Chemoselective addition of secondary phosphine oxides to alkyl phenylethynyl ketones

Full text of DOI:10.1134/S1070428008080265

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 8, pp. 1245–1246. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © M.Yu. Dvorko, T.E. Glotova, I.A. Ushakov, N.K. Gusarova, B.A. Trofimov, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 8, pp. 1256–1257.
SHORT
COMMUNICATIONS
Chemoselective Addition of Secondary Phosphine Oxides
to Alkyl Phenylethynyl Ketones
M. Yu. Dvorko, T. E. Glotova, I. A. Ushakov, N. K. Gusarova, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: glotova@irioch.irk.ru
Received February 28, 2008
DOI: 10.1134/S1070428008080265
Tertiary phosphine oxides are widely used as
ligands for metal complex catalysts [1, 2], special sol-
vents for stabilization of nanosystems in the synthesis
of semiconductors [3], and extractants for noble, rare-
earth, and transuranium elements [4, 5]. Of particular
importance are polyfunctionalized tertiary phosphine
oxides; however, their synthesis involves known dif-
ficulties. A convenient atom economy approach to such
compounds is based on reactions of PH addends with
functionalized alkenes, alkynes [6, 7], aldehydes, and
ketones [7, 8].
ols IIIa–IIIc. Thus the addition of secondary phos-
phine oxides to alkyl phenylethynyl ketones provide
a convenient method for the synthesis of previously
unknown polyfunctionalized chiral tertiary phosphine
oxides having a hydroxy group and an acetylenic frag-
ment. The products attract interest as highly reactive
building blocks for organic synthesis, synthetic inter-
mediates, and precursors of optically active amphi-
philic ligands for enantioselective processes.
Phosphine oxides IIIa–IIIc (general procedure).
A mixture of 0.5 mmol of secondary phosphine oxide
Ia or Ib, 0.5 mmol of acetylenic ketone IIa or IIb, and
0.1 mmol of potassium hydroxide in 4 ml of THF was
stirred for 35 h at room temperature; in the synthesis of
phosphine oxide IIIa, 0.05 mmol of KOH was used,
and the mixture was stirred for 4 h. The suspension
was passed through a thin layer of aluminum oxide, the
solvent was distilled off under reduced pressure, the
residue was ground with 5 ml of diethyl ether, and the
precipitate was filtered off and dried under reduced
pressure.
In the present work we examined reactions of
accessible secondary phosphine oxides [9] with dielec-
trophilic alkyl phenylethynyl ketones with a view to
synthesize new polyfunctionalized tertiary phosphine
oxides. It seemed that the reaction may be nonselec-
tive. It is known that nucleophilic addition of secon-
dary phosphine oxides to phenyl ethynyl ketone occurs
chemo- and regioselectively at the triple bond [10] and
that their reactions with 3-trialkylsilyl(or germyl)prop-
2-ynals involves the aldehyde group in the latter [11].
We have found that secondary phosphine oxides Ia
and Ib react with alkyl phenylethynyl ketones IIa and
IIb in the system KOH–THF at room temperature in
chemoselective fashion, yielding 63–71% of the corre-
sponding 1-alkyl-1-phosphoryl-3-phenylprop-2-yn-1-
2-(Diphenylphosphoryl)-4-phenylbut-3-yn-2-ol
(IIIa). Yield 0.123 g (71%), mp 140–142°C. IR spec-
trum, ν, cm–1: 3141 (OH), 2234 w (C≡C), 1175 (P=O).
1H NMR spectrum (CDCl3), δ, ppm: 1.80 d (3H, Me,
3JPH = 13.2 Hz), 4.00 br.s (1H, OH), 7.21–7.40 m (5H,
R1
O
R1
R2
O
P
R1
R2
KOH–THF, 20°C
P
H
O
+
Ph
Ph
R1
OH
IIIa–IIIc
Ia, Ib
IIa, IIb
I, R1 = Ph (a), PhCH2CH2 (b); II, R2 = Me (a), Pr (b); III, R1 = Ph, R2 = Me (a), R1 = PhCH2CH2, R2 = Me (b),
R1 = PhCH2CH2, R2 = Pr (c).
1245

DVORKO et al.
1246
The 1H, 13C, and 31P NMR spectra were recorded on
a Bruker DPX-400 spectrometer at 400.13, 101.61, and
161.98 MHz, respectively; the chemical shifts were
measured relative to hexamethyldisiloxane (1H, 13C) or
85% H3PO4 (31P). The IR spectra were obtained in KBr
on a Bruker IFS-25 instrument.
PhC≡), 7.45–7.65 m (6H, p-H, m-H in PhP), 8.00–
8.20 m (4H, o-H in PhP). 13C NMR spectrum (CDCl3),
2
δC, ppm: 25.85 d (Me, JPC = 3.7 Hz), 69.86 d (C2,
1JPC = 87.0 Hz), 89.09 d (PhC, 3JPC = 7.7 Hz), 88.90 d
2
(PhC≡C, JPC = 2.2 Hz), 122.83 (Ci in Ph); 129.1–
129.6, 130.7–132.2 (Carom). 31P NMR spectrum (CDCl3):
δP 34.32 ppm. Found, %: C 76.56; H 5.87; P 9.09.
C22H19O2P. Calculated, %: C 76.29; H 5.53; P 8.94.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-00562).
2-[Bis(2-phenylethyl)phosphoryl]-4-phenylbut-3-
yn-2-ol (IIIb). Yield 0.134 g (67%), mp 103–105°C.
IR spectrum, ν, cm–1: 3131 (OH), 2225 w (C≡C), 1158
REFERENCES
1
(P=O). H NMR spectrum (CDCl3), δ, ppm: 1.90 d
(3H, Me, 3JPH = 12.4 Hz), 2.1–2.6 m (4H, CH2P), 2.9–
3.2 m (4H, CH2Ph), 5.63 br.s (1H, OH), 7.2–7.4 m
(15H, Harom). 13C NMR spectrum (CDCl3), δC, ppm:
1. Hayashi, M., Takezaki, H., Hashimoto, Y., Takaoki, K.,
and Saigo, K., Tetrahedron Lett., 1998, vol. 39, p. 7529.
2. Tolis, E.I., Vallianatou, K.A., Andreadaki, F.J., and
Kostas, I.D., Appl. Organomet. Chem., 2006, vol. 20,
p. 335.
2
1
24.69 d (Me, JPC = 3.6 Hz), 26.90 d (CH2P, JPC
=
1
60.8 Hz), 27.65 d (CH2P, JPC = 57.2 Hz), 28.19 d
(CH2Ph, JPC = 3.6 Hz), 28.26 d (CH2Ph, JPC
2
2
=
3. Snee, P.T., Somers, R.C., Nair, G., Zimmer, J.P., Bawen-
di, M.G., and Nocera, D.G., J. Am. Chem. Soc., 2006,
vol. 128, p. 13320.
2.8 Hz), 67.96 d (C2, JPC = 80.0 Hz), 87.75 d (PhC≡,
3JPC = 7.2 Hz), 88.33 d (PhC≡C, 2JPC = 2.0 Hz), 121.97
(Ci in PhC≡), 126.46 m (Co in CH2Ph), 128.15–128.95
(Cm, Cp in CH2Ph, PhC≡), 131.70 (Co in PhC≡), 141.15–
141.28 (Ci in CH2Ph). 31P NMR spectrum (CDCl3):
δP 51.49 ppm. Found, %: C 77.86; H 6.89; P 7.99.
C26H27O2P. Calculated, %: C 77.59; H 6.76; P 7.70.
1
4. Alguacil, F.J. and Alonso, M., Hydrometallurgy, 2004,
vol. 74, p. 157.
5. Chan, Z., Yan-zhao, Y., Tao, Z., Jian, H., and Chang-
Hong, L., J. Radioanal. Nucl. Chem., 2005, vol. 265,
p. 419.
3-[Bis(2-phenylethyl)phosphoryl]-1-phenylhex-
1-yn-3-ol (IIIc). Yield 0.135 g (63%), mp 117–119°C.
IR spectrum, ν, cm–1: 3083 (OH), 2221 w (C≡C), 1145
6. Arbuzova, S.N., Gusarova, N.K., and Trofimov, B.A.,
Arkivoc, 2006, part (v), p. 12.
7. Trofimov, B.A., Sukhov, B.G., Malysheva, S.F., and
1
(P=O). H NMR spectrum (CDCl3), δ, ppm: 1.05 t
Gusarova, N.K., Katal Promst., 2006, p. 18.
(3H, Me, 3JHH = 7.0 Hz), 1.87 m (2H, 5-H), 2.1–2.6 m
(6H, CH2P, 4-H), 2.9–3.2 m (4H, CH2Ph), 4.32 br.s
8. Well, M. and Schmutzler, R., Phosphorus, Sulfur Silicon
Relat. Elem., 1992, vol. 72, p. 171.
(1H, OH), 7.2–7.4 m (15H, Harom). 13C NMR spectrum
9. Malysheva, S.F. and Arbuzova, S.N., Sovremennyi orga-
nicheskii sintez (Contemporary Organic Synhtesis),
Rakhmankulov, D.L., Ed., Moscow: Khimiya, 2003,
p. 160.
3
(CDCl3), δC, ppm: 14.30 s (Me), 16.91 d (C5, JPC
=
1
7.9 Hz), 27.11 d (PCH2, JPC = 60.0 Hz), 27.60 d
(PCH2, JPC = 58.0 Hz), 28.23 s (PhCH2), 38.33 d (C4,
1
2JPC = 2.4 Hz), 71.40 d (C3, JPC = 79.5 Hz), 87.15 d
1
10. Glotova, T.E., Dvorko, M.Yu., Arbuzova, S.N., Usha-
kov, I.A., Verkhoturova, S.I., Gusarova, N.K., and Trofi-
mov, B.A., Lett. Org. Chem., 2007, vol. 4, p. 109.
(C2, 2JPC = 1.9 Hz), 88.72 d (C1, 3JPC = 7.6 Hz), 122.01
(Ci in PhC≡), 126.39 m (Co in CH2Ph), 128.14–128.88
(Cm, Cp in CH2Ph, PhC≡), 131.73 (Co in PhC≡), 141.21–
141.65 (Ci in CH2Ph). 31P NMR spectrum (CDCl3):
δP 51.45 ppm. Found, %: C 78.38; H 7.49; P 7.31.
C28H31O2P. Calculated, %: C 78.12; H 7.26; P 7.19.
11. Gusarova, N.K., Reutskaya, A.M., Ivanova, N.I., Med-
vedeva, A.S., Demina, M.M., Novopashin, P.S., Afo-
nin, A.V., Albanov, A.I., and Trofimov, B.A., J. Organo-
met. Chem., 2002, vol. 659, p. 172.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008