Efficient palladium-catalyzed double arylation of phosphonoalkynes and diarylalkynes in water: Use of a dinuclear palladium(I) catalyst

Article abstract of DOI:10.1002/adsc.201000579

A novel use of the dinuclear palladium(I) catalyst [(OCH ₂CMe₂CH₂O)P-S-Pd(PPh₃)]₂ in aqueous medium for the double arylation of phosphonoalkynes as well as diarylalkynes is reported. This double arylation requires both the iodoarene and arylboronic acid along with the catalyst. The structures of some key products have been proven by X-ray crystallography. Copyright

Full text of DOI:10.1002/adsc.201000579

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DOI: 10.1002/adsc.201000579
Efficient Palladium-Catalyzed Double Arylation of
Phosphonoalkynes and Diarylalkynes in Water: Use of a
Dinuclear Palladium(I) Catalyst
K. V. Sajna,a Venu Srinivas,a and K. C. Kumara Swamya,*
a
School of Chemistry, University of Hyderabad, Hyderabad – 500046 A. P., India
Fax : (+91)-40-2301-2460; e-mail: kckssc@uohyd.ernet.in or kckssc@yahoo.com
Received: July 22, 2010; Revised: September 30, 2010; Published online: November 17, 2010
Dedicated to Professor S. S. Krishnamurthy on the occasion of his 70th birthday.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201000579.
Abstract: A novel use of the dinuclear palladium(I) of some key products have been proven by X-ray
catalyst [(OCH2CMe2CH2O)P-S-PdACTHNUGRTNEG(UN PPh3)]2 in aque- crystallography.
ous medium for the double arylation of phospho-
noalkynes as well as diarylalkynes is reported. This Keywords: diarylalkynes; double arylation; palladi-
double arylation requires both the iodoarene and ar- um catalysis; phosphonoalkynes; vinylphosphonates;
ylboronic acid along with the catalyst. The structures water medium
Introduction
organophosphonates,[7] we needed vinylphosphonates
for our synthetic work and hence wanted to explore
Palladium-catalyzed reactions have been in the fore- phosphonoalkynes as substrates. We also surmised
front of organic synthesis during the last couple of de- that if our modification is viable for phosphonoal-
cades.[1] It is known that subtle variations in the cata- kynes, it should be so for other alkynes and hence
lyst environment can improve the yields dramatically have included a few examples using diphenyl- or
and hence there have been numerous new variations phenylACTHNUTRGENN(GU p-tolyl)ACHUTNGTRENaNUGN cetylene. We also note that use of the
of the known reactions like Heck, Suzuki–Miyaura green solvent water for organic synthesis has been
and Sonogashira couplings. Thus, for the Pd-catalyzed one of the thrust areas in recent years.[8] In many
synthesis of tetrasubstituted olefins (including those cases, due to hydrophobic effects, water can acceler-
with internal cyclization) via alkynes several modifica- ate the reaction rates, even when the reactants are
tions have become available; in favorable cases using sparingly soluble or insoluble in this medium.[8c] Thus,
appropriate stoichiometry, cyclization or multiple-cou- we planned to perform our palladium-catalyzed reac-
pling may also be accomplished (Scheme 1).[2] If the tions in water, which obviously is the most inexpen-
alkyne moiety and the iodoaryl entity are in the mole- sive and environmentally benign solvent. In this con-
cule, cyclization in conjunction with arylation can be text, we have developed a method for the synthesis of
accomplished.[3] However, despite all these elegant highly substituted alkenephosphonates in aqueous
studies, to the best of our knowledge, phosphonoal- medium by Pd-catalyzed three component coupling of
kynes as substrates have not been explored to date. organophosphonylalkynes, arylboronic acids and aryl
These reactions lead to multiply substituted vinyl- iodides.
phosphonates (alkenephosphonates) many of which
are synthetically useful reagents. Other known syn-
thetic routes to alkenephosphonates with defined ste- Results and Discussion
reochemistry involve palladium-catalyzed coupling re-
action of alkenyl halides and hydrogen phosphonates The phosphonate/phosphine oxide precursors for this
[HP(O)(OR)2],[4] Rh-catalyzed addition of hydrogen study are prepared by the routes shown in
phosphonates to alkynes,[5] and Wittig-type reaction Scheme 2.[9] The dinuclear Pd(I) catalyst 9 (Figure 1)
with methylenebisphosphonates.[6] In our studies on
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Scheme 1. Examples of palladium-catalyzed double arylation of alkynes and an allene from the literature.
Scheme 2. Phosphonoalkynes prepared in the present study.
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Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water
Table 1. Details on optimization studies for double arylation
as per Scheme 3.[a]
Entry
1
Catalyst
Solvent/duration
Yield [%][b]
9
CH3CN/0.5 h
CH3CN/2 h
THF/0.5 h
THF/2 h
dioxane/0.5 h
dioxane/2 h
DMF/0.5 h
PEG-400/0.5 h
water/0.5h
water/0.5 h
water/2 h
n.r.
20
n.r
60
n.r.
30
40
quantitative
quantitative
n.r.
2
3
9
9
Figure 1. Dinuclear palladium(I) catalyst 9 used in the pres-
ent study
4
5
6
7
9
9
9
Pd
Pd
Pd
was prepared by the reaction of Pd
(OCH2CMe2CH2O)P(S)H.[10]
ACHTUNGTERN(NUNG PPh3)4 with
(dba)3
E
G
~60
water/4 h
~90[c]
Initially we optimized the conditions for the reac-
tion of 1 with iodobenzene and phenylboronic acid
(Scheme 3, Table 1) that leads to the vinylphospho-
nate 10. As can be seen from the Table 1, in both
PEG-400 and water, using the new dinuclear palladi-
8
9
10
11
12
PdCl
PdCl
N
water/0.5 h
water/0.5 h
water/0.5 h
water/0.5 h
water/0.5 h
water/0.5 h
water/0.5 h
10
40
20
30
80
80
Pd
N
PdCl2
9+Na2CO3
9+NaHCO3
9+KHCO3
[d]
ACHTUNGTRENNUNGum(I) complex 9 (at 1 mol% of Pd), the reaction was
[d]
quantitative with all the alkyne 1 consumed in 0.5 h
(entries 5 and 6). In DMF/H2O (4:1) mixture, there
was no improvement in the rate of reaction compared
to water alone as a solvent (75% after 6 h). Although
[d]
quantitative
[a]
The ratio of alkyne:iodobenzene:arylboronic acid was
1:2:3. Alkyne 1 (0.5 mmol), PhI (1.0 mmol), PhB(OH)2
(1.5 mmol), K2CO3 (1.5 mmol), catalyst (0.005 mmol) in
solvent (5 mL) under reflux. The isolated yields are in
general ca. 5% lower than the 31P NMR yields.
There was no reaction in the absence of catalyst; in
DMSO and C2H4Cl2 in the presence of catalyst 9 also,
there was no reaction. Yields were based on 31P NMR
spectra.
Pd2ACHTUNGTRENNUNG(dba)3 also worked well, it needed a longer reac-
tion time (entry 7, cf. Figure 2) and at the end of 4 h,
there were some other unidentified minor peaks in
the 31P NMR spectrum of the reaction mixture. Other
[b]
Pd catalysts PdCl2ACTHNUGRTEN(NNGU PPh3)2, PdCl2ACHTNUTRGEG(NUNN PhCN)2, PdACHTNUGRTEN(NUGN OAc)2,
or PdCl2 were less effective (entries 8–11). In the case
of PdCl2 the reaction was incomplete even after 12 h
reflux. Either K2CO3 or KHCO3 as a base was better
than Na2CO3 or NaHCO3. Hence we have used the
system 9/K2CO3/water as the medium for the double
arylation of several phosphonoalkynes 1–8 that led to
the products 10–28 (Table 2). The yields are quantita-
[c]
[d]
Although the starting material was absent, there were
several minor peaks in the 31P NMR.
Here, Na2CO3, NaHCO3 or KHCO3 was used in lieu of
K2CO3.
tive with the only minor limitation being the forma- same Rf values of the biaryls and 29–34; otherwise,
tion of the biaryls.[11] X-ray structures of the symmet- the arylation process was quantitative.
rically double arylated products 18 (Figure 3) and 22
We have also prepared unsymmetrically double ary-
(see Supporting Information; Figure S101) have been lated products 35–44 by using the above methodology.
determined. As a demonstration of the efficacy of this The yields (31P NMR) were again quantitative with
novel route, we have extended the methodology to in- the incoming aryl groups cis to each other. In most
clude the disubstituted alkynes and obtained the tet- cases, the isomer with the aryl moiety from the boron-
rasubstituted alkenes 29–34 by double arylation. In ic acid entering the position geminal to the phospho-
these cases also, compounds 29–34 were the sole ary- rus was dominant and the other isomer was the minor
lated products. The slightly lower isolated yields of product. This assertion is based on (i) a report on
the pure products are only because of the nearly double arylation of nonphosphorylated alkynes,[11]
Scheme 3. Palladium(I)-catalyzed symmetrical double arylation of alkyne 1 with PhI and PhB(OH)2.
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Table 2. Details on the products obtained in double ary-
AHCTUNGTRENNUNG
lation.[a]
Com
pound
R
R’
R’’
d
Isolated
AHCTUNGTRENNUNG
(31P)[b] yield [%]
Symmetrically substituted vinylphosphonates 10–28
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Ph
Ph
Ph
H
Me
H
Me
10.2
10.8
92
87
85
86
81
81
79
85
84
80
82
79
85
84
88
82
79
85
80
OMe OMe 11.3
H
Me
OMe OMe 11.5
H
Me
4-Me-C6H4
4-Me-C6H4
4-Me-C6H4
Me
Me
Me
H
Me
10.5
11.1
H
Me
12.2
12.8
Figure 2. A diagram showing 31P NMR spectra of the reac-
tion shown in Scheme 3 by (a) using Pd(I) complex 9 after
OMe OMe 13.1
H
[c]
cyclo-C6H9[c]
H
Me
11.7
12.4
cyclo-C6H9[c] Me
0.5 h, (b) using Pd
after 2 h and (d) using Pd CTHUGNTRENNNUG
G
2ACHTUNGERTN(NUNG dba)3
cyclo-C6H9
OMe OMe 12.8
15.7
OMe OMe 16.5
13.7
OMe OMe 14.4
Ph
Ph
Ph
Ph
Me
Me
Me
H
H
H
H
and (ii) X-ray structures of the major products 39b
and 40b (Figure 5). Distinction between the two iso-
mers, we should admit, has not always been easy in
the 31P NMR because of the closeness of the chemical
shifts; however, the OCH2 carbons showed distinct
13C NMR signals in all the cases. For the numbering
of compounds obtained as per Scheme 4/Table 3, see
Figure 4. These compounds (35–44) were not separat-
ed into individual isomers.
In addition to the above, we also note the following
points. (i) Under the conditions employed, there was
no reaction (31P NMR evidence) with the use of only
one of the arylating agents, ArI or PhB(OH)2 even
after 10 h of reflux. This is to say that it was mandato-
ry to use both ArI and ArB(OH)2 for the disubstitu-
tion to occur. It must be noted that in these reactions
the monoarylated addition product was not observed
in the 31P NMR. (ii) Despite being conducted in a het-
erogeneous system the reaction works extremely well
affording the phosphonate products in high yields
(quantitative on the basis of alkyne used, by
31P NMR). (iii) Using our phosphonate precursors, by
H
Me
H
Me
28.7
28.9
OMe OMe 29.1
Tetrasubstituted alkenes 29–34
29
30
31
32
33
34
Ph
Ph
Ph
H
Me
OMe OMe
H
Me
OMe OMe
H
Me
–
–
–
–
–
–
60[d]
58[d]
55[d]
66[d]
62[d]
62[d]
4-Me-C6H4
4-Me-C6H4
4-Me-C6H4
H
Me
[a]
The ratio of alkyne:iodobenzene:arylboronic acid was
1:2:3. Alkyne (0.4 mmol), ArI (0.8 mmol), ArB(OH)2
(1.2 mmol), K2CO3 (1.2 mmol), 9 (1.0 mol% based on
Pd) in H2O (5 mL) at 1008C for 0.5 h.
[b]
The variation in chemical shifts was within ꢀ0.3 ppm for
the reaction mixture and pure compounds.
[c]
[d]
Cyclohexenyl group.
Here, although the reaction was quantitative, the isolated
yields of the pure products are somewhat lower, mainly
because of the closeness of the Rf values for the products
and the biaryls. In the literature also a similar problem
was encountered; it is reported that the purity of a
sample was only ~95%[11c]
using Pd
lecular sieves[2c,d] mono- and disubstituted products
(n-Bu)4NCl/DMF/1008C.[12] (v) The monoarene
were formed along with unreacted starting material. PPh3/ACHNUTTGRENNUNG
ACHTUNGTRENNUNG(OAc)2/O2/DMSO in the presence of 4 ꢁ mo-
Hence this procedure was not adapted in the present (Ar-H) addition products were obtained exclusively
work. (iv) There was no reaction of 1 with (a) under the conditions shown in Scheme 5. A similar
PhB(OH)2 using Pd
ACHTUNGTRENNUNG
(9:1)/1208C[2b] or (b) PhI using Pd
AHCTUNGTRENNUNG
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Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water
ꢁ
ꢁ
Figure 3. An ORTEP diagram of 18 [P1 O1 1.449(2), P1
O2 1.573(2), P1 O3 1.567(2), P1 C6 1.786(2), C6 C7
1.346(3) ꢁ].
ꢁ
ꢁ
ꢁ
Figure 5. ORTEP diagrams of the major isomers 39b
(entry 10 in Table 3) [top: P1 O3 1.455(2), P1 O2
Scheme 4. Palladium-catalyzed unsymmetrical double aryla-
tion of phosphonoalkynes with ArI and ArB(OH)2.
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
1.5722(17), P1 O1 1.574(2), P1 C6 1.805(2), C6 C7
1.342(3) ꢁ] and 40b (entry 12 in Table 3) [bottom: P O1
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
1.456(2), P O2 1.578(2), P O3 1.576(2), P C6 1.789(2), C6
C7 1.344ACTHNUGRTNEUNG(3 ꢁ].
kynes but by using NaBPh4 in place of phenylboronic
acid.[13]
Based on the available literature,[11] for the double
arylation, we propose that the Pd complex first reacts
with iodoarene and then with arylboronic acid. The
aryl group from the iodoarene preferentially goes to
the carbon b to the phosphonyl group. As regards the
role of the catalyst (or procatalyst) 9, at least four
possible intermediates (I–IV, Figure 6) are possible in
ꢁ
the initial stages, either by retaining the Pd Pd bond
or by its cleavage[14] leading to the formation of a
mononuclear species. In either case, one of the active
species should be of the type V (Figure 6). In a pre-
liminary experiment, when a solution of the catalyst 9
(1 equiv.) and PhI (2 equiv.) was heated at 1008C in
1,4-dioxane for 30 min, the color changed from yellow
Figure 4. Structures of the unsymmetrical diarylated vinyl
phosphonates 35–44.
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Table 3. Details on the unsymmetrical double arylation products (cf. Scheme 4).[a]
Entry
Product
R
R’
R’’
d (31P)[b]
Combined isolated yield [%][c]
Unsymmetrically substituted vinylphosphonates 29–38
1
2
3
4
5
6
7
8
35
35
36
36
37
37
38
38
39
39
40
40
41
41
42
42
43
43
44
44
Ph
Ph
Ph
Ph
H
Me
H
OMe
H
Me
H
OMe
H
Me
H
OMe
H
Me
H
Me
H
OMe
H
Me
H
OMe
H
Me
H
OMe
H
Me
H
OMe
H
10.57; 10.64
same as above
10.7; 10.8
same as above
10.5; 10.6
same as above
10.8; 10.9
same as above
12.7
same as above
12.81; 12.85
same as above
11.9
same as above
12.1
same as above
12.4
same as above
12.8
87
80
83
83
93
81
71
71
75
86
84
75
87
87
90
92
81
87
86
84
4-Me-C6H4
4-Me-C6H4
4-Me-C6H4
4-Me-C6H4
Me
Me
Me
Me
cyclo-C6H9
cyclo-C6H9
cyclo-C6H9
cyclo-C6H9
C6H13
C6H13
C6H13
C6H13
9
10
11
12
13
14
15
16
17
18
19
20
OMe
H
Me
H
Me
H
OMe
H
OMe
same as above
[a]
The molar ratio of alkyne:iodobenzene: arylboronic acid was 1:2:3. Alkyne (0.4 mmol), ArI (0.8 mmol), ArB(OH)2
(1.2 mmol), K2CO3 (1.2 mmol), 9 (1.0 mol% based on Pd) in H2O (5 mL) at 1008C for 0.5 h. Two entries are there for
each compound because of the interchange of the aryl group between the boronic acid and the iodoarene.
[b]
[c]
In some cases, the dACTHNUTRGNEUNG
(31P) values of the two isomers were the same.
Two isomers are obtained generally in the ratio 7:3 to 9:1 in favor of boronic acid residue geminal to phosphorus moiety.
In the case of compound 38 only, both the isomers are formed in nearly equal quantities.
Scheme 5. Synthesis of monosubstituted alkenyl-phosphonates 45–48 and the alkenylphosphine oxide 49.
to dark brown and the peaks corresponding to the (3 equiv.), the intensity of alkyne (1) peak gradually
catalyst (d=15.3 and 148.0) disappeared in the decreased (after 1 h) with the increase in intensity of
31P NMR spectrum. New peaks were seen at d=30.2 a peak at d=10.2 (31P NMR) due to diarylated prod-
and d=86.0; these may be due to the PPh3 and/or thi- uct (10). In lieu of the peak at d(P)=86.0 a new peak
ophosphorus (P=S) bound ArPdI moiety (II or IV). appeared at d(P)=23.0. After 3 h, the alkyne fully
Addition of alkyne 1 [1.0 equiv.; d(P)=ꢁ12.0] at this disappeared and the product 10 was formed quantita-
stage did not give any change in the 31P NMR. Upon tively. There was no change in the 31P NMR when Pd
addition of PhB(OH)2 (3 equiv.) and K2CO3 catalyst 9 was heated with only PhB(OH)2 under the
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Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water
above-mentioned conditions. Attempts towards the
isolation of the intermediate/s have not been success-
ful as yet.
To explore the efficacy of our dinuclear palladi-
AHCTUNGTRENNUNG
tional palladium [PdACHTNUGTRENNU(G OAc)2 and PdCAHUTGNTRNEN(UGN PPh3)4] catalyzed
reactions[2b,15] as shown in Scheme 6. The results sug-
gest that our catalyst is at least as active as or better
than the other catalysts under the similar conditions.
The added advantage in the case of 9 is its stability to
air. Further work in utilizing the catalyst 9 is under-
way in our laboratory.[10]
Figure 6. Possible intermediates in the formation of diarylat-
ed products.
Scheme 6. Utility of the catalyst 9 in some selected coupling reactions.
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K. V. Sajna et al.
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Conclusions
30 mL), the combined organic layer washed thrice (3ꢂ
20 mL) with water and brine solution (20 mL), and finally
dried over anhydous Na2SO4. Removal of the solvent afford-
ed yellow colored gummy material, which was chromato-
graphed (EtOAc/hexane=3:7) to afford the pure product 1.
Compounds 2–4 were also synthesized in a manner similar
to compound 1 using the same molar quantities.
A novel Pd-catalyzed protocol for the double aryla-
tion of phosphonoalkynes and diarylalkynes in water
as the reaction medium has been developed using a
new dinuclear Pd(I) catalyst and by the combined use
of an aryl iodide and arylboronic acid. The aryl group
from the boronic acid preferentially goes to the
carbon connected to the phosphonyl group. Despite
the heterogeneous nature of the components used,
the reaction works well in aqueous medium affording
the phosphonate products in yields that are essentially
quantitative.
Compound 1: Isolated yield: 6.10 g (67%); white solid;
mp 161–1628C; IR (KBr): n=2975, 2186, 1823, 1489, 1373,
1283, 1055, 1001, 918 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
d=7.41–7.61 (m, 5H, Ar-H), 4.23–4.26 and 3.95–4.04 (2 m,
4H, 2 OCH2), 1.34 and 0.93 (2 s, 6H, 2 CH3); 13C NMR
(100 MHz, CDCl3): d=132.7 (d, J=2.2 Hz), 131.0, 128.7,
119.2 (d. J=5.4 Hz, PCCC), 100.7 (d, J=50.4 Hz, PCC),
77.5, 77.4, 76.5 (d, J=287.2 Hz, PC), 32.4 [d, J=6.0 Hz,
CACTHNUTRGNEUNG
(CH3)2], 22.0, 20.4; 31P NMR (162 MHz, CDCl3): d=
ꢁ11.7; LC/MS: m/z=251 [M+1]+; anal. calcd. for
Experimental Section
C15H19O3P: C 64.74, H 6.88; found: C 64.82, H 6.87.
Compound 2: Isolated yield: 6.70 g (70%); white solid;
mp 172–1748C; IR (KBr): n=2976, 2184, 1605, 1510, 1476,
Chemicals were procured from Aldrich or local manufactur-
ers and were purified when required.[16] 1H, 13C and
31P NMR spectra operating at 400, 100 or 125, and 162 MHz
were recorded in CDCl3 solutions, with shifts referenced to
SiMe4 (d=0) or 85% H3PO4 (d=0). Infrared spectra were
recorded neat or by using KBr pellets on an FT/IR spec-
trometer. Melting points were determined by using a local
hot-stage melting point apparatus and are uncorrected. Mi-
croanalyses were performed using a CHNS analyzer. For
TLC, glass micro slides were coated with silica gel GF254
(mesh size 75m) and spots were identified using iodine or
UV chamber as appropriate. For column chromatography,
silica gel of 100–200 mesh size was used. LC-MS data were
obtained using electrospray ionization (positive mode) on a
C-18 column at a flow rate 0.2 mLminꢁ1 using MeOH/water
(90:10) as eluent.
1372, 1285, 1053, 999, 916 cmꢁ1
;
1H NMR (400 MHz,
CDCl3): d=7.48 (d, J=8.0, 2H, Ar-H), 7.20 (d, J=8.0 Hz,
2H, Ar-H), 4.21–4.24 and 3.93–4.01 (2 m, 4H, 2 OCH2), 2.40
(s, 3H, C6H4CH3), 1.33 and 0.91 (2 s, 6H, 2 CH3); 13C NMR
(100 MHz, CDCl3): d=141.7, 132.7 (d, J=2.5 Hz), 129.5,
116.1 (d, J=5.4 Hz, PCCC), 101.3 (d, J=51.0 Hz, PCC),
77.4, 77.3, 75.9 (d, J ~295.6 Hz, PC), 32.4 [d, J=6.0 Hz,
CACTHNUTRGNEUNG
(CH3)2], 21.8, 20.5, 22.0; 31P NMR (162 MHz, CDCl3): d=
ꢁ14.0; LC/MS: m/z=265 [M+1]+; anal. calcd. for
C14H17O3P: C 63.63, H 6.48; found: C 63.49, H 6.53.
Compound 3: Isolated yield: 6.00 g (65%); white solid;
mp 125–1268C; IR (KBr): n=2948, 2353, 2168, 1624, 1478,
1373, 1285, 1181, 916, 843 cmꢁ1
;
1H NMR (400 MHz,
CDCl3): d=6.48 [s, 1H, PCCACTHNUTRGENUGN(C=CH)], 4.13–4.15 (m, 2H,
OCH2), 3.88–3.96 (m, 2H, OCH2), 2.17–2.18 [m, 4H,
(CH2)2], 1.62–1.66 [m, 4H, (CH2)2], 1.30 and 0.90 (2 s, 6H,
2CH3); 13C NMR (100 MHz, CDCl3): d=142.6 (d, J=
3.1 Hz), 118.2 (d, J=5.7 Hz, PCCC), 103.1 (d, J=50.4 Hz,
PCC), 77.3, 77.2, 73.8 (d, J=290.0 Hz, PC), 32.4 [d, J=
Precursors 1–4 were prepared by using a slightly modified
version
of
a
literature
procedure.[9a]
Alkynes
ꢂ
ꢂ
(OCH2CMe2CH2O)P(O)C CCH3 (5) and Ph2P(O)C CCH3
(6) were synthesized by treatment of corresponding allenes
[(OCH2CMe2CH2O)P(O)CH=C=CH2 and Ph2P(O)CH=C=
CH2, respectively] with triethylamine (80% yield).[9b] Al-
kynes 7 and 8 were prepared according to the reported pro-
cedure.[9c] The dinuculear palladium(I) catalyst 9 [mp 2208C
(dec); 31P NMR (162 MHz, CDCl3): d=15.3 and 148.0 (d
5.9 Hz, CACHTUNGTRNEUNG
(CH3)2], 28.0, 25.9, 22.0, 21.8, 21.0, 20.5; 31P NMR
(162 MHz, CDCl3): d=ꢁ11.1; LC/MS m/z=255 [M+1]+;
anal. calcd. for C13H19O3P: C 61.41, H 7.53; found: C 61.55,
H 7.57.
Compound 4: Isolated yield: 6.80 g (72%); brown liquid;
IR (neat): n=3482, 2932, 2201, 1824, 1634, 1374, 1294, 1188,
each, J=12.2 Hz)] was prepared by reacting PdACTHUNTRGNE(UNG PPh3)4 with
1
1059, 1068, 947, 916 cmꢁ1; H NMR (400 MHz, CDCl3): d=
(OCH2CMe2CH2O)P(S)H in 1:1 molar stoichiometry in 1,4-
dioxane at 608C.[10,17]
4.11–4.14 and 3.87–3.96 (2 m, 4H, 2 OCH2), 2.36–2.39 (m,
2H, PCCCH2), 1.59–1.63 (m, 2H), 1.41–1.44 (m, 2H), 1.29–
1.31 (many lines, 7H), 0.89–0.91 (many lines, 6H); 13C NMR
(100 MHz, CDCl3): d=104.9 (d, J=50.7 Hz, PCC), 77.2,
Representative Procedure for the Synthesis of
Alkynes 1–4
77.1, 68.7 (d, J=290.5 Hz, PC), 32.3 [d, J=6.0 Hz, CACHTUNGTRENNUNG(CH3)2],
31.1, 28.5, 27.44, 27.42, 22.4, 22.0, 20.5, 19.3, 19.2, 14.0;
31P NMR (162 MHz, CDCl3): d=ꢁ12.0; LC/MS m/z=259
[M+1]+; anal. calcd. for C13H23O3P: C 60.45, H 8.98; found:
C 60.56, H 9.05.
A solution of phenylacetylene (3.72 g, 36.5 mmol) in THF
(5 mL) was added dropwise to a stirred solution of EtMgBr
(36.5 mmol) in THF (30 mL) at ꢁ108C under a nitrogen at-
mosphere. The contents were stirred further at room tem-
perature for 30 min. To this mixture was added a solution of
(OCH2CMe2CH2O)P(=O)Cl (36.5 mmol) in THF (45 mL)
dropwise keeping the temperature at ꢁ108C. After attaining
room temperature (258C), stirring was continued for further
3 h, the mixture quenched with saturated NH4Cl solution
(10 mL) and extracted with dichloromethane (20 mL). The
aqueous layer was washed with dichloromethane (2ꢂ
General Procedure for the Synthesis of
Tetrasubstituted Olefins 10–44
A mixture of the alkyne (1) (0.10 g, 0.40 mmol), phenylbor-
onic acid (0.15 g, 1.20 mmol), K2CO3 (0.17 g, 1.20 mmol), 9
(4.0 mg, 1.0 mol% based on Pd) and iodobenzene (0.16 g,
3076
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Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water
0.80 mmol) in water (5 mL) was heated under reflux for
0.5 h. The reaction mixture was extracted with EtOAc (2ꢂ
20 mL), dried over anhydrous Na2SO4, the solvent removed
and pure compound 10 was isolated by silica gel column
chromatography (EtOAc/hexane=1:1).
Compound 14: Isolated yield: 0.14 g (81%); white solid;
mp 245–2478C; IR (KBr): n=2961, 1613, 1512, 1404, 1254,
1
1115, 1063, 1013, 988 cmꢁ1; H NMR (400 MHz, CDCl3): d=
7.33 (d, J=7.6 Hz, 2H, Ar-H), 7.15–7.18 (m, 4H, Ar-H),
6.99 (d, J=7.6 Hz, 2H, Ar-H), 6.86 (br s, 4H, Ar-H), 3.78
(dd!t, J ~12.8 Hz, 2H, OCH2), 3.62 (dd!t, J=10.0 Hz,
2H, OCH2), 2.35 (s, 3H, C6H4CH3), 2.26 (s, 3H, C6H4CH3),
2.19 (s, 3H, C6H4CH3), 1.01 and 0.71 (2 s, 6H, 2 CH3);
13C NMR (100 MHz, CDCl3): d=159.5, 159.4, 139.0, 138.8,
138.7, 138.1, 137.2, 136.6, 134.7, 134.6, 131.0, 130.9, 129.7,
129.0, 128.6, 128.5, 128.3, 127.3, 75.7, 75.6, 32.2 (d, J=
Compounds 11–44 were also synthesized similarly by
using same molar quantities.
Compound 10: Isolated yield: 0.15 g (92%); white solid;
mp 244–2468C; IR (KBr): n=2965, 1591, 1491, 1445, 1372,
1
1253, 1061, 1013, 980 cmꢁ1; H NMR (400 MHz, CDCl3): d=
6.98–7.46 (m, 15H, Ar-H), 3.77–3.84 (m, 2H, OCH2), 3.61
(dd!t, J ~10.4 Hz, 2H, OCH2), 0.99 and 0.70 (2 s, 6H, 2
CH3); 13C NMR (100 MHz, CDCl3): d=159.5, 159.4, 141.5,
141.3, 141.13, 141.06, 137.4, 137.3, 131.1, 131.0, 129.5, 129.4
5.9 Hz, CACTHNUGTRNEUNG(CH3)2), 21.9, 21.4, 21.3, 21.2, 21.1, [the doublet
1
due to JP, C was not clear]; 31P NMR (162 MHz, CDCl3): d=
11.1; LC/MS: m/z=447 [M+1]+; anal. calcd. for C28H31O3P:
C 75.32, H 7.00; found: C 75.36, H 7.12.
1
(d, JP, C =173.0 Hz), 128.94, 128.93, 128.3, 127.8, 127.6, 127.4,
127.1 (d, J=2.0 Hz), 75.7, 75.6, 32.1 [d, J=6.0 Hz, C
G
Compound 15: Isolated yield: 0.15 g (81%); white solid;
mp 208–2108C; IR (KBr): n=2959, 1609, 1512, 1462, 1250,
21.7, 21.1; 31P NMR (162 MHz, CDCl3): d=10.2; LC/MS:
m/z=405 [M+1]+; anal. calcd. for C25H25O3P: C 74.24, H
6.23; found: C 74.21, H 6.32.
1
1181, 1059, 1011, 984 cmꢁ1; H NMR (400 MHz, CDCl3): d=
7.30 (d, J=7.6 Hz, 2H, Ar-H), 7.15–7.21 (m, 4H, Ar-H),
6.87 (d, J=8.4 Hz, 2H, Ar-H), 6.73 (d, J=8.0 Hz, 2H, Ar-
H), 6.57 (d, J=8.4 Hz, 2H, Ar-H), 3.74–3.84 (m, 5H,
C6H4OCH3 +OCH2), 3.67 (s, 3H, C6H4OCH3), 3.61 (dd!t,
J ~10.6 Hz, 2H, OCH2), 2.36 (s, 3H, C6H4CH3), 0.98 and
0.70 (2 s, 6H, 2CH3); 13C NMR (100 MHz, CDCl3): d=
159.2, 159.1, 158.7, 158.52, 158.50, 138.84,138.77, 138.0, 134.3,
134.1, 132.44, 132.39, 131.5, 130.2, 130.1, 129.2, 128.5, 127.0
(d, J=174.5 Hz), 113.4, 113.0, 75.5, 75.4, 55.1, 55.0, 32.1 [d,
Compound 11: Isolated yield: 0.15 g (87%); white solid;
mp 260–2628C; IR (KBr): n=2971, 1589, 1510, 1447, 1252,
1
1157, 1013, 986 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.43–
7.45 (m, 2H, Ar-H), 7.34–7.35 (m, 3H, Ar-H), 7.18 (d, J=
7.6 Hz, 2H, Ar-H), 7.00 (d, J=7.6 Hz, 2H, Ar-H), 6.87 (s,
4H, Ar-H), 3.72–3.79 (m, 2H, OCH2), 3.61 (dd!t, J
~9.8 Hz, 2H, OCH2), 2.27 (s, 3H, C6H4CH3), 2.19 (s, 3H,
C6H4CH3), 1.00 and 0.71 (2 s, 6H, 2CH3); 13C NMR
(100 MHz, CDCl3): d=159.0, 158.9, 141.6, 141.5, 138.7,
138.4, 137.2, 136.7, 134.5, 134.4, 130.9, 130.8, 129.6, 129.5,
J=5.9 Hz, CACTHNUTRGNEUNG
(CH3)2], 21.8, 21.4, 21.1; 31P NMR (162 MHz,
CDCl3): d=11.5; LC/MS: m/z=479 [M+1]+; anal. calcd.
for C28H31O5P: C 70.28, H 6.53; found: C 70.41, H 6.52.
Compound 16: Isolated yield: 0.15 g (79%); white solid;
mp 192–1948C; IR (KBr): n=2969, 1607, 1441, 1369, 1260,
129.0, 128.3, 128.2, 127.8, 75.7, 75.6, 32.1 [d, J=5.9 Hz, C-
(CH3)2], 21.8, 21.21, 21.15, 21.1, [the doublet due to JP, C was
1213, 1094, 1059, 1005, 982 cmꢁ1
;
1H NMR (400 MHz,
CDCl3): d=7.07–7.08 (br m, 8H, Ar-H), 6.95 (d, J=6.8 Hz,
2H, Ar-H), 3.96 (dd!t, J ~12.2 Hz, 2H, OCH2), 3.56 (dd!
t, J ~10.2 Hz, 2H, OCH2), 2.64 (d, J=3.2 Hz, 3H, C=
CCH3), 1.08 and 0.70 (2 s, 6H, 2CH3); 13C NMR (100 MHz,
CDCl3): d=157.5, 157.4, 142.8, 142.6, 137.6, 137.5, 130.8,
130.7, 128.5, 127.72, 127.66, 126.73, 126.71, 75.6, 75.5, 32.3 [d,
Compound 12: Isolated yield: 0.16 g (85%); white solid;
mp 216–2188C; IR (KBr): n=2961, 2835, 1611, 1510, 1445,
1252, 1182, 1059, 1009 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
d=7.35–7.41 (m, 5H, Ar-H), 7.21 (d, J=7.2 Hz, 2H, Ar-H),
6.88 (d, J=8.4 Hz, 2H, Ar-H), 6.74 (d, J=8.4 Hz, 2H, Ar-
H), 6.58 (d, J=8.8 Hz, 2H, Ar-H), 3.76–3.83 (m, 5H,
OCH2 +C6H4OCH3), 3.69 (s, 3H, C6H4OCH3), 3.60 (dd!t,
J=10.4 Hz, 2H, OCH2), 0.98 and 0.71 (2 s, 6H, 2CH3);
13C NMR (100 MHz, CDCl3): d=158.7, 158.5, 134.0, 133.8,
132.42, 132.36, 131.5, 130.1, 130.0, 129.2, 128.2, 127.8, 127.4
(d, J=174.0 Hz, PC), 113.5, 113.0, 75.5, 75.4, 55.2, 55.1, 32.1
J=6.0 Hz, CACHTUNGTENR(UNNG CH3)2], 24.1 (d, J=7.0 Hz, C=CCH3), 21.8,
1
21.1, [the doublet due to JP, C was not clear]; 31P NMR
(162 MHz, CDCl3): d=12.2 ; LC/MS: m/z=343 [M+1]+;
anal. calcd. for C20H23O3P: C 70.16, H 6.77; found: C 70.32,
H 6.82.
Compound 17: Isolated yield: 0.17 g (85%); white solid;
mp 179–1818C; IR (KBr): n=2961, 1611, 1510, 1406, 1370,
[d, J=6.0 Hz, CACHTUNGTRENNUNG
(CH3)2], 21.7, 21.2; 31P NMR (162 MHz,
CDCl3): d=11.3; LC/MS m/z=465 [M+1]+; anal. calcd. for
C27H29O5P: C 69.82, H 6.29; found: C 69.75, H 6.38.
1258, 1057, 1003, 916 cmꢁ1; H NMR (400 MHz, CDCl3): d=
1
6.83–6.96 (m, 8H, Ar-H), 3.87–3.94 (m, 2H, OCH2), 3.56
(dd!t, J ~9.8 Hz, 2H, OCH2), 2.59 (d, J=3.6 Hz, 3H, C=
CCH3), 2.23 (s, 3H, C6H4CH3), 2.21 (s, 3H, C6H4CH3), 1.10
and 0.71 (2 s, 6H, 2CH3); 13C NMR (100 MHz, CDCl3): d=
156.8, 156.6, 139.9, 139.6, 136.7, 136.2, 134.6, 134.5, 130.52,
130.47, 128.5, 128.4, 127.8, 126.2, 75.7, 75.6, 32.3 [d, J=
Compound 13: Isolated yield: 0.14 g (86%); white solid;
mp 244–2468C; IR (KBr): n=2967, 1586, 1481, 1440, 1250,
1
1059, 1013, 984 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.36
(d, J=7.6 Hz, 2H, Ar-H), 7.28 (d, J=8.0 Hz, 2H, Ar-H),
7.13–7.18 (m, 5H, Ar-H), 7.04–7.05 (m, 3H, Ar-H), 6.97–
6.99 (m, 2H, Ar-H), 3.82 (dd!t, J ~12.6 Hz, 2H, OCH2),
3.62 (dd!t, J=10.4 Hz, 2H, OCH2), 2.36 (s, 3H, C6H4CH3),
1.00 and 0.69 (2 s, 6H, 2CH3); 13C NMR (100 MHz, CDCl3):
d=159.9, 159.8, 141.7, 141.5, 138.2, 137.6, 137.5, 131.1, 131.0,
129.7, 129.5, 128.9, 128.6, 128.0, 127.8, 127.6, 127.3, 127.0,
6.1 Hz, CACHTNUGTERN(UNGN CH3)2], 24.2 (d, J=6.9 Hz, C=CCH3), 21.2, 21.1,
1
21.0, [the doublet due to JP, C was not clear]; 31P NMR
(162 MHz, CDCl3): d=12.8; LC/MS: m/z=372 [M+1]+;
anal. calcd. for C22H27O3P: C 71.33, H 7.35; found: C 71.45,
H 7.43.
75.6, 75.5, 32.1 [d, J=5.9 Hz, C
(CH3)2], 21.8, 21.4, 21.0, [the
Compound 18: Isolated yield: 0.18 g (84%); white solid;
mp 161–1638C; IR (KBr): n=2838, 1605, 1508, 1464, 1291,
1
doublet due to JP, C was not clear]; 31P NMR (162 MHz,
CDCl3): d=10.7; LC/MS: m/z=419 [M+1]+; anal. calcd. for
C26H27O3P: C 74.62, H 6.50; found: C 74.45, H 6.61.
1240, 1181, 1059, 1005, 916 cmꢁ1
;
1H NMR (400 MHz,
CDCl3): d=6.95–6.98 (m, 2H, Ar-H), 6.88 (d, J=8.4 Hz,
Adv. Synth. Catal. 2010, 352, 3069 – 3081
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FULL PAPERS
2H, Ar-H), 6.62–6.67 (m, 4H, Ar-H), 3.88–3.94 (m, 2H,
OCH2), 3.72 (s, 3H, C6H4OCH3), 3.70 (s, 3H, C6H4OCH3),
3.55 (dd!t, J ~10.0 Hz, 2H, OCH2), 2.58 (d, J=3.6 Hz, 3H,
C=CCH3), 1.09 and 0.71 (2 s, 6H, 2CH3); 13C NMR
(100 MHz, CDCl3): d=158.4, 158.20, 158.18, 156.4, 156.3,
135.1, 134.9, 131.90, 131.85, 131.0, 130.0, 129.4, 126.3 (d,
1JP, C =173.0 Hz), 113.25, 113.24, 113.1, 75.6, 75.5, 55.1, 32.3 [d,
126.9, 61.92, 61.86, 16.03, 15.97; LC/MS: m/z=393 [M+1].+
See Supporting Information for X-ray structure.
Compound 23: Isolated yield: 0.15 g (84%); white solid;
mp 98–1008C; IR (KBr): n=2982, 2838, 1605, 1508, 1248,
1
1179, 1028 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.40–7.42
(m, 2H, Ar-H), 7.32–7.36 (m, 3H, Ar-H), 7.19–7.21 (m, 2H,
Ar-H), 6.80–6.82 (m, 2H, Ar-H), 6.72–6.74 (m, 2H, Ar-H),
6.54–6.56 (m, 2H, Ar-H), 3.79–3.86 (m, 2H, OCH2CH3),
3.75 (s, 3H, OCH3), 3.67 (s, 3H, OCH3), 3.55–3.63 (m, 2H,
OCH2CH3), 0.98–1.01 (m, 6H, 2 OCH2CH3); 13C NMR
(100 MHz, CDCl3): d=158.5, 158.4, 156.1 (d, J=10.9 Hz),
142.4 (d, J=7.3 Hz), 134.4 (d, J=20.4 Hz), 132.8, 132.7,
J=7.0 Hz, CACHTUNGTRENNUNG(CH3)2], 24.0 (d, J=7.0 Hz, C=CCH3), 21.9,
21.1; 31P NMR (162 MHz, CDCl3): d=13.1; LC/MS: m/z=
403 [M+1]+; anal. calcd. for C22H27O5P: C 65.66, H 6.76;
found: C 65.56, H 6.88.
Compound 19: Isolated yield: 0.13 g (80%); white solid;
mp 200–2028C; IR (KBr): n=2928, 1584, 1489, 1439, 1372,
1
131.6, 130.4 (d, J=10.0 Hz), 129.7, 129.2 (d, JP, C =181.6 Hz,
1
1252, 1061, 1013, 984 cmꢁ1; H NMR (400 MHz, CDCl3): d=
P-C), 127.8, 127.6, 113.2, 112.9, 61.8, 61.7, 55.1, 55.0, 16.1,
7.03–7.16 (m, 10H, Ar-H), 6.09 [br s, 1H, PC=CACTHNUTRGNEUNG
(C= 16.0; 31P NMR (162 MHz, CDCl3): d=16.5; LC/MS: m/z=
CH)(Ph)], 4.00 (dd!t, J ~11.4 Hz, 2H, OCH2), 3.60 (dd!t,
J=11.4 Hz, 2H, OCH2), 2.23 (br s, 2H), 2.02 (br s, 2H),
1.63 (br s, 4H), 1.01 and 0.70 (2 s, 6H, 2CH3); 13C NMR
(100 MHz, CDCl3): d=163.1, 163.0, 139.1, 138.9, 138.6,
138.4, 137.4, 137.2, 131.2, 129.1, 128.1, 127.5, 127.3, 126.9,
453 [M+1]+.
Compound 24: Isolated yield: 0.15 g (88%); gummy mate-
rial; IR (neat): n=2978, 2187, 1597, 1491, 1445, 1385, 1238,
1
1107, 1015 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.45–7.47
(m, 2H, Ar-H), 7.29–7.36 (m, 3H, Ar-H), 7.24–7.27 (m, 2H,
Ar-H), 7.10–7.16 (m, 3H, Ar-H), 7.00–7.03 (m, 3H, Ar-H),
126.3, 75.4, 75.3, 32.2 [d, J=5.3 Hz, CACTHNURGTNEG(UN CH3)2], 27.5, 25.5,
1
22.4, 21.7, 21.6, 21.1, [the doublet due to JP, C was not clear];
31P NMR (162 MHz, CDCl3): d=11.7; LC/MS: m/z=409
[M+1]+; anal. calcd. for C25H29O3P: C 73.51, H 7.16; found:
C 73.45, H 7.23.
6.91–6.93 (m, 2H, Ar-H), 4.37–4.45 [m, 2H, 2 OCH
1.13 [d, J=6.4 Hz, 6H, OCH(CH3)2], 0.85 [d, J=6.4 Hz,
6H, OCH
(CH3)2]; 13C NMR (125 MHz, CDCl3): d=156.3
ACHTUNGTRENNUNG(CH3)2],
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
(d, J=10.0 Hz), 142.5, 142.3, 142.1 (d, J=7.1 Hz), 138.4 (d,
J=9.9 Hz), 131.53, 131.49, 129.7, 129.6, 128.8, 127.6, 127.54,
127.47, 127.4, 127.2 (d, J=10.6 Hz), 126.9, 126.7 (d, J=
2.0 Hz), 70.8 (d, J=5.4 Hz), 24.0 (d, J=2.8 Hz), 23.2 (d, J=
Compound 20: Isolated yield: 0.14 g (82%); white solid;
mp 245–2478C; IR (KBr): n=2919, 1588, 1510, 1250, 1179,
1
1061, 1013, 920 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.04
1
(d, J=7.6 Hz, 2H, Ar-H), 6.87–6.94 (m, 6H, Ar-H), 6.04 [br
4.5 Hz), [the doublet due to JP, C was not clear]; 31P NMR
s, 1 H, PC=C
(C=CH)
E
(162 MHz, CDCl3): d=13.7; LC/MS: m/z=421 [M+1]+.
Compound 25: Isolated yield: 0.16 g (82%); gummy mate-
rial; IR (neat): n=2978, 2836, 1605, 1508, 1248, 1179, 1019,
OCH2), 3.60 (dd!t, J=10.8 Hz, 2H, OCH2), 2.21–2.23 (m,
8H, cyclohexenyl CH2 +2C6H4CH3), 1.78 (br s, 2H), 1.62
(br s, 4H), 1.02 and 0.71 (2 s, 6H, 2CH3); 13C NMR
(100 MHz, CDCl3): d=162.8, 162.6, 138.8, 138.7, 137.2,
136.4, 136.1, 135.9, 134.5, 134.4, 131.2, 131.1, 129.3, 128.4,
128.3, 128.0, 126.5 (d, J=179.3 Hz), 75.4, 75.3, 32.3 [d, J=
988 cmꢁ1 1H NMR (400 MHz, CDCl3): d=7.27–7.40 (m,
;
4H, Ar-H), 7.14–7.20 (m, 2H, Ar-H), 7.00–7.02 (m, 1H, Ar-
H), 6.79–6.90 (m, 3H, Ar-H), 6.65–6.72 (m, 2H, Ar-H),
6.53–6.55 (m, 1H, Ar-H), 4.37–4.46 (m, 2H, 2 OCH
3.74 and 3.66 (2 s, 6H, OCH3), 1.11 [d, J=5.6 Hz, 6H, CH-
(CH3)2], 0.89 [d, J=6.8 Hz, 6H, CH
(CH3)2]; 13C NMR
ACHTUNGTRENNUNG(CH3)2),
5.7 Hz, CACHTUNGTRENNUNG
(CH3)2], 27.7, 25.6, 21.9, 21.8, 21.3, 22.5; 31P NMR
(162 MHz, CDCl3): d=12.4; LC/MS: m/z=437 [M+1]+;
anal. calcd. for C27H33O3P: C 74.29, H 7.62; found: C 74.45,
H 7.59.
A
ACHTUNGTRENNUNG
(100 MHz, CDCl3): d=158.4, 156.2, 142.6, 137.5, 135.9,
135.0, 134.8, 132.9, 131.5, 130.8, 129.9, 129.1, 127.5 (d, J=
8.7 Hz), 113.5, 113.1, 112.8, 70.8 (d, J=6.7 Hz), 55.1, 55.0,
24.0 (d, J=4.0 Hz), 23.4 (d, J=5.0 Hz), [the doublet due to
1JP, C was not clear]; 31P NMR (162 MHz, CDCl3): d=14.4;
LC/MS: m/z=481 [M+1]+.
Compound 21: Isolated yield: 0.15 g (79%); white solid;
mp 186–1888C; IR (KBr): n=2932, 1607, 1510, 1373, 1248,
1
1109, 1061, 1011 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.08
(d, J=8.0 Hz, 2H, Ar-H), 6.97 (d, J=8.0 Hz, 2H, Ar-H),
6.68 (d, J=8.0 Hz, 2H, Ar-H), 6.61 (d, J=8.0 Hz, 2H, Ar-
Compound 26: Isolated yield: 0.13 g (79%); white solid;
mp 129–1318C; IR (KBr): n=2919, 1589, 1487, 1437, 1192,
H), 6.01 [br s, 1H, PC=C
G
G
1
10.0 Hz, 2H, OCH2), 3.73 (s, 3H, C6H4OCH3), 3.71 (s, 3H,
C6H4OCH3), 3.59 (dd!t, J=12.0 Hz, 2H, OCH2), 2.22 (br s,
2H), 1.98 (br s, 2H), 1.63 (br s, 4H), 1.00 and 0.71 (2 s, 6H,
2CH3); 13C NMR (100 MHz, CDCl3): d=162.5, 162.4, 158.8,
158.3, 138.9, 138.8, 132.63, 132.58, 131.2, 130.9, 129.9, 129.8,
128.17, 128.15, 125.5 (d, J=181.0 Hz), 113.2, 113.0, 75.2, 75.1,
1105, 1024, 914 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.62–
7.67 (m, 4H, Ar-H), 7.31–7.42 (m, 6H, Ar-H), 7.01–7.11 (m,
5H, Ar-H), 6.79–6.80 (m, 3H, Ar-H), 6.71–6.72 (m, 2H, Ar-
H), 2.53 (d, J=2.8 Hz, 3H, C=CCH3); 13C NMR (100 MHz,
CDCl3): d=157.1, 157.0, 143.4, 143.3, 138.7, 138.6, 134.4,
133.4, 133.3, 132.5, 131.6, 131.5, 131.18, 131.15, 130.9, 130.8,
128.2, 128.0, 127.73, 127.70, 127.33, 127.31, 126.9, 125.93,
125.91, 24.6 (d, J=7.0 Hz, C=CCH3), [the doublet due to
1JP, C was not clear]; 31P NMR (162 MHz, CDCl3): d=28.7;
LC/MS: m/z=395 [M+1]+; anal. calcd. for C27H23OP: C
82.21, H 5.88; found: C 82.31, H 5.87.
Compound 27: Isolated yield: 0.15 g (85%); white solid;
mp 173–1758C; IR (KBr): n=2917, 1894, 1597, 1510, 1435,
1290, 1181, 1113, 1020, 912; 1H NMR (400 MHz, CDCl3):
d=7.61–7.63 (m, 4H, Ar-H), 7.30–7.41 (m, 6H, Ar-H), 6.89–
6.91 (m, 4H, Ar-H), 6.57–6.62 (m, 4H, Ar-H), 2.50 (s, 3H,
55.1, 55.0, 32.2 [d, J=6.0 Hz, CACHTNUGRTNEUNG(CH3)2], 27.7, 25.5, 22.5, 21.8,
21.3; 31P NMR (162 MHz, CDCl3): d=12.8; LC/MS: m/z=
469 [M+1]+; anal. calcd. for C27H33O5P: C 69.22, H 7.10;
found: C 69.31, H 7.12.
Compound 22: Isolated yield: 0.14 g (86%); white solid;
mp 92–948C; 1H NMR data are consistent with those report-
ed in the literature;[18] 13C NMR (100 MHz, CDCl3): d=
156.9 (d, J=8.5 Hz), 141.9 (d, J=5.8 Hz), 141.8 (d, J=
6.7 Hz), 137.9, 137.8, 134.3, 131.4 (d, J=4.4 Hz), 131.1 (d,
J=180.1 Hz), 129.7, 129.4, 127.9, 127.7, 127.6, 127.5, 127.1,
3078
asc.wiley-vch.de
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 3069 – 3081

Efficient Palladium-Catalyzed Double Arylation of Phosphonoalkynes and Diarylalkynes in Water
C=CCH3), 2.06 (s, 3H, C6H4CH3),1.86 (s, 3H, C6H4CH3);
13C NMR (100 MHz, CDCl3): d=156.8, 156.7, 140.6, 140.5,
136.5, 135.7, 135.6, 135.39, 135.37, 134.6, 133.6, 132.8, 131.9,
131.7, 131.6, 131.03, 131.01, 130.8, 130.7, 128.4, 128.1, 128.0,
127.8, 24.6 (d, J=7.0 Hz, C=CCH3), 21.1, 20.9, [the doublet
(8.42 mg, 3 mol%) and HOAc (46 mL, 0.80 mmol) in water
(2 mL) were refluxed for 2 h. The reaction mixture was ex-
tracted with EtOAc (2ꢂ10 mL), organic layer was dried
over anhydrous Na2SO4, the solvent removed and pure com-
pound 45 was isolated by silica gel column chromatography
(EtOAc/hexane=1:1).
Compounds 46–49.were synthesized in a manner similar
to compound 45 using the same molar quantities.
1
due to JP, C was not clear]; 31P NMR (162 MHz, CDCl3): d=
28.9; LC/MS: m/z=424 [M+1]+; anal. calcd. for C29H27OP:
C 82.44, H 6.44; found: C 82.51, H 6.41.
Compound 28: Isolated yield: 0.15 g (80%); white solid;
mp 120–1228C; IR (KBr): n=3056, 2838, 1750, 1607, 1439,
1377, 1177, 1113, 1032, 910; 1H NMR (400 MHz, CDCl3):
d=7.60–7.65 (m, 4H, Ar-H), 7.32–7.42 (m, 6H, Ar-H), 6.96
(d, J=8.0 Hz, 2H, Ar-H), 6.59–6.65 (m, 4H, Ar-H), 6.36 (d,
J=8.0 Hz, 2H, Ar-H), 3.71 (s, 3H, C6H4OCH3), 3.60 (s, 3H,
C6H4OCH3), 2.50 (s, 3H, C=CCH3); 13C NMR (100 MHz,
CDCl3): d=158.3, 157.6, 156.5, 135.8, 135.7, 134.7, 133.6,
132.1, 131.6, 131.5, 131.3, 131.1, 129.3, 128.2, 128.1, 113.1,
112.9, 55.1, 55.0, 24.5 (d, J=8.0 Hz, C=CCH3), [the doublet
Compound 45: Isolated yield: 0.09 g (69%); white solid;
mp 184–1868C; IR (KBr): n=2974, 1595, 1572, 1471, 1447,
1373, 1263, 1059, 1007, 914 cmꢁ1
;
1H NMR (400 MHz,
CDCl3): d=7.30–7.42 (m, 10H, Ar-H), 6.14 (d, J=16.0 Hz,
1H, PCH=CPh), 3.72–3.82 (m, 4H, OCH2), 1.13 and 0.85
(2 s, 6H, 2 CH3); 13C NMR (100 MHz, CDCl3): d=162.2,
162.1, 141.3, 141.1, 138.33, 138.26, 129.8, 129.7, 129.2, 128.4,
128.3, 128.0, 112.3 (d, J=182.0 Hz), 76.1, 76.0, 32.3 [d, J=
6.2 Hz, CACHTUNGTRNEUNG
(CH3)2], 21.8, 21.0; 31P NMR (162 MHz, CDCl3):
d=11.6; LC/MS: m/z=329 [M+1]+; anal. calcd. for
C19H21O3P: C 69.50, H 6.45; found: C 69.71, H 6.31.
1
due to JP, C was not clear]; 31P NMR (162 MHz, CDCl3): d=
29.1; LC/MS: m/z=455 [M+1]+; anal. calcd. for C29H27O3P:
C 76.64, H 5.99; found: C 76.35, H 5.85.
Compound 29: Isolated yield: 0.12 g (60%); white solid;
mp 218–2208C (lit.[2d] mp 222–2248C); spectral data are con-
sistent with those reported in the literature;[2d] LC/MS:
m/z=333 [M+1].+
Compound 30: Isolated yield: 0.12 g (58%); white solid;
mp 140–1428C (lit.[2c,19a] mp 143–1458C); spectral data are
consistent with those reported in the literature;[2c,19a] LC/
MS: m/z=361 [M+1].+
Compound 31: Isolated yield: 0.11 g (55%); white solid;
mp 182–1848C (lit.[19b] mp 186–1878C); spectral data are
consistent with those reported in the literature;[19b] LC/MS:
m/z=393 [M+1].+
Compound 46: Isolated yield: 0.09 g (69%); white solid;
mp 180–1828C; IR (KBr): n=2967, 1586, 1508, 1346, 1267,
1059, 1005, 918 cmꢁ1
;
1H NMR (400 MHz, CDCl3): d=
1H NMR (400 MHz, CDCl3): d=7.27–7.33 (m, 8H, Ar-H),
7.20 (br s, 1H, Ar-H), 6.07 (d, J=16.0 Hz, 1H, PCH), 3.75–
3.79 (m, 4H, OCH2), 2.38 (s, 3H, C=CC6H4CH3), 1.14 and
0.85 (2 s, 6H, 2 CH3); 13C NMR (100 MHz, CDCl3): d=
162.54, 162.48, 141.6, 141.4, 139.3, 135.42, 135.36, 129.7, 128.7,
128.4, 128.3, 111.6 (d, J=181.0 Hz, PCH), 76.1, 76.0, 32.3 [d,
J=8.0 Hz, CACTHNUTRGNEUNG
(CH3)2], 21.8, 21.4, 21.0; 31P NMR (162 MHz,
CDCl3): d=11.9; LC/MS: m/z=343 [M+1]+; anal. calcd.
for C20H23O3P: C 70.16, H 6.77; found: C 70.35, H 6.69.
Compound 47: Isolated yield: 0.10 g (71%); white solid;
mp 88–908C; IR (KBr): n=2969, 1605, 1572, 1472, 1256,
Compound 32: Isolated yield: 0.12 g (66%); white solid;
mp 150–1528C (lit.[11b,19c] mp 146–1488C; spectral data are
consistent with those reported in the literature;[11c,19c] LC/
MS: m/z=347 [M+1].+
1
1055, 999, 947 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.39–
7.49 (m, 5H, Ar-H), 5.95 (d, J=20.0 Hz, 1H, PCH), 4.17
(dd!t, J=12.0 Hz, 2H, OCH2), 3.89 (dd!t, J ~10.0 Hz,
2H, OCH2), 2.55 (s, 3H, C=CCH3), 1.15 and 1.06 (2 s, 6H, 2
CH3); 13C NMR (100 MHz, CDCl3): d=160.2, 141.5 (d, J=
23.0 Hz), 129.0, 128.6 (d, J=18.0 Hz), 127.1, 126.0, 111.3 (d,
J=186.0 Hz, PCH), 75.51, 75.45, 32.6 [d, J=6.0 Hz, C-
Compound 33: Isolated yield: 0.11 g (62%); white solid;
mp 140–1428C; IR (KBr): n=2920, 1904, 1597, 1510, 1443,
1265, 1182, 1111, 1022 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
d=7.02–7.09 (m, 5H, Ar-H), 6.90–6.91 (m, 12H, Ar-H), 2.27
(s, 6H, 2C6H4CH3), 2.25 (s, 3H, C6H4CH3); 13C NMR
(100 MHz, CDCl3): d=144.4, 141.14, 141.12, 140.3, 139.9,
135.81, 135.79, 135.76, 131.4, 131.3, 131.2, 128.34, 128.28, 127.6,
126.1, 21.20, 21.17; LC/MS: m/z=375 [M+1]+; anal. calcd.
for C29H26: C 93.00, H 7.00; found: C 92.85, H 7.06.
AHCTUNGTRENNUNG
(CH3)2], 21.6, 21.4, 19.7 (d, J=7.0 Hz); 31P NMR (162 MHz,
CDCl3): d=14.0; LC/MS: m/z=267 [M+1]+; anal. calcd.
for C14H19O3P: C 63.15, H 7.19; found: C 63.31, H 7.15.
Compound 48: Isolated yield: 0.08 g (62%); white solid;
mp 140–1428C; IR (KBr): n=2934, 1738, 1595, 1263, 1059,
1007, 818 cmꢁ1 1H NMR (400 MHz, CDCl3): d=7.43–7.45
;
Compound 34: Isolated yield: 0.13 g (62%); white solid;
mp 139–1418C; IR (KBr): n=2836, 1605, 1508, 1246, 1173,
(m, 2H, Ar-H), 7.37–7.38 (m, 3H, Ar-H), 6.09 [br s, 1H,
PC=C(C=CH)(Ph)], 5.79 (d, J=19.6 Hz, 1H, PCH), 4.02–
AHCTUNGTRENNUNG
1
1107, 1028, 824 cmꢁ1; H NMR (400 MHz, CDCl3): d=7.04–
4.09 (m, 2H, OCH2), 3.88 (dd!t, J ~10.2 Hz, 2H, OCH2),
2.24 (br s, 2H), 2.00 (br s, 2H), 1.68 (br s, 4H), 1.18 and 0.99
(2 s, 6H, 2 CH3); 13C NMR (100 MHz, CDCl3): d=165.9,
165.8, 139.0, 138.8, 135.6, 135.5, 130.89, 130.87, 129.5, 128.5,
127.4, 110.2 (d, J=186.6 Hz, PCH), 75.82, 75.76, 32.5 [d, J=
7.26 (m, 5H, Ar-H), 6.92–6.99 (m, 8H, Ar-H), 6.67 (d, J=
8.0 Hz, 4H, Ar-H), 3.77 (s, 6H, 2C6H4OCH3), 2.27 (s, 3H,
C6H4CH3); 13C NMR (100 MHz, CDCl3): d=157.93, 157.88,
144.5, 141.2, 139.6, 139.2, 136.7, 135.8, 132.5, 131.4, 131.3,
128.3, 127.6, 126.1, 113.1, 55.1, 21.2; LC/MS: m/z=407 [M+
1]+; anal. calcd. for C29H26O2: C 85.68, H 6.45; found: C
85.48, H 6.55.
5.8 Hz, CACHTUNGTRNEUNG
(CH3)2], 28.0, 25.5, 22.5, 21.8, 21.3; 31P NMR
(162 MHz, CDCl3): d=13.3. LC/MS: m/z=333 [M+1]+;
anal. calcd. for C19H25O3P: C 68.66, H 7.58; found: C 68.55,
H 7.76.
Compound 49: Isolated yield: 0.10 g (77%); white solid;
mp 68–708C; IR (KBr): n=3057, 1595, 1435, 1316, 1231,
General Procedure for the Synthesis of Trisubstituted
Olefins (45–49)
1
1169, 1119, 1101, 995 cmꢁ1; H NMR (400 MHz, CDCl3): d=
Alkyne (1) (0.10 g, 0.40 mmol), phenylboronic acid (0.05 g,
0.40 mmol), K2CO3 (0.06 g, 0.40 mmol), PdCl2ACHTNUTRGNEUNG(PPh3)2
7.77–7.82 (m, 4H, Ar-H), 7.36–7.51 (m, 11H, Ar-H), 6.14 (d,
J=23.6 Hz, 1H, PCH=CCH3), 2.51 (d, J=1.2 Hz, 3H, C=
Adv. Synth. Catal. 2010, 352, 3069 – 3081
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3079

K. V. Sajna et al.
FULL PAPERS
CCH3); 13C NMR (100 MHz, CDCl3): d=159.34, 159.32,
142.2, 142.1, 135.3, 134.2, 131.6, 131.5, 131.2, 131.0, 130.9,
129.2, 128.9, 128.6, 128.5, 126.0, 118.4 (d, J=103.9 Hz,
PCH), 19.7 (d, J=7.4 Hz, CH3); 31P NMR (162 MHz,
CDCl3): d=21.6; LC/MS: m/z=317 [Mꢁ1]+; anal. calcd. for
C21H19OP: C 79.23, H 6.02; found: C 79.35, H 5.88.
CCDC 794596, CCDC 781601 and CCDC 781602 contain
the supplementary crystallographic data for the compounds
of this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
18: C22H27O5P, M=402.41, triclinic, space group P-1, a=
8.751(2), b=9.402(2), c=14.290(3) ꢁ, a=103.871(3)8 b=
105.484(3)8, g=101.307(3)8, V=1056.7(4) ꢁ3, Z=2, m=
0.159 mmꢁ1, data/restraints/parameters: 5655/0/356, R indi-
ces [I>2 s(I)]: R1=0.0510 wR2 (all data)=0.1316 [CCDC
781600].
Procedure for the Synthesis of Compound 50
A mixture of diphenylacetylene (0.20 g, 1.1 mmol), phenyl-
boronic acid (0.14 g, 1.1 mmol), Ag2CO3 (0.31 g, 2.2 mmol),
Pd catalyst 9 (6.0 mg, 0.005 mmol) or PdACTHNURTGNENG(U OAc)2 (6.5 mg,
22: C24H25O3P, M=392.41, triclinic, space group P-1, a=
0.025 mmol) in 2-propanol/water mixture (2 mL, 9:1) was
heated at 1208C for 0.5 h. The solvent (2-propanol) was re-
moved under vacuum, the mixture extracted with EtOAc
(20 mL), dried (Na2SO4) and the solvent removed. Pure
compound 50 was isolated by silica gel column chromatogra-
phy (hexane); isolated yield: 0.46 g (80%, by using catalyst
11.2268(12),
b=13.6175(15),
c=15.0322(17) ꢁ,
a=
83.132(9)8 b=73.282(10)8, g=79.617(9)8, V=2159.4(4) ꢁ3,
Z=4, m=0.148 mmꢁ1, data/restraints/parameters: 6211/0/
509, R indices [I>2 s(I)]: R1=0.0688 wR2 (all data)=
0.2017 [CCDC 794596].
39 (major isomer): C21H25O3P, M=356.38, monoclinic,
space group P21/c, a=16.838(5), b=6.207(2), c=
19.499(6) ꢁ, b=104.944(5)8, V=1969.06(10) ꢁ3, Z=4, m=
0.155 mmꢁ1, data/restraints/parameters: 3487/0/230, R indi-
ces [I>2 s(I)]: R1=0.0560, wR2 (all data)=0.1377 [CCDC
781601].
40 (major isomer): C21H25O4P, M=372.38, monoclinic,
space group P21/c, a=9.309(1), b=20.331(2), c=
10.625(1) ꢁ, b=99.477(2)8, V=1983.6(3) ꢁ3, Z=4, m=
0.161 mmꢁ1, data/restraints/parameters: 3492/0/239, R indi-
ces [I>2 s(I)]: R1=0.0475, wR2 (all data)=0.1271 [CCDC
781602].
9), 0.38 g [67%, by using PdACTHNUTRGNE(UNG OAc)2]. Spectral data are con-
sistent with those reported in the literature.[2b]
General Procedure for the Synthesis of Compounds
51 and 52
A mixture of aryl bromide (1.0 mmol), phenylboronic acid
(0.15 g, 1.2 mmol), K3PO4 (0.44 g, 2.0 mmol), catalyst 9
(5.0 mg, 0.005 mmol) or PdACHTNUGTRNEUNG(PPh3)4 (12 mg, 0.01 mmol) in
water (3 mL) was heated at 1008C for 4–6 h. The mixture
was extracted with diethyl ether (20 mL), dried (Na2SO4),
the solvent removed and pure compound 51 was isolated by
silica gel column chromatography (hexane); isolated yield
0.13 (82%, by using catalyst 9), 0.11 g [74%, by using
Supporting Information
Spectroscopic and analytical data for compounds 35–44,
copies of 1H and 13C NMR spectra, ORTEP diagram of
compound 22, CIF files (for compounds 18, 22, 39b and
40b) are available in the Supporting Information.
PdACHTUNGTRENNUNG(PPh3)4]. Spectral data are consistent with those reported
in the literature.[15a]
Compound 52: Isolated yield: 0.14 g (78%, by using cata-
lyst 9); 0.13 g [76%, by using PdACHTUNTRGNEUNG(PPh3)4]. Spectral data are
consistent with those reported in the literature.[15a]
General Procedure for the Synthesis of Compounds
53 and 54
Acknowledgements
ꢂ
A mixture of ArC CH (0.5 mmol), aryl iodide (0.6 mmol),
We acknowledge Department of Science and Technology and
University Grants Commission (both in New Delhi) for fund-
ing and equipment. We also thank CSIR (New Delhi) for fel-
lowships (KVS and VS).
Pd catalyst 9 (1.3 mg, 0.0025 mmol) or Pd
N
0.05 mmol) in piperidine (3 mL) was heated at 708C for 5–
10 min. The reaction mixture was quenched with dil. HCl
(5 mL, 10% v/v) and extracted with diethyl ether (2ꢂ
20 mL), The combined organic layer was washed with brine
solution (10 mL) followed by water (2ꢂ10 mL) and dried
(Na2SO4). The solvent was removed and pure compound 53
was isolated by silica gel column chromatography (hexane);
isolated yield: 0.08 g (89%, by using catalyst 9), 0.078 g
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asc.wiley-vch.de
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 3069 – 3081

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