Nucleophilic addition of secondary phosphine chalcogenides to, α,β-acetylenic γ-hydroxy acid nitriles and a rearrangement of the adducts

Article abstract of DOI:10.1016/j.mencom.2007.11.008

Bis(2-phenylethyl)phosphine oxide and sulfide and bis[2-(2-pyridyl)ethyl]phosphine sulfide add easily (LiOH-THF, 28-30 °C) to 4-hydroxy-4-methyl-2-pentynenitrile to give regio- and stereoselectively 3-substituted (Z)-4-hydroxy-4-methyl-2-pentenenitriles i

Full text of DOI:10.1016/j.mencom.2007.11.008

Mendeleev
Communications
Mendeleev Commun., 2007, 17, 325–326
Nucleophilic addition of secondary phosphine
chalcogenides to α,β-acetylenic γ-hydroxy acid
nitriles and a rearrangement of the adducts
Svetlana N. Arbuzova, Nina K. Gusarova, Maria V. Bogdanova,
Igor A. Ushakov, Anastasiya G. Mal’kina and Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
64033 Irkutsk, Russian Federation. Fax: +7 3952 41 9346; e-mail: arbuzova@irioch.irk.ru
6
DOI: 10.1016/j.mencom.2007.11.008
Bis(2-phenylethyl)phosphine oxide and sulfide and bis[2-(2-pyridyl)ethyl]phosphine sulfide add easily (LiOH–THF, 28–30 °C) to
-hydroxy-4-methyl-2-pentynenitrile to give regio- and stereoselectively 3-substituted (Z)-4-hydroxy-4-methyl-2-pentenenitriles
in 82–91% yield; the latter, upon heating (58–60 °C) in the presence of LiOH in THF, rearrange cleanly to the corresponding
-cyano-2-propen-1-yl phosphinates and phosphinothioates (isolated yields of 82–86%).
4
3
The addition of secondary phosphine oxides or sulfides to
The structure of adducts 2a–c follows from their 31P NMR
chemical shifts (~46–49 ppm), the observed P–C coupling
1
substituted acetylenes is an attractive route to promising ligands
ethenyl
2
1(d)
1
13
for usable metallocomplexes and rewarding building blocks
( J
~47–49 Hz) in their C NMR spectra and the stretching
P–C
–
1
for organic synthesis. In addition, these reactions contribute to
the basic chemistry of both organophosphorus and acetylenic
compounds.3
However, the above addition reactions for the nitriles of
α,β-acetylenic γ-hydroxy acids have not been reported, though
they would lead to new highly functionalised tertiary phosphine
oxides and sulfides and provide additional information on the
reactivity of P–H and CºC bonds.
For this reason, we studied the addition of bis(2-phenyl-
ethyl)phosphine oxide 1a and sulfide 1b and bis[2-(2-pyridyl)-
ethyl]phosphine sulfide 1c to the nitriles of α,β-acetylenic
γ-hydroxy acids using 4-hydroxy-4-methyl-2-pentynenitrile as
a typical representative. These experiments showed that while
the uncatalysed reaction did not occur at 35–40 °C (20 h, THF)
the base-catalysed addition (LiOH–THF) proceeded readily at
vibrations of the OH group (3300–3350 cm ) in their IR
spectra. These data provide unequivocal evidence for the presence
of the X=P–C=C–C–OH fragment (X = O, S) and hence the
molecular structures of 2a–c. The Z-configurations of phosphine
X
R
R
P
CN
X
H
Me
OH
LiOH
THF
R2P
+ Me
CN
HO
Me
Me
2a–c
1a–c
a R = PhCH CH , X = O
2
2
b R = PhCH CH , X = S
2
2
c R = 2-PyCH CH , X = S
2
2
Scheme 1
2
8–30 °C to afford selectively adducts 2a–c in almost quanti-
(
Z)-3-[Bis(2-phenylethyl)phosphorothioyl]-4-hydroxy-4-methyl-2-pentene-
†
tative yields (82–91%) (Scheme 1).
1
nitrile 2b: yield 91% (0.35 g); yellow oil. H NMR (CDCl ) d: 1.66 (s,
3
Sulfides 1b,c were found much more reactive than phosphine
oxide 1a (the reaction time of 2.5–3 h against 22 h) owing to
their higher nucleophilicity.
6
H, Me), 2.44–2.54 (m, 2H, CH P), 2.89–2.99 (m, 4H, CH P, CH Ph),
2
2
2
3.05–3.17 (m, 2H, CH Ph), 5.25 (s, 1H, OH), 6.20 (d, 1H, =CH,
2
3
13
JPH 32.3 Hz), 7.22–7.34 (m, 10H, Ph). C NMR (CDCl ) d: 29.30
3
1
(
CH Ph), 31.41 (Me), 36.11 (d, CH P, J 49.1 Hz), 77.15 (d, CMe ,
JPC 5.2 Hz), 105.54 (=CH), 116.50 (d, CºN, J 9.2 Hz), 127.73 (Cp),
2
2
PC
2
†
2
3
General procedure for the preparation of compounds 2. To a mixture
PC
3
of secondary phosphine chalcogenide 1 (1.00 mmol) and LiOH (0.02 g,
129.39 (C ), 129.78 (C ), 140.90 (d, C , J 16.3 Hz), 165.90 (d, =CP,
o
m
i
PC
1
31
–1
0.84 mmol) in 4 ml of THF, a solution of 4-hydroxy-4-methyl-2-pentyne-
JPC 47.4 Hz). P NMR (CDCl ) d: 46.30. IR (n/cm ): 3350 (OH), 3100
3
nitrile (0.11 g, 1.00 mmol) in 4 ml of THF was added dropwise for 10 min.
The reaction mixture was stirred at 28–30 °C for 22 (1a) or 2.5–3 h (1b,c),
passed through a layer of Al O (0.5 cm), then THF was removed under
(=CH), 2210 (CºN), 1660 (C=C), 680 (P=S). Found (%): C, 68.73; H,
6.67; N, 3.89; P, 8.20; S 8.15. Calc. for C H NOPS (%): C, 68.90;
2
2
26
H, 6.83; N, 3.65; P, 8.08; S 8.36.
2
3
reduced pressure; the residue was dried in a vacuum.
(Z)-3-{Bis[2-(2-pyridyl)ethyl]phosphorothioyl}-4-hydroxy-4-methyl-
2-pentenenitrile 2c: purified by precipitation from chloroform to hexane;
yield 88% (0.34 g); yellow powder, mp 60–62 °C (hexane). H NMR
The H, C and 31P NMR spectra were measured on a Bruker DPX 400
spectrometer (400.13, 101.61 and 161.98 MHz, respectively). The IR
spectra were recorded on a Bruker IFS-25 spectrometer in films.
1
13
1
(CDCl ) d: 1.59 (s, 6H, Me), 2.67–2.77 (m, 2H, CH P), 3.07–3.18 (m,
3
2
(
Z)-3-[Bis(2-phenylethyl)phosphoryl]-4-hydroxy-4-methyl-2-pentene-
4H, CH P, CH Py), 3.25–3.35 (m, 2H, CH Py), 5.40 (s, 1H, OH), 6.15
2 2 2
3
5
3
nitrile 2a: yield 82% (0.30 g); white powder, mp 100–101 °C (Et O)
lit., 100–102 °C). 1H NMR (CDCl ) d: 1.55 (s, 6H, Me), 2.30–2.45,
.52–2.65 (m, 4H, CH P), 2.85–2.98, 3.00–3.10 (m, 4H, CH Ph), 5.25
s, 1H, OH), 6.02 (d, 1H, =CH, J 32.2 Hz), 7.18–7.31 (m, 10H, Ph),
non-equivalence of protons in the CH P and CH Ph moieties resulted
from their diastereotopy. P NMR (CDCl ) d: 46.93. IR (n/cm ):
300 (OH), 2210 (CºN), 1160 (P=O). Found (%): C, 71.62; H, 7.39;
(d, 1H, =CH, J 32.1 Hz), 7.12 (m, 2H, H , Py), 7.20 (d, 2H, H , Py,
2
PH
7
3
1
1
4
6
3
(
2
(
J3–4 7.7 Hz), 7.59 (m, 2H, H , Py), 8.51 (d, 2H, H , Py, J 4.6 Hz).
3
5–6
3
C NMR (CDCl ) d: 30.51 (Me), 30.58 (CH Py), 32.49 (d, CH P,
2
2
3
2
2
3
2
JPC 50.9 Hz), 76.05 (d, CMe , J 4.2 Hz), 105.30 (=CH), 115.36 (d, CºN,
2 PC
3J 9.2 Hz), 121.80 (C , Py), 123.15 (C , Py), 136.65 (C , Py), 149.48
(C , Py), 159.33 (d, C , Py, J 16.2 Hz), 164.29 (d, =CP, J 48.7 Hz).
PC PC
PH
5
3
4
2
2
PC
6
3
1
–1
2
3
1
3
31
–1
3
P NMR (CDCl ) d: 48.65. IR (n/cm ): 3350 (OH), 2210 (CºN), 640
3
N, 3.60; P, 8.69. Calc. for C H NO P (%): C, 71.92; H, 7.13; N, 3.81;
P, 8.43.
(P=S). Found (%): C, 62.49; H, 6.48; N, 10.65; P, 7.85; S, 8.26. Calc. for
C H N OPS (%): C, 62.32; H, 6.28; N, 10.90; P, 8.04; S, 8.32.
2
2
26
2
2
0
24
3
©
2007 Mendeleev Communications. All rights reserved.
– 325 –

Mendeleev Commun., 2007, 17, 325–326
chalcogenides 2a–c were confirmed by the cross peaks of the
R
P
Li+
X
1
1
R
P
ethenyl and methyl protons in the H– H NOESY spectra,
indicating their cis disposition relative to the double bond.
Upon heating (58–60 °C, 7–10 h) in the presence of equimolar
amounts of LiOH in THF, adducts 2a–c cleanly and quanti-
R
X
R
CN
CN
LiOH
2
a–c
+Li
– H2O
O
O
Me
Me
Me
X
Me
3
1
tatively ( P NMR) rearranged to (2E)-3-cyano-1,1-dimethyl-
R
2-propen-1-yl bis(2-phenylethyl)phosphinate 3a, O-[(2E)-3-cyano-
1,1-dimethyl-2-propen-1-yl] bis(2-phenylethyl)phosphinothioate
3b and O-[(2E)-3-cyano-1,1-dimethyl-2-propen-1-yl] bis[2-
R
+ CN
Li
H O
2
P
3
a–c
O
– LiOH
(
2-pyridyl)ethyl]phosphinothioate 3c (Scheme 2) with isolated
Me
Scheme 3
Me
‡
yields of 82–86% after purifying on Al O .
2
3
CN
1
3a–c is supported by the 31P NMR chemical shifts (54.92 ppm
for 3a and 96–97 ppm for 3b,c), the availability of signals for
X
2
LiOH
O
2
a–c
R
P
1
THF, 58–60 °C
Me
two ethenyl protons in the H NMR spectra, the absence of a
Me
a–c
a R = PhCH CH , X = O
R
1
13
JP–Cethenyl coupling in the C NMR spectra and the absence of
3
the stretching vibrations of the OH group in the IR spectra.
To the best of our knowledge, a rearrangement of this type
for β-hydroxyalkylphosphine chalcogenides is unknown, although
α-hydroxy analogues are reported to isomerise with oxygen
atom insertion into the neighbouring P–C bond, most often in
the presence of bases.4
2
2
b R = PhCH CH , X = S
2
2
c R = 2-PyCH CH , X = S
2
2
Scheme 2
In the absence of LiOH this process did not occur. The
mechanism of the rearrangement observed can be rationalised
as intramolecular nucleophilic substitution at the four-coordinated
phosphorus atom by the alkoxide anion. It seems likely that the
Thus, the synthesis of two families of functionalised unsaturated
organophosphorus compounds from available secondary phosphine
5
chalcogenides and the nitriles of α,β-acetylenic γ-hydroxy
+
6
process is Li -assisted (Scheme 3).
acids has been developed, and a new intramolecular rearrange-
The mechanism shown in Scheme 3 is in accordance with the
E-configuration of rearrangement products 3a–c. The presence
of the X=P–O–C–CH=CH fragment (X = O, S) in products
ment of the initial adducts involving oxygen atom insertion into
the P–C bond has been observed.
This work was supported by the Russian Foundation for
Basic Research (grant no. 07-03-00562).
‡
General procedure for the preparation of compounds 3. A mixture of
pentenenitrile 2 (0.60 mmol) and LiOH (0.014 g, 0.60 mmol) in 5 ml
of THF was stirred at 58–60 °C for 7 (2a) or 10 h (2b,c), cooled and
passed through a layer of Al O (0.5 cm). Then, THF was removed under
reduced pressure; the residue was dried in a vacuum.
2E)-3-Cyano-1,1-dimethyl-2-propen-1-yl bis(2-phenylethyl)phosphinate
References
2
3
1
(a) A. F. Parsons, D. J. Sharpe and P. Taylor, Synlett, 2005, 2981;
b) S. N. Arbuzova, N. K. Gusarova, M. V. Bogdanova, N. I. Ivanova,
I. A. Ushakov, A. G. Mal’kina and B. A. Trofimov, Mendeleev Commun.,
005, 183; (c) S. N. Arbuzova, N. K. Gusarova and B. A. Trofimov,
(
(
1
3
a: yield 86% (0.19 g); brown oil. H NMR (CDCl ) d: 1.63 (s, 6H,
3
2
Me), 1.97–2.02 (m, 4H, CH P), 2.80–2.87 (m, 4H, CH Ph), 5.38 (d, 1H,
2
2
Arkivoc, 2006, (v), 12; (d) M. Niu, H. Fu, Y. Jiang and Y. Zhao, Chem.
Commun., 2007, 272; (e) T. E. Glotova, M. Yu. Dvorko, S. N. Arbuzova,
I. A. Ushakov, S. I. Verkhoturova, N. K. Gusarova and B. A. Trofimov,
Lett. Org. Chem., 2007, 4, 109; (f) B. A. Trofimov, S. F. Malysheva,
N. K. Gusarova, N. A. Belogorlova, S. F. Vasilevsky, V. B. Kobychev,
B. G. Sukhov and I. A. Ushakov, Mendeleev Commun., 2007, 17, 181.
(a) Asymmetric Catalysis in Organic Synthesis, ed. R. Noyori, John
Wiley & Sons, New York, 1994; (b) Comprehensive Asymmetric Catalysis,
eds. E. N. Jacobsen, A. Pfaltz and H. Yamamoto, Springer, Berlin, 1999;
2
3
1
3
4
H , J 16.4 Hz), 6.66 (dd, 1H, H , J 16.4 Hz, J 1.5 Hz), 7.10–7.27
HH
HH
PH
(
1
m, 10H, Ph). 13C NMR (CDCl ) d: 28.30 (Me, CH Ph), 32.17 (d, CH P,
3 2 2
2
2
JPC 88.0 Hz), 80.81 (d, CMe , J 8.1 Hz), 98.22 (C ), 116.76 (CºN),
2
PC
3
1
1
3
9
26.65 (C ), 128.10 (C ), 128.80 (C ), 140.49 (d, C , JPC 14.6 Hz),
p o m i
1
3
31
–1
57.93 (d, C , J 6.13 Hz). P NMR (CDCl ) d: 54.92. IR (n/cm ):
PC
3
100 (=CH), 2210 (CºN), 1640 (C=C), 1160 (P=O), 1145 (C–OP),
80 (P–O). Found (%): C, 71.65; H, 7.36; N, 3.64; P, 8.55. Calc. for
2
C H NO P (%): C, 71.92; H, 7.13; N, 3.81; P, 8.43.
2
2
26
2
O-[(2E)-3-Cyano-1,1-dimethyl-2-propen-1-yl] bis(2-phenylethyl)phos-
(c) Catalytic Asymmetric Synthesis, ed. I. Ojima, 2 edn., VCH Pubishers,
nd
1
phinothioate 3b: yield 83% (0.19 g); brown oil. H NMR (CDCl ) d:
Weinheim, 2000; (d) J. W. Faller, J. C. Wilt and J. Parr, Org. Lett., 2004,
6, 1301; (e) D. Liu, Q. Dai and X. Zhang, Tetrahedron, 2005, 61, 6460;
(f) G. C. Fu, Acc. Chem. Res., 2006, 39, 853; (g) Q. Dai, W. Gao, D. Liu,
L. M. Kapes and X. Zhang, J. Org. Chem., 2006, 71, 3928; (h) D. K.
Whelligan and C. Bolm, J. Org. Chem., 2006, 71, 4609.
3 B. A. Trofimov, Curr. Org. Chem., 2002, 6, 1121.
4 (a) L. Hall, C. Stephens and J. Dryzda, J. Am. Chem. Soc., 2007, 129,
305; (b) S. A. Buckler and M. Epstein, Tetrahedron, 1962, 18, 1211;
3
1
5
7
2
.67 (s, 6H, Me), 2.21–2.29 (m, 4H, CH P), 2.87–2.94 (m, 4H, CH Ph),
2 2
2
3
1
3
4
.37 (d, 1H, H , J 16.3 Hz), 6.78 (dd, 1H, H , J 16.3 Hz, J 1.4 Hz),
HH
HH
PH
13
3
.14–7.30 (m, 10H, Ph). C NMR (CDCl ) d: 28.92 (d, Me, J 3.7 Hz),
3
PC
2
1
9.92 (d, CH Ph, J 2.0 Hz), 39.14 (d, CH P, J 67.8 Hz), 81.87 (d,
2
PC
2
PC
2
2
CMe , J 8.1 Hz), 98.16 (C ), 116.78 (CºN), 127.46 (C ), 129.07 (C ),
1
3
2
PC
p
1
o
3
3
29.61 (C ), 140.42 (d, C , J 14.7 Hz), 158.25 (d, C , J 5.2 Hz).
m i PC PC
P NMR (CDCl ) d: 96.08. IR (n/cm ): 3100 (=CH), 2220 (CºN), 1653
1
–1
3
(c) V. S. Abramov, N. I. Dyakonova and V. D. Efimova, Zh. Obshch.
(
C=C), 1132 (C–OP), 984 (P–O), 617 (P=S). Found (%): C, 68.73; H,
Khim., 1969, 39, 1971 (in Russian); (d) A. N. Pudovik and M. G. Zimin,
Pure Appl. Chem., 1980, 52, 989; (e) F. Hammerschmidt, Monatsh.
Chim., 1993, 124, 1063; (f) S. Jankowski, J. Marczak, A. Olczak and
M. Glowka, Tetrahedron Lett., 2006, 47, 3341.
6
.68; N, 3.94; P, 8.28; S 8.17. Calc. for C H NOPS (%): C, 68.90;
22 26
H, 6.83; N, 3.65; P, 8.08; S 8.36.
O-[(2E)-3-Cyano-1,1-dimethyl-2-propen-1-yl] bis[2-(2-pyridyl)ethyl]-
1
phosphinothioate 3c: yield 82% (0.19 g); brown oil. H NMR (CDCl ) d:
3
5
(a) B. A. Trofimov, S. N. Arbuzova and N. K. Gusarova, Usp. Khim.,
1999, 68, 240 (Russ. Chem. Rev., 1999, 68, 215); (b) N. K. Gusarova,
M. V. Bogdanova, N. I. Ivanova, N. A. Chernysheva, B. G. Sukhov, L. M.
Sinegovskaya, O. N. Kazheva, G. G. Alexandrov, O. A. D’yachenko and
B. A. Trofimov, Synthesis, 2005, 3103.
1
5
7
.67 (s, 6H, Me), 2.46–2.53 (m, 4H, CH P), 3.09–3.15 (m, 4H, CH Py),
2 2
2
3
1
3
4
.43 (d, 1H, H , J 16.4 Hz), 6.80 (dd, 1H, H , J 16.4 Hz, J 1.7 Hz),
HH
HH
PH
5
3
4
.11 (m, 2H, H , Py), 7.16 (m, 2H, H , Py), 7.59 (m, 2H, H , Py), 8.50
6
13
3
(m, 2H, H , Py). C NMR (CDCl ) d: 28.08 (d, Me, J 2.0 Hz), 31.27
3 PC
1
2
(
CH Py), 35.81 (d, CH P, J 69.1 Hz), 81.86 (d, CMe , J 8.8 Hz),
6 S. R. Landor, B. Demetriou, R. Grzeskowiak and D. F. Pavey, J. Organomet.
Chem., 1975, 93, 129.
7 S. N. Arbuzova, S. I. Shaikhutdinova, N. K. Gusarova, M. V. Nikitin,
A. G. Mal’kina, B. G. Sukhov, M. V. Bogdanova and B. A. Trofimov,
Zh. Obshch. Khim., 2005, 75, 552 (Russ. J. Gen. Chem., 2005, 75, 514).
2
2
PC
2
3
PC
2
5
9
8.22 (C ), 116.88 (CºN), 121.71 (C , Py), 123.08 (C , Py), 136.64
4
6
1
3
2
(C , Py), 149.51 (C , Py), 158.24 (d, C , J 5.4 Hz), 159.79 (d, C , Py,
3
PC
31
–1
JPC 15.5 Hz). P NMR (CDCl ) d: 97.01. IR (n/cm ): 3100 (=CH),
3
2
210 (CºN), 1640 (C=C), 1140 (C–OP), 980 (P–O), 620, 605 (P=S).
Found (%): C, 62.45; H, 6.48; N, 10.65; P, 7.85; S, 8.09. Calc. for
C H N OPS (%): C, 62.32; H, 6.28; N, 10.90; P, 8.04; S, 8.32.
2
0
24
3
Received: 15th June 2007; Com. 07/2963
–
326 –