Synthesis of tris[2-(2-furyl)ethyl]phosphine its chalcogenides and PdII complex

Article abstract of DOI:10.1016/j.mencom.2016.07.016

Nucleophilic addition of PH₃ to 2-vinylfuran in the KOH/DMSO(H₂O) suspension affords 65% of tris[2-(2-furyl)ethyl]-phosphine, whose treatment with H₂O₂, Se or PdCl gives the corresponding phosphine oxide, selenide and complex of trans-[Pd(L)₂Cl₂] type in good to excellent yields.

Full text of DOI:10.1016/j.mencom.2016.07.016

Mendeleev
Communications
Mendeleev Commun., 2016, 26, 314–316
Synthesis of tris[2-(2-furyl)ethyl]phosphine,
ii
its chalcogenides and Pd complex
a
a
a
Alexander V. Artem’ev, Nina K. Gusarova, Anastasiya O. Sutyrina,
b,c
a
Yurii V. Gatilov and Boris A. Trofimov*
a
b
c
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
64033 Irkutsk, Russian Federation. Fax: +7 395 241 9346; e-mail: boris_trofimov@irioch.irk.ru
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy
of Sciences, 630090 Novosibirsk, Russian Federation
6
Novosibirsk State University, 630090 Novosibirsk, Russian Federation
DOI: 10.1016/j.mencom.2016.07.016
O
Nucleophilic addition of PH to 2-vinylfuran in the KOH/
3
DMSO(H O) suspension affords 65% of tris[2-(2-furyl)ethyl]-
2
PH3
phosphine, whose treatment with H O , Se or PdCl gives
2
2
2
O
KOH/DMSO(H2O),
75 °C, 1.5 h
P
the corresponding phosphine oxide, selenide and complex
of trans-[Pd(L) Cl ] type in good to excellent yields.
O
2
2
O
6
5%
The reaction of phosphine with unsaturated compounds is a
1
convenient atom-economic route to various organic phosphines,
KOH
H2O/toluene,
0–100 °C
O
O
Pred
[PH /H ]
P
3
2
which are useful in-demand ligands for multi-purpose metal
complexes, stabilizing agents for quantum dots as well as the
reagents for organic synthesis. In this line, nucleophilic addition
KOH/DMSO(H O),
2
9
75°C, 1.5 h
3
2
1, 65%
of phosphines to the C=C and CºC bonds in the KOH/DMSO
system attracts a special attention. This superbase system allows
Scheme 1
3
one to implement the addition of phosphine to weakly electro-
of PH to 2-vinylfuran occurred under the following conditions.
2-Vinylfuran was heated at 75°C for 1.5 h in the suspension
3
4
5
philic C=C bond of substituted styrenes and vinylpyridines and
thereby to synthesize the corresponding primary, secondary and
tertiary phosphines. Also, the preparation of bis[2-(2-furyl)ethyl]-
KOH/DMSO with 20 wt% water (relative to KOH∙0.5H O) with
2
the steady passing of phosphine through the reaction mixture.
The isolated yield of phosphine 1 reached 65% (Scheme 1).
The expected intermediate primary and secondary phosphines
phosphine by hydrophosphination of 2-vinylfuran with PH in
3
the KOH/DMSO system containing ~70 wt% water (relative to
6
31
KOH∙0.5H O) at 60–65°C for 2.5 h was shortly reported. Note
( P NMR) in the crude product were detected in about 10 mol%.
2
that under above conditions, tris[2-(2-furyl)ethyl]phosphine has not
been obtained. It should be emphasized that this phosphine was
The phosphine 1 is easily oxidized by aqueous hydrogen
peroxide (25°C, 2 min) or elemental selenium (EtOH, 25°C,
1 h) to afford the corresponding phosphine chalcogenides 2 and
6
once formed from 2-vinylfuran and red phosphorus in the complex
t
7
‡
superbase system Kmet/NH /THF/Bu OH in 20% yield.
3 in 97 and 90%, respectively (Scheme 2).
3
Here, we briefly report the elaboration of a more efficient
The coordination proprieties of phosphine 1 were preliminarily
and convenient synthesis of tris[2-(2-furyl)ethyl]phosphine 1
evaluated by the formation of its complex with PdCl (Scheme 3).
2
by nucleophilic addition of PH to 2-vinylfuran in the presence
The complexation readily occurs at ambient temperature (CH Cl ,
5 h) to furnish complex 4 in 72% yield.
3
2
2
†
§
of superbase suspension KOH/DMSO(H O). As a phosphine
2
source, its mixture with hydrogen generated from red phosphorus
and aqueous KOH was utilized (Scheme 1). Exhaustive addition
Tris[2-(2-furyl)ethyl]phosphine 1. To a suspension of powdered
KOH∙0.5H O (20.0 g, 307 mmol), DMSO (50 ml) and water (4 ml),
2
†
1H, 13C and 31P NMR spectra were recorded on a Bruker DPX-400
saturated with phosphine, a solution of 2-vinylfuran (10.0 g, 106 mmol)
in DMSO (10 ml) was added dropwise for 1.5 h at 75°C under stirring and
continuous passing of phosphine. The mixture was cooled to 20–25°C,
diluted with water (100 ml) and extracted with diethyl ether (2×60 ml).
spectrometer (at 400.13, 100.62 and 161.98 MHz) at ambient temperature
and referenced to internal HDMS ( H, C) and external 85% H PO ( P)
standards. FT-IR spectra were recorded on a Bruker Vertex 70 spectro-
meter. The microanalyses were performed on a Flash EA 1112 Series
1
13
31
3
4
The extract was washed with water (2×30 ml), dried over K CO , the
2
3
solvent was removed, and the residue was fractionized in vacuo to give
7.28 g (65%) of phosphine 1. Colourless oil, bp 200°C (1.5 Torr). It should
be handled under inert atmosphere to prevent its oxidation. H NMR
analyzer. 2-Vinylfuran was synthesized by CuSO -catalyzed decarboxyla-
4
tion of 3-(2-furyl)acrylic acid. KOH∙0.5H O, DMSO (1% water content)
2
1
and red phosphorus (KSAN ‘SIA’) were employed as purchased. The PH3
was generated as mixture with H by dropwise addition of 50%-aqueous
(CDCl3) d: 1.80–2.05 (m, 6H, CH2P), 2.82–2.83 (m, 6H, CH2Fur), 6.05,
2
13
KOH solution to stirred and heated (90–100°C) suspension of red phos-
phorus (10 g) in toluene (20 ml).4 All reactions were carried out under
argon atmosphere.
6.24 and 7.28 (br.s, 9H, Fur). C NMR (CDCl3) d: 19.1 (d, CH2Fur,
(a)
2
1
JPC 11.1 Hz), 26.5 (d, CH2P, JPC 11.5 Hz), 105.1 (s, C-3 Fur), 109.5 (s,
31
1
C-4 Fur), 140.3 (s, C-5 Fur), 154.6 (s, C-2 Fur). P{ H} NMR (CDCl3) d:
–28.96 (lit., d –27.8). Found (%): C, 68.05; H, 7.12. Calc. for C H O P
7
Safety Note. Phosphine gas is toxic and explosive. It should be handled
with extreme care.
P
18 21
3
(%): C, 68.34; H, 6.69.
©
2016 Mendeleev Communications. Published by ELSEVIER B.V.
–
314 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2016, 26, 314–316
Se
H2O2
1
P
Se
P
O
EtOH,
25 °C, 1 h
EtOH/H O,
25 °C, 2 min
O(2)
2
O
O
3
3
3
, 90%
2, 97%
C(9)
C(8)
C(7)
Cl(1)
Scheme 2
P(1)
C(1)
Pd(1)
¶
According to X-ray diffraction analysis, the Pd atom in
complex 4 is located on 2-fold rotation axis and coordinated
by two phosphorus atoms and by two chlorine atoms in trans-
configuration (Figure 1). The values of the P–Pd–P and Cl–Pd–Cl
C(13A)
C(14A)
C(15A)
C(2)
C(13B)
C(3) C(14B)
C(15B)
O(1)
O(3A)
O(3B)
Cl
Pd
O
PdCl2
1
P
P
CH2Cl2,
O
Figure 1 X-ray structure of complex 4 (the H atoms are omitted for clarity).
Selected bond lengths (Å) and bond angles (°): Pd(1)–Cl(1) 2.2921(7),
Pd(1)–P(1) 2.3136(6), P(1)–C 1.819(3)–1.843(6); P(1)–Pd(1)–P(1') 176.08(3),
Cl(1')–Pd(1)–Cl(1) 179.52(6). The torsion angle Cl(1')–Pd(1)–P(1)–C(13A)
2.8(6).
3
3
2
5 °C, 5 h
Cl
4
, 72%
Scheme 3
‡
Tris[2-(2-furyl)ethyl]phosphine oxide 2. To a solution of phosphine 1
bond angles [176.08(3)° and 179.52(6)°, respectively] indicate the
distorted square planar geometry of the Pd atom. The deviation
of the latter from the mean PdP Cl plane is 0.028 Å. The Pd–P
(0.344 g, 1.1 mmol) in ethanol (15 ml), 35% aqueous H O (0.5 ml,
2
2
~
5.8 mmol) was added. The mixture was stirred at ambient temperature
2
2
for 1–2 min, then diluted with water (30 ml) and extracted with CHCl3
and Pd–Cl distances are comparable with those in related com-
(2×20 ml). The extract was washed with water (2×20 ml) and dried over
8
plexes. Note that the one of three 2-(2-furyl)ethyl fragments of
K CO . The solvent was removed and residue was dried in vacuo to give
0
d: 1.98–2.05 (m, 6H, CH P), 2.89–2.86 (m, 6H, CH Fur), 6.04, 6.27 and
7
CH P, J 64.2 Hz), 105.6 (s, C-3 Fur), 110.3 (s, C-4 Fur), 141.3 (s, C-5
Fur), 153.6 (d, C-2 Fur, J 13.7 Hz). P{ H} NMR (CDCl ) d: 46.33.
FT-IR (KBr, n/cm ): 1162, 1148 (nP=O), 731 (nP–C). Found (%): C, 64.88;
H, 6.45. Calc. for C H O P (%): C, 65.05; H, 6.37.
2
3
the ligand, viz. C(13)–C(18), is disordered over two positions
in the ratio of 0.53(1):0.47(1).
In summary, a novel atom-economic expedient synthesis
of previously inaccessible tris[2-(2-furyl)ethyl]phosphine has
been elaborated based on nucleophilic addition of phosphine to
1
.350 g (97%) of 2. Colorless powder, mp 108–109°C. H NMR (CDCl )
3
2
2
13
.30 (br.s, 9H, Fur). C NMR (CDCl ) d: 20.2 (s, CH Fur), 26.4 (d,
3
2
1
2
PC
3
31
1
PC
3
–1
2-vinylfuran in the KOH/DMSO(H O) suspension. Some basic
2
18
21
4
reactions of the synthesized phosphine (oxidation with H O or
2
2
Tris[2-(2-furyl)ethyl]phosphine selenide 3. To a solution of phosphine 1
elemental selenium and complexation with PdCl ) demonstrate
2
(0.445 g, 1.4 mmol) in ethanol (15 ml), powdered gray selenium (0.111 g,
its high reactivity and potential for diverse applications. For
example, the synthesized compounds with furyl moieties can
be of interest for drug-oriented products since numerous furan
1
.4 mmol) was added and the suspension was stirred at ambient tem-
perature for 1 h. Ethanol was removed in vacuo and the residue was
washed with hexane and dried in vacuo to give 0.500 g (90%) of 3.
Colorless powder, mp 78–80°C (light petroleum). H NMR (CDCl ) d:
9
1
derivatives are important pharmaceuticals and bioactive natural
3
1
0
products. Furthermore, tris[2-(2-furyl)ethyl]phosphine and its
chalcogenides can be promising polydentate ligands for design
of in-demand polynuclear complexes.
2
.17–2.24 (m, 6H, CH P), 2.92–2.99 (m, 6H, CH Fur), 6.05, 6.27 and
2
2
7
.29 (m, 9H, Fur). 13C NMR (CDCl ) d: 21.9 (s, CH Fur), 28.5 (d, CH P,
3 2 2
1
JCP 43.1 Hz), 105.9 (s, C-3 Fur), 110.2 (s, C-4 Fur), 141.3 (s, C-5 Fur),
3
31
1
1
53.1 (d, C-2 Fur, JCP 14.8 Hz). P{ H} NMR (CDCl ) d: 38.25
3
1
1
–1
(satellites: J 43.1 Hz, J 706 Hz). FT-IR (KBr, n/cm ): 735 (nP–C),
PC PSe
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant no. NSh-7145.2016.3). Authors are grateful to the the Multi-
Access Chemical Service Centre SB RAS for XRD measure-
ments. Authors also acknowledge Baikal Analytical Center for
collective use SB RAS for the equipment.
5
30 (nP=Se). Found (%): C, 54.61; H, 5.56. Calc. for C H O PSe (%):
18 21 3
C, 54.69; H, 5.35.
§
trans-Dichloro-bis{tris[2-(2-furyl)ethyl]phosphine}palladium(ii) 4. To
a solution of phosphine 1 (0.192 g, 0.61 mmol) in CH Cl (7 ml), PdCl
2
2
2
(0.049 g, 0.28 mmol) was added. The suspension was stirred at ambient
temperature for 5 h, then filtered and evaporated in vacuo. The residue
obtained was re-crystallized from hot hexane/CH Cl mixture and dried
2
2
in vacuo to give 0.161 g (72%) of complex 4.Yellow crystals, mp 112–113°C
hexane). The X-ray quality crystals were grown by slow evaporation
References
(
1
1 (a) B. A. Trofimov, S. N. Arbuzova and N. K. Gusarova, Russ. Chem. Rev.,
of CH Cl solution of 4 (20–23°C, several days). H NMR (CDCl ) d:
2
2
3
1
999, 68, 215 (Usp. Khim., 1999, 68, 240); (b) C. Baillie and J. Xiao,
2
6
.15–2.25 (m, 12H, CH P), 2.92–3.02 (m, 12H, CH Fur), 6.01–6.06,
2
2
31
1
Curr. Org. Chem., 2003, 7, 477; (c) O. Delacroix and A. C. Gaumont,
Curr. Org. Chem., 2005, 9, 1851.
.21–6.26 and 7.20–7.25 (m, 18H, Fur). P{ H} NMR (CDCl ) d: 12.13.
3
Found (%): C, 53.25; H, 5.40; P, 7.65. Calc. for C H Cl O P Pd (%):
36
42
2
6 2
2
3
(a) L. D. Quin, A Guide to Organophosphorus Chemistry, Wiley-VCH,
Weinheim, 2000; (b) Organophosphorus Reagents, ed. P. J. Murphy, Oxford
University Press, Oxford, 2004.
C, 53.38; H, 5.23; P, 7.37.
¶
–1
Crystal data for 4. C H Cl O P Pd, M = 809.94 g mol , monoclinic,
36
42
2
6 2
space group C /c, a = 13.1944(4), b = 18.0483(5) and c = 16.0088(5) Å,
2
(a) B. A. Trofimov and N. K. Gusarova, Mendeleev Commun., 2009, 19,
3
–3
–1
b
= 91.661(1)°, V = 3810.7(2) Å , Z = 4, dcalc = 1.412 g cm , m = 0.753 mm
T = 200(2) K, scanning area 2q < 61.0°, 19825 reflections measured,
725 unique (Rint = 0.0248), 4835 reflections with I ³ 2s(I), 277 refined
parameters, R [I ³ 2s(I)] = 0.0365, wR = 0.1296 (all data). Data were
,
2
95; (b) N. K. Gusarova, S. N. Arbuzova and B. A. Trofimov, Pure Appl.
Chem., 2012, 84, 439.
4 (a) N. K. Gusarova, S. F. Malysheva, V. A. Kuimov, N. A. Belogorlova,
V. L. Mikhailenko and B. A. Trofimov, Mendeleev Commun., 2008,
5
1
2
collected on a Bruker Apex II CCD diffractometer using graphite mono-
chromated MoKa radiation (l = 0.71073 Å). The structure was solved by
direct methods and refined by full-matrix least-squares method against
all F2 in anisotropic approximation for non-hydrogen atoms using the
SHELX-97 programs set. Hydrogen atoms were included at geometrically
calculated positions during the refinement using the riding model.
CCDC 1447020 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk.
1
8, 260; (b) S. F. Malysheva, N. K. Gusarova, A. V. Artem’ev, N. A.
Belogorlova, V. I. Smirnov, V. A. Shagun, V. A. Kuimov and B. A. Trofimov,
Synth. Commun., 2012, 42, 1685; (c) A. V. Artem’ev, S. F. Malysheva,
N. K. Gusarova, A. O. Korocheva, L. V. Timokhina and B. A. Trofimov,
Russ. Chem. Bull., Int. Ed., 2013, 62, 2495 (Izv. Akad. Nauk, Ser. Khim.,
2013, 2495).
5 (a) N. K. Gusarova, B. A. Trofimov, S. F. Malysheva, S. I. Shaikhudinova,
N. A. Belogorlova, S. N. Arbuzova, K. V. Nepomnyashchikh and V. I.
Dmitriev, Russ. J. Gen. Chem., 1997, 67, 65 (Zh. Obshch. Khim., 1997,
11
–
315 –

Mendeleev Commun., 2016, 26, 314–316
6
7, 70); (b) B. A. Trofimov, S. I. Shaikhudinova, V. I. Dmitriev, K. V.
Nepomnyashchikh, T. I. Kazantseva and N. K. Gusarova, Russ. J. Gen.
hem., 2000, 70, 40 (Zh. Obshch. Khim., 2000, 70, 43); (c) S. F. Malysheva
(d) D. S. Mortensen, A. L. Rodriguez, K. E. Carlson, J. Sun, B. S.
Katzenellenbogen and J. A. Katzenellenbogen, J. Med. Chem., 2001,
44, 3838.
C
,
A. V. Artem’ev, N. K. Gusarova, B. V. Timokhin, A. A. Tatarinova and
B. A. Trofimov, Russ. J. Gen. Chem., 2009, 79, 1617 (Zh. Obshch. Khim.,
10 (a) B. A. Keay, J. M. Hokins and P. W. Dibble, in Comprehensive
Heterocyclic Chemistry III, eds. G. Jones and C. A. Ramsden, Elsevier,
Amsterdam, 2008, pp. 571–628; (b) B. M. Fraga, Nat. Prod. Rep., 1992,
9, 217; (c) A. T. Merritt and S. V. Ley, Nat. Prod. Rep., 1992, 9, 243.
11 (a) G. M. Sheldrick, Program for the Solution of Crystal Structures
SHELXS-97, University of Göttingen, Germany, 1997; (b) G. M. Sheldrick,
Program for Refinement of Crystal Structures SHELXL-97, University
of Göttingen, Germany, 1997.
2
009, 79, 1259).
6
7
8
B. A. Trofimov, L. Brandsma, S. N. Arbuzova, S. F. Malysheva and
N. K. Gusarova, Tetrahedron Lett., 1994, 35, 7647.
L. Brandsma, S.Arbuzova, R.-J. De Lang, N. Gusarova and B. Trofimov,
Phosphorus Sulfur Silicon Relat. Elem., 1997, 126, 125.
(a) A. J. Nawara, T. Shima, F. Hampel and J. A. Gladysz, J. Am. Chem.
Soc., 2006, 128, 4962; (b)A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva,
N. A. Belogorlova, O. N. Kazheva, G. G. Alexandrov, O. A. Dyachenko
and B. A. Trofimov, Mendeleev Commun., 2015, 25, 196.
9
(a) X. Huang, B. Peng, M. Luparia, L. F. R. Gomes, L. F. Veiros and
N. Maulide, Angew. Chem. Int. Ed., 2012, 51, 8886; (b) Z. Cui, Y. Li,
Y. Ling, J. Huang, J. Cui, R. Wang and X. Yan, Eur. J. Med. Chem.,
2
010, 45, 5576; (c) Q. Huang and V. H. Rawal, Org. Lett., 2006, 8, 543;
Received: 29th January 2016; Com. 16/4826
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