL solvent, 5 mol % catalyst under argon.
E/Z isomers ratio and % conversion was determined by 31P NMR.
Precipitation of metallic Cu.
b
c
d
High yield 90% and selectivity 90% for the system CuI/EDA in DMSO was also reported previously.13
Catalysis by nickel salts NiCl2 and NiBr2 showed only poor effi-
addition with the formation of
b
-E-isomer. It is known that
ciency (entry 2), while Ni(acac)2 led to reaction in CH3CN with high
hydrophosphinylation of internal alkynes is much more difficult to
carry out than the addition to terminal alkynes.
yield and high
were obtained with CuI in different solvents (100% yield and 100%
-E-selectivity) (entry 4). Cu(OAc)2 gave similar result also (entry
b-E-selectivity (entry 3). However, the best results
However, the Cu(acac)2-catalyzed hydrophosphinylation of
diphenylacetylene and oct-4-yne with Ph2P(O)H gave the product
in good yield and high syn-selectivity, although it required
longer time for completion than the addition to terminal alkynes
(Scheme 2).
b
6), but Cu(acac)2 in DMF/THF at 70 ꢀC provided a quantitative yield
and 100% selectivity in short reaction times (entry 12). Considering
the availability and good solubility of this catalyst we used this
system to perform the reactions with various alkynes (Table 2). For
all aliphatic alkynes studied, with substituents of different
The addition of H-phosphinates to alkynes is the least studied
reaction in the chosen triad. It is known that the reaction of Ph(EtO)
Table 2
Cu(acac)2-catalyzed addition of diphenylphosphine oxide to terminal alkynes
R
5mol% Cu(acac)2
+
Ph2P(O)H
R
P(O)Ph2
DMF/THF (3:1), 70-75 °C
1 a-e
E
2a
3 a-e
Entry
R
Product
Time, (h)
Conversion,a,b,c (%)
Yield, (%)d
1
2
3
4
5
Ph (1a)
Bu (1b)
Me2NCH2 (1c)
HOCH2 (1d)
3aa
3ba
3ca
3da
3ea
6
8
6
6
10
100
100
85
100
100
98
98
83
98
98
Me2C(OH) (1e)
a
Reaction conditions: diphenylphosphine oxide (1 mmol), alkyne (1 mmol), Cu(acac)2 5 mol %, 1.5 mL DMF, 0.5 mL THF, 70e75 ꢀC under argon.
b
c
Conversion determined by 31P NMR.
The heating above 70e75 ꢀC leads to formation of metallic Cu.
Isolated yield.
d

2558
I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
R
R
5mol% Cu(acac)2
R
R
+
Ph2P(O)H
DMF/THF (3:1), 75 °C
H
P(O)Ph2
E
1f, R = Ph
1g, R = Bu
2a
R=Ph, 22h, 84%; (3f,a)
R=Bu, 30h, 76%;
(3g,a)
Scheme 2. Hydrophosphinylation of internal alkynes.
P(O)H with phenylacetylene catalyzed by Rh11i,18,19 and Ni(0)15
complexes and by CuI/ethylenediamine13 leads to anti-
Markovnikov product with E-configuration, and the catalysis by
Pd complexes is less regioselective although also gives mainly the
Our study of the reaction of phenylacetylene with dieth-
ylphosphite in the presence of ligand-free salts Ni and Cu(I) and
Cu(II) reveals that this reaction is sensitive to the nature of the
metal catalyst and is significantly less facile than the reactions with
diphenylphosphine oxide and H-phosphinates (Table 4). All cata-
lysts (Ni(acac)2 (entry 2)), CuI (entry 3), Cu(OAc)2 (entry 4) or CuSO4
(entry 5) showed poor activity. Catalysis with these copper salts
mainly leads to the isomers of 1,4-diphenylbut-1-en-3-yne21 up to
70% according to NMR spectroscopic data. However the use of
Cu(acac)2 and a more prolonged reaction time than for phosphine
b
-isomer.19c
We showed (Table 3) that the addition of Ph(EtO)P(O)H and
9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide to various
alkynes is catalyzed by ligand-free salts Ni(acac)2, CuI, but the most
effective catalyst was Cu(acac)2. The use of Cu(acac)2 significantly
reduces the reaction time compared to Ni(acac)2 (entries 2, 3, 7)
and CuI (entries 3e5, 7). In most cases high product yields and
b
-E-
oxides and H-phosphinates gave b-E-isomers of alkenylphospho-
selectivity are obtained (Table 3, entries 2e4, 7, 8), except for
dimethylpropargyl amine (1c) and propargyl alcohol (1d) for which
the yields were lower (entries 5, 6). Somewhat lower selectivity
was also observed for Ni(acac)2 (entry 7).
nates in moderate to high yields from various alkynes (entries
7e10). The reaction is complicated by the formation of side prod-
ucts, associated with alkyne phosphorylation22 (entries 7, 9, 10) and
double bond isomerization in the addition product formed (entry
Table 3
Cu (II, I) and Ni (II)-catalyzed addition of H-phosphinates to alkynes
R1
R2O
R
5mol% [Cu] or [Ni]
DMF/THF (3:1), 70-75 °C
R1
P(O)H
+
R
(O)P
OR2
4 ab; bb; cb; db; ac; ec
1 a-d, e
2b,c
Entry
R
H-Phosphinate
[Cu] or [Ni}
Product
Time, (h)
Conversion, (%)a,b
Yield, (%)c
1
2
3
Ph (1a)
Ph (1a)
Ph (1a)
Ph(EtO)P(O)H (2b)
Ph(EtO)P(O)H (2b)
Ph(EtO)P(O)H (2b)
None
4ab
4ab
4ab
50
40
14
20
24
48
14
25
16
n. d.
90
94
89
98
96
78
78
80
n. d.
86
92
86
95
94
75
75
72
Ni(acac)2 CH3CN
Cu(acac)2
CuId
Cu(acac)2
CuI
Cu(acac)2
CuI
Cu(acac)2
4
5
C5H13 (1b)
Ph(EtO)P(O)H (2b)
Ph(EtO)P(O)H (2b)
Ph(EtO)P(O)H (2b)
4bb
4cb
Me2NCH2 (1c)
6
7
OHCH2 (1d)
Ph (1a)
4db
4ac
Cu(acac)2
CuI
Ni(acac)2 CH3CN
16
25
100
100
100
98
98
(2c)
48 (80 ꢀC)
96 (E/Z 90/10)
O P(O)H
O P(O)H
8
Me2C(OH) (1e)
Cu(acac)2
4ec
18
98
96
(2c)
a
Reaction conditions: H-phosphinate (1 mmol), alkyne (1 mmol), 1.5 mL DMF, 0.5 mL THF, [Cu] (5 mol %), 70 ꢀC.
b
c
Conversion was determined by 31P NMR.
Isolated yield.
d
Catalysis by CuI/EDA in DMSO system processed at 90 ꢀC gives 82% yield.13
In the literature the regioselectivity of H/P addition is mostly
studied in the reaction of dialkylphosphites (H-phosphonates) with
terminal alkynes. It is shown that -isomer is selectively obtained
with Pd catalysts in the presence of Ph2P(O)OH17a,20a or
8). It should be noted that Cu(I) or Cu(II) catalyzed addition of
dialkylphosphites to alkynes prior to this work remained unknown.
However, for more acidic H-phosphonate (PhO)2P(O)H, the addi-
tion product under the same reaction conditions is not observed at
all. A mixture of enyne isomers21 (6a) and (6b) is formed with
yields up to 90% (predominantly E-isomer) together with a small
amount of phosphorylated alkyne (7) (up to 10%), the E/Z isomer
ratio of enynes strongly depending on the solvent: in DMF/THF it is
10/1, while in DMSO it is 2/1 (Scheme 3).
a
CF3COOH,20a as well as Ni (II)/dppe,20b Ni (II)/dppb,20c while the
b-
isomer is obtained in the presence of RhCI(PPh3)3,20d Ni(0) in
ethanol.15a A recent study showed that the regioselectivity of Pd-
catalyzed reactions strongly depends on steric factors in triar-
ylphosphine ligands.20e

I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
2559
Table 4
[Cu]-catalyzed addition diethylphosphite to terminal alkynes
R
5mol% [Cu]
(EtO)2P(O)H
R
+
DMF:THF=3:1, 70 °C
P(O)(OEt)2
5 ad; bd; dd; ed and 5`bd
2d
1a, b, d, e
Entry
R
Catalyst
Product
Time, (h)
Conversion,a,b (%)
Yield,c (%)
1
2
3
Ph (1a)
Ph (1a)
Ph (1a)
None
Ni(acac)2
CuI
50
50
48
n. d.
n. d.
10
d
d
5ad
d
100
24
24
100
24
48
35
25
30
10
75
86
80
70
58
4
5
6
7
8
9
10
Ph (1a)
Ph (1a)
Ph (1a)
Ph (1a)
C5H11 (1b)
HOCH2 (1d)
Me2C(OH) (1e)
Cu(OAc)2
CuSO4
Cu(acac)2 (without solvent)
Cu(acac)2
Cu(acac)2
Cu(acac)2
5add
5add
100
100
78
92
87
5ad
5ade
5bd, 50bd
5dde
30
42
78
95
Cu(acac)2
5edf
fMixture E isomers of (5bd) (Eto)2P(O)CH]CH(CH2)4CH3 and (50bd) (Eto)2P(O)CH2CH]CH(CH2)3CH3 due to isomerization of double bond.
a
Reaction conditions: H-phosphonate (1 mmol), alkyne (1 mmol), 1.5 mL DMF, 0.5 mL THF, Cu(acac)2 (5 mol %), 70 ꢀC.
b
Conversion was determined by 31P NMR.
c
Isolated yield.
d
Mixture of E/Z¼2/1 isomers of 1,4-diphenylbutene-1-yne-3 (70% by 1H and 13C NMR).
e
R
5e10% is formed (EtO)2P(O)
.
.
f
(
d
P
(EtO)2P(O)
C(OH)Me2
ꢁ6.4 ppm) is formed (w25%).
Scheme 3. Dimerization of terminal alkynes; dependency of E/Z-isomer ratio of enynes on the solvent.
The obtained data show that the activity of HeP(O) phosphorus
4. Experimental
4.1. General
compounds in the addition to the triple bond of alkynes under
Cu(acac)2 catalysis increases in the order (EtO)2P(O)H<R(R1O)P(O)
H<Ph2P(O)H, the same order as found for the HeP bond energy of
such compounds.23 The origin of this trend is as yet not quite clear,
and it is difficult to explain it by differences in the acidity of
HeP(O)-compounds.24
All reactions were performed under argon atmosphere. Solvents
were dried and purified before use by standard procedure, HeP(O)-
acids obtained by known methods, all alkynes were purchased
from commercial sources. 1H and 13C NMR spectra were recorded
with TMS (0.00 ppm) or CDCI3 (1H NMR at 7.26 ppm and 13C NMR at
77.0 ppm) as internal standards, 85% H3PO4 was used as the ex-
ternal reference of 31P NMR spectra.
3. Conclusion
We have shown that Cu(acac)2 is a new universal catalyst for
syn-addition of HeP(O)-bond to various alkynes to give
b-E-
alkenylphosphorus compounds. The activity of Cu(acac)2 is higher
than that of CuI or Ni(acac)2 and the addition of P(O)eH phos-
phonates to alkynes takes place only in the presence of the
Cu(acac)2 catalyst. The catalytic system developed is tolerant of
typical organic functional groups present in the alkynes and to
different substituents in the HeP(O)-compounds. Thus, the
Cu(acac)2-catalyzed addition of HeP(O)-compounds to alkynes
4.2. Typical experimental procedure for Cu(acac)2-catalyzed
addition of diphenylphosphine oxide, H-phosphinates, and H-
phosphonates to terminal alkynes
To a mixture of 1 mmol HeP(O)-compound, 0.013 g (5 mol %)
Cu(acac)2 in 2.0 mL of the solvents (THF/DMF¼1/3) after strong
mixing and full dissolution by Cu(acac)2 was added 1 mmol of the
correspondent alkyne. The mixture was stirred at 70e75 ꢀC for
6e48 h (Tables 1e4), cooled to room temperature and then evap-
orated under vacuum. The remainder was diluted with 10 mL
CHCl3, filtered, and concentrated under vacuum. This procedure
can be used as a preparative method for the synthesis of diverse b-
E-P(O)-containing alkenes. Mechanistic studies and application of
this methodology to other H-heteroatom bond compounds are
underway.

2560
I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
was repeated. If the conversion rate of the reaction was 98e100%
and also for diethylalkennylphosphonates (5) volatile compounds
were removed by keeping the residue under vacuum 1 mmHg at
70e75 ꢀC for 1 h. If needed the crude products were purified by
column chromatography on silica gel (EtOAc/toluene 1/3). Yields of
the alkenylphosphine oxides (3) are given in Table 2, alkenyl-
phosphinates (4)din Table 3, alkenylphosphonates (5) in Table 4.
For known compounds spectroscopic data is identical to that re-
ported in the literature.
4H); 13C NMR (100.6 MHz, CDCl3):
d
¼13.8, 22.3, 23.4, 30.5 (J
11.0 Hz), 30.8 (J 15.3 Hz), 128.4 (J 11.5 Hz), 131.3 (J 1.8 Hz), 132.3 (J
9.0 Hz),133.9 (J 96.0 Hz),135.1 (J 95.8 Hz),146.1 (J 10.0 Hz); 31P NMR
(161.9 MHz, CDCl3):
d
¼30.32.
4.2.8. E-1-(Ethoxy-phenylphosphinyl)-2-phenylethene (4ab) (entry
3, Table 3).13,15a Yield: 92% (0.258 g) as colorless oil; 1H NMR
(400 MHz, CDCl3):
6.49 (dd, JHH 16.0 Hz, JPH 20.0 Hz, 1H), 7.34e7.35 (m, 3H), 7.48e7.57
(m, 6H), 7.83e7.88 (m, 2H); 13C NMR (100.6 MHz, CDCl3):
d
¼1.37 (t, JHH 7.0 Hz, 3H), 4.02e4.18 (dm, 3H),
d
¼16.4,
4.2.1. E-1-Diphenylphosphinyl-2-phenylethene (3aa) (entry 1, Table
2).13,14,18a Yield: 92% (0.258 g) as white solid, mp 167e168 ꢀC; 1H
60.7, 117.8 (d, J 138.8 Hz), 127.6, 128.5 (d, J 14.1 Hz), 128.7, 130.0,
131.1, 131.1 (d, J 138.2 Hz), 131.3 (d, J 10.0 Hz), 135.9 (d, J 20.0 Hz),
NMR (400 MHz, CDCl3):
d
¼6.85 (dd, JHH 18.0 Hz, JPH 26 Hz, 1H),
147.7 (d, J 5.2 Hz); 31P NMR (161.9 MHz, CDCl3):
d
¼31.45.
7.36e7.79 (m, 16H); 13C NMR (100.6 MHz, CDCl3):
d
¼119.7 (d, J
100.4 Hz), 127.5, 127.8, 128.0, 128.6 (d, J 11.0 Hz), 128.7, 129.8, 131.4
4.2.9. E-1-(Ethoxy-phenylphosphinyl)hept-1-ene (4bb) (entry 4,
Table 3). Yield: 95% (0.253 g) as colorless oil; [found: C 67.50; H
8.70; P 11.38. C15H23O2P requires C 67.67; H 8.65; P 11.65]; 1H NMR
(d, J 10.1 Hz), 131.5, 134.0 (d, J 104.2 Hz), 147.7 (d, J 3.0 Hz); 31P NMR
(161.9 MHz, CDCl3):
d¼23.15.
(400 MHz, CDCl3):
d
¼0.87 (t, JHH 7.0 Hz, 3H), 1.26e1.34 (m, 7H),
4.2.2. E-1-Diphenylphosphinylhex-1-ene (3ba) (entry 2, Table
2).25 Yield: 98% (0.278 g) as white solid, mp 74e75 ꢀC; 1H NMR
1.42e1.47 (m, 2H), 2.19e2.24 (m, 2H), 3.93e3.99 (m, 1H), 4.05e4,12
(m,1H), 6.77 (ddt, JHH 17.8 Hz, JPH 24.0 Hz,1H), 6.77 (ddt, JHH 17.7 Hz,
JHH 7.0 Hz, JPH 20.1 Hz), 7.45e7.55 (m, 3H), 7.76e7.81 (m, 2H); 13C
(400 MHz, CDCl3):
d
¼0.90 (t, J 7.8 Hz, 3H), 1.34 (m, 2H), 1.45 (m, 2H),
2.29 (m, 2H), 6.23 (dd, JHH 17.0 Hz, JPH 24.8 Hz, 1H), 6.71 (ddt, JHH
NMR (100.6 MHz, CDCl3):
d
¼13.8, 16.4 (d, J 5.0 Hz), 22.2, 27.3, 31.1,
17.0 Hz, JPH 19.6 Hz, 1H), 7.66e7.71 (m, 4H); 13C NMR (100.6 MHz,
34.1 (d, J 18.1 Hz), 60.5 (d, 6.1 Hz), 120.3 (d, J 137.8 Hz), 128.3 (d,
13.1 Hz), 131.2 (d, J 8.9 Hz), 131.5 (d, J 135.6 Hz), 131.9, 153.1 (d, J
CDCl3):
d
¼13.6, 22.0, 29.8, 34.3 (d, J 9.1 Hz), 131.6, 132.8 (d, J
¼24.47.
104.6 Hz), 153.0; 31P NMR (161.9 MHz, CDCl3):
d
3.0 Hz); 31P NMR (161.9 MHz, CDCl3):
d
¼31.14.
4.2.3. E-3-(N,N-Dimethylamino)-1-(diphenylphosphinyl)prop-1-ene
(3ca) (entry 3, Table 2). Yield: 86% (0.285 g) as white solid,
mp 97e98 ꢀC; [found: C 71.92; H 7.07; P 10.80. C12H20NOP requires
4.2.10. E-1-(Ethoxy-phenylphosphinyl)-3-(N,N-dimethyl)prop-1-ene
(4cb) (entry 5, Table 3). Yield: 75% (0.190 g) as white solid,
mp 42e43 ꢀC; [found: C 61.19; H 7.98; P 12.40. C13H20NO2P requires C
C 71.58; H 7.02; P 10.88]; 1H NMR (400 MHz, CDCl3):
d
¼2.30 (s, 6H),
61.66; H 7.91; P 12.25]; 1H NMR (400 MHz, CDCl3):
d¼1.32 (t, JHH 7.2 Hz,
3.24 (br s, 2H), 6.56 (dd, JHH 16,0 Hz, JPH 24.2 Hz, 1H), 6.63e6.75 (m,
3H), 2.37 (s, 6H), 3.29 (s, 2H), 3.94e4.00 (m,1H), 4.05e4.15 (m,1H), 6.22
(dd, JHH 16.5 Hz, JPH 24.0 Hz, 1H), 6.72 (ddt, JHH 16.2 Hz, JHH 6.7 Hz, JPH
18.9 Hz), 7.37e7.52 (m, 3H), 7.75e7.80 (m, 2H); 13C NMR (100.6 MHz,
1H), 7.43e7.51 (m, 6H), 7.68e7.72 (m, 4H); 13C NMR (100.6 MHz,
CDCl3):
11.1 Hz), 131.0 (d, J 9.1 Hz), 131.6, 132.4 (d, J 105.6 Hz), 147.2 (d, J
7.0 Hz); 31P NMR (161.9 MHz, CDCl3):
¼23.47.
d¼44.8, 61.4 (d, J 17.8 Hz), 125.0 (d, J 102.6 Hz), 128.3 (d, J
CDCl3):
135.8 Hz), 128.3 (d, J 12.1 Hz), 131.1 (d, J 9.0 Hz), 130.9 (d, J 135.2 Hz),
132.0, 145.0 (d, J 8.0 Hz); 31P NMR (161.9 MHz, CDCl3):
¼28.04.
d¼16.2 (d, J 7.1 Hz), 44.0, 60.0, 60.5 (d, J 9.0 Hz), 125.4 (d, J
d
d
4.2.4. E-3-Hydroxy-1-(diphenylphosphinyl)prop-1-ene (3da) (entry
4, Table 2).26 Yield: 98% (0.252 g) as colorless oil; 1H NMR
4.2.11. E-1-(Ethoxy-phenylphosphinyl)-3-hydroxyprop-1-ene (4db)
(entry 6, Table 3).28 Yield: 72% (0.163 g) as slightly yellow oil;
[found: C 58.32; H 6.60; P 13.85. C11H15O3P requires C 58.41; H 6.64;
(400 MHz, CDCl3):
6.59e6.82 (m, 2H), 7.38e7.47 (m, 6H), 7.63e7.68 (m, 4H); 13C NMR
(100.6 MHz, CDCl3):
¼62.1 (d, J 10.0 Hz), 118.7 (d, J 104.6 Hz), 128.3
(d, J 12.1 Hz), 131.0 (d, J 10.1 Hz), 131.6, 132.3 (d, J 105.6 Hz), 152.3;
31P NMR (161.9 MHz, CDCl3):
¼21.60.
d¼2.30 (br s, 1H, OH), 4.26 (d, JHH 4.0 Hz, 2H),
d
P 13.72]; 1H NMR (400 MHz, CDCl3):
d
¼1.30 (t, JHH 6.8 Hz, 3H), 2.25
(br s, 1H, OH), 3.95e4.01 (m. 1H), 4.07e4.14 (m, 1H), 4.32 (d, JHH
4.3 Hz, 2H), 6.28 (dd, JHH 16.0 Hz, JPH 24.0 Hz, 1H), 6.85 (ddt, JHH
d
16.0 Hz, JPH 20.0 Hz, 1H), 7.34e7.53 (m, 3H), 7.74e7.83 (m, 2H); 13
C
4.2.5. E-(1-Diphenylphosphinyl)-(3-hydroxy-3-methyl)but-1-ene
NMR (100.6 MHz, CDCl3):
140.8 Hz), 128.3 (d, J 12.1 Hz), 130.7 (d, 140.2 Hz), 131.1 (d, J 9.8 Hz),
131.9, 152.1 (d, J 4.1 Hz); 31P NMR (161.9 MHz, CDCl3):
¼29.72.
d
¼16.1, 60.6, 61.9 (d, J 4.8 Hz), 117.7 (d, J
(3ea) (entry 5, Table 2).15b,18e,26b Yield: 98% (0.280 g) as colorless oil;
1H NMR (400 MHz, CDCl3):
d
¼1.31 (s, 6H), 4.75 (br s, 1H, OH), 6.58
d
(dd, JHH 16.0 Hz, JPH 24.1 Hz, 1H), 6.83 (dd, JHH 16.0 Hz, JPH 20.0 Hz,
1H), 7.37e7.45 (m, 6H), 7.64e7.68 (m, 4H); 13C NMR (100.6 MHz,
4.2.12. E-10-(Styr-2-yl)-9,10-dihydro-9-oxa-10-phosphaphenantrene-
10-oxide (4ac) (entry 7, Table 3). Yield: 98% (0.311 g) as white solid,
mp 185e187 ꢀC; [found: C 75.09; H 4.72; P 10.01. C20H15O2P requires
CDCl3):
128.1, 130.8, 131.2, 132.6 (d, J 104.6 Hz), 150.4 (d, J 2.0 Hz); 31P NMR
(161.9 MHz, CDCl3):
¼24.97.
d¼28.9 (d, J 18.1 Hz), 70.8 (d, J 13.0 Hz), 116.6 (d, J 102.6 Hz),
d
C 75.47; H 4.72; P 9.75]; 1H NMR (400 MHz, CDCl3):
d
¼6.49 (dd, JHH
16.1 Hz, JPH 20.0 Hz, 1H), 7.11e7.14 (m, 1H), 7.23e7.27 (m, 1H),
7.35e7.37 (m, 3H), 7.44e7.51 (m, 3H), 7.65e7.73 (m, 1H), 7.77e7.83
4.2.6. E-1-Diphenylphosphinyl-1,2-diphenylethene (3fa) (Scheme
2).13,27 Yield: 84% (0.305 g) as white solid, mp 152e153 ꢀC; 1H
(m, 2H), 7.93e8.00 (m, 2H); 13C NMR (100.6 MHz, CDCl3):
d¼115.1 (d,
NMR (400 MHz, CDCl3):
CDCl3):
d
¼6.92e7.87 (m); 13C NMR (100.6 MHz,
J 143.9 Hz), 123.5 (d, J 13.1 Hz), 123.6 (d, J 10.1 Hz), 124.5, 124.9, 127.9,
128.2 (d, J 15.1 Hz), 128.7, 129.5, 130.5 (d, J 21.0 Hz), 131.1, 133.0, 134.3
(d, J 21.1 Hz), 134.9 (d, J 151.4 Hz),135.6 (d, J 4.1 Hz), 148.8 (d, J 8.1 Hz),
d
¼127.9, 128.1, 128.2 (d, J 8.9 Hz), 128.6 (d, J 2.0 Hz), 128.9,
130.1 (d, J 4.5 Hz), 130.6 (d, J 1.8 Hz) 131.1 (d, J 102.8 Hz), 131.5 (d, J
2.8 Hz) 132.2 (d, J 10.0 Hz),135.0 (d, J 2.5 Hz),135.7 (d, J 75.1 Hz),135.7
150.2 (d, J 7.1 Hz); 31P NMR (161.9 MHz, CDCl3):
d¼24.20.
(d, J 25.0Hz),143.0(d, J 8.5 Hz);31P NMR (161.9MHz, CDCl3):
d¼30.22.
4.2.13. E-10-(Hydroxy-3-methylbut-1-enyl)-9,10-dihydro-9-oxa-10-
phosphaphenantrene-10-oxide (4ec) (entry 8, Table 3). Yield: 96%
(0.288 g) as white solid, mp 91e92 ꢀC; [found: C 67.89; H 5.70; P
10.23. C17H17O3P requires C 68.00; H 5.67; P 10.33]; 1H NMR
4.2.7. E-(4-Diphenylphosphinyl)oct-4-ene (3ga) (Scheme
2).14b,18a,27 Yield: 76% (0.225 g) as white solid, mp 76e77 ꢀC; 1H
NMR (400 MHz, CDCl3):
3H), 1.14e1.18 (m, 2H), 1.42e1.55 (m, 2H), 2.16e2.24 (m, 2H), 6.11
(dt, JHH 8.0 Hz, JPH 24.0 Hz, 1H), 7.26e7.46 (m, 6H), 7.70e7.75 (dd,
d
¼0.76 (t, JHH 6.9 Hz, 3H), 0.93 (t, JHH 7.0 Hz,
(400 MHz, CDCl3):
d
¼1.31(s, 6H), 4.78 (br s, 1H, OH), 6.16 (dd, JHH
16.0 Hz, JPH 24.0 Hz, 1H), 7.04e7.90 (m, 9H); 13C NMR (100.6 MHz,

I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
2561
CDCl3):
d
¼28.5 (d, J 17.1 Hz), 70.7 (d, J 17.1 Hz), 113.6 (d, J 140.8 Hz),
References and notes
120.0 (d, J 5.0 Hz), 121.8 (d, J 11.1 Hz), 123.3 (d, J 8.1 Hz), 124.1, 124.4
(d, J 130.0 Hz),124.7,127.8 (d, J 13.1 Hz),129.9 (d, J 12.1 Hz),130.0 (2C),
1. (a) Dembitsky, V. M.; Quntar, A. A. A. A.; Yaj-Yehia, A.; Srebnik, M. Mini-Rev. Org.
Chem. 2005, 2, 91e109; (b) McReynolds, M. D.; Dougherty, J. M.; Hanson, P. R.
Chem. Rev. 2004, 2239e2258; (c) Rabasso, N.; Fadel, A. Tetrahedron Lett. 2010, 51,
60e63; (d) Wang, H. Q.; Liu, Z.-J. Chin. J. Org. Chem. 2003, 23, 321e330; (e) Timmer,
M. S. M.; Ovaa, H.; Filippov, D. V.; van der Marel, G. A.; van Boom, J. H. Tetrahedron
Lett. 2000, 41, 8635e8638; (f) Hanson, P. R.; Stoianova, D. S. Tetrahedron Lett.1999,
40, 3297e3300; (g) Minami, T.; Motoyoshiya, J. Synthesis 1992, 333e349.
2. (a) Gonzalez, A. M.; Cuadrado, P.; Sarmentero, M. S. Tetrahedron 2010, 66,
9610e9619; (b) Cullen, S. C.; Rovis, T. Org. Lett. 2008, 10, 3141e3144.
3. Chudasama, V.; Ahern, J. M.; Fitzmaric, R. J.; Caddik, S. Tetrahedron Lett. 2011, 52,
1067e1069.
132.6,134.9,148.4 (d, J 8.1 Hz); 31P NMR (161.9 MHz, CDCl3):
d
¼25.1.
4.2.14. E-Diethylphosphonyl-2-phenylethene (5ad) (entry 7, Table
4).12,29 Yield: 86% (0.206 g) as slightly yellow oil; 1H NMR
(400 MHz, CDCl3):
(dd, JHH 16.5 Hz, JPH 20.0 Hz, 1H), 7.37e7.52 (m, 6H); 13C NMR
(100.6 MHz, CDCl3):
¼16.2, 61.7, 113.8 (d, J 191.1 Hz), 127.6, 128.7,
130.1, 134.7 (d, J 23.1 Hz), 148.6 (d, J 1.7 Hz); 31P NMR (161.9 MHz,
d¼1.36 (t, JHH 6.9 Hz, 6H), 4.10e4.14 (m, 4H), 6.26
d
4. (a) Page, P.; Blonski, C.; Perie, J. Eur. J. Org. Chem. 1999, 2853e2857; (b) Jakeman,
D. L.; Ivory, A. J.; Williamson, M. F.; Blackburn, G. M. J. Med. Chem. 1998, 41,
4439e4452.
CDCl3):
d
¼19.71.
Summary yield of 5bd and 50bd: 80% (0.187 g) as colorless oil
5. (a) Buscca, C. A.; Farber, E.; DeYuong, J.; Cambell, S. N.; Gonnella, C.; Grinberg,
N.; Haddad, N.; Lee, H.; Ma, S.; Reeves, D.; Shen, S.; Senanayake, C. H. Org. Lett.
2009, 11, 5594e5597; (b) Defieberg, H.; Grutzmacher, H.; Carreira, E. M. Angew.
Chem., Int. Ed. 2008, 47, 4482e4502; (c) Shi, W. W.; Luo, Y.; Luo, X.; Chao, L.;
Zhang, H.; Wang, J.; Lei, A. J. Am. Chem. Soc. 2008, 130, 14713e14720; (d) Duan,
Z.-C.; Hu, X.-P.; Wang, D.-Y.; Huang, J.-D.; Yu, S.-B.; Deng, J.; Zheng, Z. Adv. Synth.
Catal. 2008, 350, 1979e1983; (e) Zhou, Y. G. Acc. Chem. Res. 2007, 40,
1357e1366; (f) Tang, W. J.; Zhang, X. M. Chem. Rev. 2003, 103, 3029e3069; (g)
Brunner, H.; Limmer, S. J. Organomet. Chem. 1991, 417, 173e180.
6. (a) Minova, N.; Hirayama, M.; Fukutsu, S. Bull. Chem. Soc. Jpn.1987, 60,1761e1766;
(b) Hoechst, A. -G. Belg. Patent 854753, 1977; Chem. Abstr. 1978, 89, 141899.
7. (a) Levchik, S. V.; Weil, E. D. Polym. Int. 2005, 54, 11e35; (b) Price, D.; Pyrah, K.;
Hull, T. R.; Milnes, G. J.; Ebdon, J. R.; Hunt, B. J.; Joseph, P. Polym. Degrad. Stab.
2002, 77, 227e233; (c) Jin, S.; Gonsalves, K. E. Macromolecules 1998, 31,
1010e1015; (d) Shukla, J. R. U.S. Patent 4,241,145, 1980, Chem. Abstr., 94, 141383.
(e) Welch, F. J. U.S. Patent 3,312,674, 1967, Chem. Abstr. 1967, 67, 44417d.
8. (a) Delomenede, M.; Bedos-Belval, F.; Duran, H.; Vindis, C.; Baltas, M.; Negre-
Salvayre, A. J. Med. Chem. 2008, 51, 3171e3181; (b) Ettari, R.; Nizi, E.; Di Fran-
cesco, M. E.; Micale, N.; Grasso, S.; Zappala, M.; Vicik, R.; Schirmeister, T.
ChemMedChem 2008, 3, 1030e1033; (c) Whitteck, J. T.; Ni, W.; Griffin, B. M.;
Eliot, A. C.; Thomas, P. M.; Kelleher, N. L.; Metcalf, W. W.; van der Donk, W. A.
Angew. Chem., Int. Ed. 2007, 46, 9089e9092; (d) Quantar, A. A. A. A.; Gallily, R.;
Katzavian, G.; Srebnik, M. Eur. J. Pharmacol. 2007, 556, 9e13; (e) Quantar, A. A.
A. A.; Baum, O.; Reich, R.; Srebnik, M. Arch. Pharm. Pharm. Med. Chem. 2004, 337,
76e86; (f) Harden, M. R.; Parkin, A.; Parratt, M. J.; Perkin, R. M. J. Med. Chem.
1993, 36, 1343e1355.
9. (a) Swamy, K. C. K.; Allu, S.; Srinvas, V.; Balaraman, E.; Pavan Kumar, K. V. P.
Cryst. Growth Des. 2011, 11, 2302e2310 (and Ref. therein); (b) Ruiz, M.; Fer-
nandez, M. C.; Diaz, A.; Quintela, J. M.; Ojea, V. J. Org. Chem. 2003, 68,
7634e7645 (and Ref. therein).
10. (a) Beletskaya, I. P.; Ananikov, V. P. Chem. Rev. 2011, 111, 1596e1636 (and Ref.
therein); (b) Ananikov, V. P.; Beletskaya, I. P. Chem.dAsian J. 2011, 6, 1423e1430
(and Ref. therein).
11. General reviews on addition of HeP(O) bond to alkynes: (a) Tanaka, M. Top.
Organomet. Chem. 2013, 43, 167e202; (b) Queffelec, C. Q.; Petit, M.; Janvier, P.;
Knight, D. A.; Bujoli, B. Chem. Rev. 2012, 112, 3777e3807; (c) Beletskaya, I. P.;
Ananikov, V. P.; Khemchyan, L. L. Phosphorus Compounds; Springer Scienceþ-
Business Media B, 2011; Chapter 8, pp 213e264; (d) Demmer, C. S.; Krogsgaard-
Larsen, N.; Bunch, L. Chem. Rev. 2011, 111, 7981e8006; (e) Xu, Q.; Han, L.-B. J.
Organomet. Chem. 2011, 696, 130e140; (f) Belabassi, Y.; Bravo-Altamirano, K.;
Montchamp, J.-L. J. Organomet. Chem. 2011, 696, 105e111; (g) Glueck, D. S. Top.
Organomet. Chem. 2010, 31, 65e100; (h) Coudray, L.; Montchamp, J.-L. Eur. J. Org.
Chem. 2008, 3601e3613; (i) Ide, D. M.; Eastlund, M. P.; Upe, C. L.; Stockland, R. A.
Curr. Org. Chem. 2008, 12, 1258e1278; (k) Montchamp, J.-L. J. Organomet. Chem.
2005, 690, 2388e2406; (l) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004,
104, 3079e3160; (m) Tanaka, M. Top. Organomet. Chem. 2004, 232, 25e54; (n)
Beletskaya, I. P.; Kazankova, M. A. Russ. J. Org. Chem. 2002, 38, 1391e1430; (o)
Han, L.-B.; Tanaka, M. Chem. Commun. 1999, 395e402; (p) Chen, T.; Zhou, Y.;
Han, L.-B. Chem. Lett. 2013, 1065e1067.
(entry 8, Table 4).
4.2.15. E-(1-Diethylphosphonyl)hept-1-ene
(400 MHz, CDCl3):
1.42e1.50 (m, 2H), 1.81e1.87 (m, 2H), 2.20e2.26 (m, 2H), 2.48e2.52
(m, 2H), 4.06e4.12 (m, 4H). 5.64 (dd, JHH 16.8 Hz, JPH 24.0 Hz, 1H),
6.79 (ddt, JHH 16.8 Hz, JPH 20.0 Hz,1H); 13C NMR (100.6 MHz, CDCl3):
(5bd).30 1H
NMR
d¼0.87e0.93 (m, 3H), 1.32 (t, JHH 7.8 Hz, 6H),
d
¼13.7, 16.1, 22.0, 32.7, 29.0, 33.9 (d, J 11.1 Hz), 61.5, 116.1 (d, J
188.1 Hz), 154.2 (d, J 2.6 Hz); 31P NMR (161.9 MHz, CDCl3):
d¼19.04.
4.2.16. E-1-(Diethylphosphonyl)hept-2-ene
(400 MHz, CDCl3):
(50bd).31 1H
NMR
d
¼1.90 (t, JHH 7.8 Hz, 6H), 1.32 (t, JHH 7.0 Hz,
6H), 1.48e1.54 (m, 2H), 2.04e2.10 (m, 2H), 2.20e2.35 (m, 4H),
3.96 (m, 4H), 5.45 (dt, JHH 16.2 Hz, JPH 17.2 Hz, 1H), 6.04 (dt, JHH
16.0 Hz, JPH 16.0 Hz, 1H); 13C NMR (100.6 MHz, CDCl3):
d
¼13.9,
19.2, 22.3 (d, J 25.2 Hz), 28.5 (d, J 5.0 Hz), 31.1 (d, J 17.1 Hz), 32.8,
67.6, 109.7 (d, J 189.2 Hz), 143.2 (d, J 2.1 Hz); 31P NMR (161.9 MHz,
CDCl3):
d
¼19.20.
4.2.17. E-1-Diethylphosphonyl-3-hydroxyprop-1-ene (5dd) (entry 9,
Table 4).32 Yield: 70% (0.135 g) as colorless oil; 1H NMR (400 MHz,
CDCl3):
d
¼1.33 (t, JHH 7.0 Hz, 6H), 4.06e4.17 (m, 4H), 4.30e4.34
(m, 2H), 5.34 (br s, 1H, OH), 6.02 (tdd, JHH 17.1 Hz, JPH 21.0 Hz, 1H),
6.88 (tdd, JHH 17.0 Hz, JPH 22.0 Hz, 1H); 13C NMR (100.6 MHz,
CDCl3):
190.1 Hz), 152.6 (d, J 5.1 Hz); 31P NMR (161.9 MHz, CDCl3):
¼19.33.
d
¼16.1, 61.8 (d, J 5.1 Hz), 62.1 (d, J 23.1 Hz), 114.3 (d, J
d
4.2.18. E-1-Diethylphosphonyl-(3-hydoxy-3-methyl)but-1-ene (5ed)
(entry 10, Table 4).32a,33 Yield: 58% (0.128 g) as slightly yellow oil;
1H NMR (400 MHz, CDCl3):
d
¼1.33 (t, JHH 7.0 Hz, 6H), 1.78 (dd, JHH
8.0 Hz, 6H), 4.06e4.13 (m, 4H), 5.18 (br s, 1H, OH), 5.93 (ddd, JHH
17.1 Hz, JPH 21.0 Hz, 1H), 6.83 (ddd, JHH 17.1 Hz, JPH 24.1 Hz, 1H); 13
NMR (100.6 MHz, CDCl3):
¼15.8 (d, J 7.0 Hz), 18.7 (d, J 7.5 Hz), 28.8
(d, J 40.1 Hz), 61.9 (d, J 6.9 Hz), 68.2, 112.0 (d, J 187.0 Hz), 159.7 (d, J
1.7 Hz); 31P NMR (161.9 MHz, CDCl3):
¼16.62.
C
d
d
4.2.19. 1,4-Diphenylbut-1-en-3-yne (6a and 6b) (Scheme 3).21 Yield:
90% (0.183 g) as white solid, mp 92e94 ꢀC (E-isomer 6a) 1H NMR
12. Kuramshin, A. I.; Nikolaev, A. A.; Cherkasov, R. A. Mendeleev Commun. 2005, 15,
155e156.
13. Niu, M.; Fu, H.; Jiang, Y.; Zhao, Y. Chem. Commun. 2007, 272e274.
14. (a) Han, L.-B.; Choi, N.; Tanka, M. Organometallics 1996, 15, 3259e3261; (b) Han,
L.-B.; Hua, R.; Tanaka, M. Angew. Chem., Int. Ed. 1998, 37, 94e96.
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5080e5081; (b) Han, L.-B.; Ono, Y.; Yazawa, H. Y. Org. Lett. 2005, 7, 2909e2911.
16. Kanada, J.; Tanaka, M. Adv. Synth. Catal. 2011, 353, 890e896.
17. (a) Xu, Q.; Shen, R.; Ono, Y.; Nagahata, R.; Shimada, S.; Goto, M.; Han, L.-B. Chem.
Commun. 2011, 2333e2335; (b) Dobashi, N.; Fuse, K.; Hoshino, T.; Kanada, J.;
Kashiwabara, T.; Kobata, C.; Nune, S. K.; Tanaka, M. Tetrahedron Lett. 2007, 48,
4669e4673.
18. (a) Han, L.-B.; Zhao, C.-Q.; Tanaka, M. J. Org. Chem. 2001, 66, 5929e5932; (b)
Duraud, M.; Toffano, M.; Fiaud, J.-C. Eur. J. Org. Chem. 2009, 4400e4403; (c)
Huang, Y.; Hao, W.; Ding, G.; Cai, M.-Z. J. Organomet. Chem. 2012, 715, 141e146;
(d) Stockland, R. A.; Lipman, A. J.; Bawiec, J. A., III; Morrison, P. E.; Guzei, J. A.;
Findeis, P. M.; Tamblin, J. F. J. Organomet. Chem. 2006, 691, 4042e4053; (e)
Stone, J. J.; Stockland, R. A.; Reyes, J. M.; Kovach, J.; Goodman, C. C.; Tillman, E. S.
J. Mol. Catal. 2005, 226, 11e21; (f) Van Rooy, S.; Cao, C.; Patrick, B. O.; Lam, A.;
Love, J. A. Inorg. Chim. Acta 2006, 2916e2923; (g) Yao, F.; Peng, J.; Hao, W.; Cai,
M. Catal. Lett. 2012, 142, 803e808.
(400 MHz, CDCl3):
7.28e7.34 (m, 6H), 7.44e7.48 (m, 4H); 13C NMR (100.6 MHz,
CDCl3):
¼88.6, 91.4, 107.9, 123.2, 126.1, 128.0, 128.2, 128.5, 131.3,
136.1, 141.1; (Z-isomer 6b) 1H NMR (400 MHz, CDCl3):
¼5.91 (d, J
12.0 Hz, 1H), 6.69 (d, J 12.0 Hz, 1H), 7.25e7.32 (m, 6H), 7.42e7.48
(m, 2H), 7.90e7.99 (m, 2H); 13C NMR (100.6 MHz, CDCl3):
d
¼6.38 (d, J 16.0 Hz, 1H), 7.03 (d, J 16.0 Hz, 1H),
d
d
d
¼87.9,
95.5, 107.2, 127.5, 128.1, 128.2, 128.2, 128.3, 128.5, 130.1, 131.2,
138.5.
Acknowledgements
The authors thank Dr. P. Sazonov (M.V. Lomonosov MSU) for
help in preparing the manuscript.

2562
I.G. Trostyanskaya, I.P. Beletskaya / Tetrahedron 70 (2014) 2556e2562
19. (a) Han, L. -B.; Zhao, C. -Q.; Tanaka, M. U.S. Patent 2,004,092,752; Chem. Abstr.,
137, 247817. (b) Han, L. -B.; Zhao, C. -Q.; Tanaka, M. WO Pat. 2002064604; Chem.
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Nifant’ev, E. E. J. Gen. Chem. USSR 1985, 55, 1201e1202 (Engl. Trans. 1985, 55,
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