Chemo- and regiospecific monoaddition of secondary phosphine sulfides to 1-acyl-2-phenylacetylenes

Article abstract of DOI:10.1080/10426500701648069

Secondary phosphine sulfides react with 1-acyl-2-phenylacetylenes under mild conditions (KOH, THF, r.t.) to afford chemo-and regiospecifically 3-diorganophosphorothioyl-1-R-3-phenyl-2-propen-1-ones in high yield, with the E-isomers being formed exclusivel

Full text of DOI:10.1080/10426500701648069

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Chemo- and Regiospecific
Monoaddition of Secondary
Phosphine Sulfides to 1-Acyl-2-
phenylacetylenes
Tatyana E. Glotova a , Marina Yu. Dvorko a , Nina
K. Gusarova a , Svetlana N. Arbuzova a , Igor A.
Ushakov a , Tatyana I. Kazantseva a & Boris A.
Trofimov a
a A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of
Sciences , Irkutsk, Russia
Published online: 05 Jun 2008.
To cite this article: Tatyana E. Glotova , Marina Yu. Dvorko , Nina K. Gusarova ,
Svetlana N. Arbuzova , Igor A. Ushakov , Tatyana I. Kazantseva & Boris A. Trofimov
(2008) Chemo- and Regiospecific Monoaddition of Secondary Phosphine Sulfides to 1-
Acyl-2-phenylacetylenes, Phosphorus, Sulfur, and Silicon and the Related Elements,
183:6, 1396-1401, DOI: 10.1080/10426500701648069
To link to this article: http://dx.doi.org/10.1080/10426500701648069
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Phosphorus, Sulfur, and Silicon, 183:1396–1401, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701648069
Chemo- and Regiospecific Monoaddition of Secondary
Phosphine Sulfides to 1-Acyl-2-phenylacetylenes
Tatyana E. Glotova, Marina Yu. Dvorko,
Nina K. Gusarova, Svetlana N. Arbuzova,
Igor A. Ushakov, Tatyana I. Kazantseva,
and Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch
of the Russian Academy of Sciences, Irkutsk, Russia
Secondary phosphine sulfides react with 1-acyl-2-phenylacetylenes under
mild conditions (KOH, THF, r.t.) to afford chemo- and regiospecifically 3-
diorganophosphorothioyl-1-R-3-phenyl-2-propen-1-ones in high yield, with the E-
isomers being formed exclusively (R = Ph and 2-thienyl) or predominantly (60%,
R = Me).
Keywords 1-Acyl-2-phenylacetylenes; 3-(diphenethylphosphorothioyl)-1-R-3-phenyl-2-
propen-1-one; bis(2-phenylethyl)phosphine sulfide; nucleophilic monoaddition
INTRODUCTION
The development of a convenient method for the preparation of sec-
ondary phosphines and phosphine chalcogenides from elemental phos-
phorus, organohalides1 and aryl or hetarylalkenes,2 in the presence
of strong bases has opened new opportunities for atom-economic syn-
theses of tertiary phosphines and phosphine chalcogenides—including
functionalized and unsaturated derivatives—based on the nucleophilic
and radical addition of the PH-function to multiple C C3,4and double
C O5,6 bonds. At the same time, reactions of secondary phosphine sul-
fides with acetylenes have been poorly investigated.
To the best of our knowledge the only report in the literature
describing a nucleophilic addition of secondary phosphine sulfides
to a C C triple bond concerns the double α,β-addition of bis(2-
phenylethyl)phosphine sulfide to 3-phenyl-2-propynenitrile in the
Received 27 April 2007; accepted 14 August 2007.
Address correspondence to Boris A. Trofimov, A. E. Favorsky Irkutsk Institute of
Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street,
664033, Irkutsk, Russia. E-mail: glotova@irioch.irk.ru
1396

Addition of Secondary Phosphine Sulfides to Acylacetylenes
1397
presence of KOH to form 2,3-bis[bis(2-phenylethyl)phosphorothioyl]-
3-phenylpropanenitriles.7 3-(Trialkylsilyl)- and 3-(trialkylgermyl)-2-
propynals were also reported to react with secondary phosphine chalco-
genides at the carbonyl group under catalyst-free conditions to give the
corresponding tertiary phosphine chalcogenides with acetylenic and hy-
droxyl moieties in high yield.6
In order to extend the synthetic potential of the chemistry of sec-
ondary phosphine sulfides, acetylenes, and carbonyl compounds, and
to synthesize new polyfunctional tertiary phosphine sulfides, we have
investigated the reaction of bis(2-phenylethyl)phosphine sulfide 1 with
1-acyl-2-phenylacetylenes.
RESULTS AND DISCUSSION
We have found that the phosphine sulfide 1 reacts readily (KOH, THF,
20–22◦C, 4 h) with 1,3-diphenyl-2-propyn-1-one 2 and 3-phenyl-1-(2-
thienyl)-2-propyn-1-one 3 to give chemo-, regio-, and stereospecifically
the E-isomers of the addition products 4, 5 in 80–85% yield (Scheme 1).
This contradicts the conventional trans-mode addition of nucleophiles
to monosubstituted acetylenes, usually producing the Z-isomers.
SCHEME 1
Under similar conditions, addition of the phosphine sulfide 1 to
4-phenyl-3-butyn-2-one 6 proceeds non-stereospecifically to give 4-
(diphenethylphosphorothioyl)-4-phenyl-3-buten-2-one 7 in 67% yield as
a 3 : 2 mixture of the E- and Z-isomer (Scheme 2).
SCHEME 2

1398
T. E. Glotova et al.
It is unlikely that the E-isomer of the phosphine sulfide 7 is formed
because of post-isomerization of the Z-isomer formed initially, since the
ratio of these isomers remains practically unchanged upon prolonged
heating (100◦C, 8 h) in DMSO.
At the same time the violation of trans-mode addition in the above
reactions agrees with the known data on the addition of nucleophiles
to acylacetylenes8 or methyl propiolate9 to give the vinylic carbanions
A and C, which readily isomerize to each other via the allenic interme-
diate B (Scheme 3). The formation of allenic intermediates of the type
B was observed, for example, in the reaction of organocuprates with
alkynyl carbonyl compounds.10
SCHEME 3
The preferred or exclusive formation of E-adducts in the reactions
studied (Schemes 2 and 3) is likely to be influenced by steric effects.3
The configurations of the E- and Z-isomer of compound 7 were de-
1
termined based on 1D and 2D homo- and heteronuclear H, 13C and
31P NMR spectroscopy. The positions of the thiophosphoryl and acyl
groups relative to the double bond in compound 7 were established by
comparison of the heteronuclear trans and cis coupling constants 3 J
,
PH
3 J
and 3 J (Cipso PhC CH), which are known to be highly stere-
PC
O
CH
ospecific. The data obtained allowed us to assign the E-configuration to
compounds 4 and 5.
Thus, the reaction of phosphine sulfides with acylacetylenes proves
to be a general approach to the expedient atom-economic synthe-
sis of polyfunctional tertiary phosphine sulfides, possible polydentate
(“hemilabile”) ligands for the design of metal complex catalysts,11 in-
termediates and coordinating solvents for the preparation of conduc-
tive nanomaterials,12 as well as reactive building blocks for organic
synthesis.
EXPERIMENTAL
1H, 13C, and 31P NMR spectra were recorded with a Bruker DPX 400
(400.13, 101.61, and 161.98 MHz, respectively) spectrometer in CDCl3
solutions and referenced to internal HMDS and external 85% H3PO4,
3
respectively. The values of the coupling constants J were obtained
CH

Addition of Secondary Phosphine Sulfides to Acylacetylenes
1399
by the analysis of sections of the 2D HMBC NMR spectra. IR spectra
were measured with a Bruker IFS 25 instrument in microlayer and as
KBr pellets.
Synthesis of Bis(2-phenylethyl)-(1-phenyl-2-acylethenyl)
phosphine Sulfides 4, 5, and 7—General Procedure
To a solution of bis(2-phenylethyl)phosphine sulfide (0.55 mmol) and 1-
acyl-2-phenylacetylene (0.55 mmol) in 3 mL of THF, KOH 0.5 H2O (15%
water content) (0.11 mmol) was introduced. The suspension thus ob-
tained was stirred at 20–22◦C for 4 h. KOH was filtered off, and the sol-
vent was removed from the filtrate under reduced pressure. The crude
honey-like product was washed with a mixture of ether and petroleum
ether (1 : 3) (2 mL). After drying under vacuum (1 Torr), the phosphine
sulfides 4,5, and 7 were obtained.
(E)-3-(Diphenethylphosphorothioyl)-1,3-diphenyl-2-propen-1-
one (4)
1
Light-yellow powder, m.p. 94–96◦C, 224 mg (85%) yield. H NMR,
δ (ppm), J (Hz): 2.15, 2.31 (br. m, 4H, CH2P), 3.03, 3.19 (br. m, 4H,
CH2Ph), 7.10–7.91 (m, 20H, Ph), 8.32 (d, 3 J
22.5, 1H, CH).
P
C C H
13C NMR, δ (ppm), J (Hz): 28.6 (d, 2 J 2.0, CH2Ph), 31.5 (d, 1 J 51.6,
PC
PC
CH2P), 126.6, 128.2, 128.3, 128.6, 128.8, 128.9, 133.8 (C-o, C-m, C-p
PhCH2, PhC C, PhC O), 134.3 (d, 2 J 7.4, 3 J 9.4, C-i PhC CH),
PC
CH
136.8 (C-i PhC O), 140.6 (d, 3 JPC 16.2, C-i PhCH2), 144.0 (d, 2 JPC 11.1,
P
C CH), 144.8 (d, 1 JPC 55.3, P C CH), 192.0 (d, 3 JPC 17.0, C O). 31
P
NMR, δ (ppm): 50.8. IR ν (cm−1): 1660 (C O), 680 (P S). Anal. Calcd.
for C31H29OPS: C, 77.47; H, 6.08; P, 6.44; S, 6.67. Found: C, 77.23; H,
6.28; P, 6.78; S, 6.38.
(E)-3-(Diphenethylphosphorothioyl)-3-phenyl-1-(2-thienyl)-2-
propen-1-one (5)
Yellow oil, 214 mg (80%) yield. 1H NMR, δ (ppm), J (Hz): 2.05,
2.19 (br. m, 4H, CH2P), 2.92, 3.06 (br. m, 4H, CH2Ph), 7.11 (2H, o H
PhC C), 7.16 (dd, 3 J
o-H PhCH2), 7.22 (2H, p-H PhCH2), 7.28 (4H, m-H PhCH2), 7.38 (3H,
m-H, p-H PhC C), 7.70 (m, 1H, H-5 thienyl), 7.86 (m, 1H, H-3 thienyl),
3.7, 3 J
4.9, 1H, H-4 thienyl), 7.18 (4H,
H4−H3
H4−H5
8.28 (d, 3 JP
22.0, 1H, CH). 13C NMR, δ (ppm), J (Hz): 28.5 (d,
H
C
C
2 JPC 2.0, CH2Ph), 31.4 (d, 1 JPC 51.5, CH2P), 126.7 (C-pPhCH2), 127.9 (d,
3 JPC 3.2, C-o PhC C), 128.3 (C-o PhCH2), 128.5 (C-4 thienyl), 128.7 (C-p
PhC C), 128.8 (C-m PhCH2), 128.9 (C-m PhC C), 133.7 (C-3 thienyl),
134.5 (d, 2 J 7.2, 3 J 9.4, C-i PhC CH), 135.2 (C-5 thienyl), 140.6
PC
CH
(d, 3 J 15.0, C-i PhCH2), 141.5 (d, 2 J 12.0, P C CH), 144.8 (C-2
PC
PC

1400
T. E. Glotova et al.
1
3
thienyl), 146.3 (d, J 54.3, P C CH), 182.8 (d, J 18.0, C O). 31P
PC
PC
NMR, δ (ppm): 50.7. IR ν (cm−1): 1620 (C O), 680 (P S). Anal. Calcd.
for C29H27OPS2: C, 71.58; H, 5.59; P, 6.36; S, 13.18. Found: C, 71.76; H,
5.82; P, 6.52; S, 13.01.
4-(Diphenethylphosphorothioyl)-4-phenyl-3-buten-2-one (7)
1
Red oil, 154 mg (67%) yield. (E)-isomer: H NMR, δ (ppm), J (Hz):
2.00 (s, 3H, Me), 2.00, 2.40 (br. m, 4H, CH2P), 2.80, 3.10 (br. m, 4H,
CH2Ph), 7.04–7.45 (m, 15H, Ph), 7.54 (d, 3 J
22.3, 1H, CH).
P
C C H
13C NMR, δ (ppm), J (Hz): 28.5 (d, 2 J 1.6, CH2Ph), 30.9 (s, Me), 31.3
PC
(d, 1 J 52.0, CH2P), 126.6, 128.1, 128.3, 128.6, 129.1 (C-o, C-m, C-p
PC
2
3
PhCH2, PhC C), 134.5 (d, J 7.2, J 9.9, C-i PhC CH), 140.5 (d,
PC
CH
3 J 15.5, C-i PhCH2), 144.3 (d, 1 J 54.7, P C CH), 144.5 (d, 2 J
PC
PC
PC
10.4, P C CH), 199.1 (d, 3 J 17.6, C O). 31P NMR, δ (ppm): 50.4.
PC
1
(Z)-isomer: H NMR, δ (ppm), J (Hz): 2.54 (s, 3H, Me), 2.00, 2.40 (m
br., 4H, CH2P), 2.80, 3.10 (m br., 4H, CH2Ph), 7.04–7.45 (m, 15H, Ph),
3
6.74 (d, J
PC
33.8, 1H, CH). 13C NMR, δ (ppm), J (Hz): 28.7 (d,
P
C C H
2 J 2.0, CH2Ph), 31.7 (s, Me), 34.4 (d, 1 J 50.3, CH2P), 126.42, 128.1,
PC
128.3, 128.6, 128.7, 129.0 (C-o, C-m, C-p PhCH2, PhC C), 138.8 (d, 2 J
PC
3
3
8.0, J 7.2, C-i PhC CH), 140.8 (d, J 16.4, C-i PhCH2), 144.0 (d,
CH
PC
1 J 55.9, P C CH), 145.0 (d, J 7.6, P C CH), 200.8 (d, J 5.2,
2
3
PC
PC
PC
C O). 31P NMR, δ (ppm): 44.9. IR ν (cm−1): 1675 (C O), 1690 (C O),
695 (P S). Anal. Calcd. for C26H27OPS: C, 74.61; H, 6.50; P, 7.40; S,
7.66. Found: C, 74.33; H, 6.32; P, 7.77; S, 7.39.
REFERENCES
[1] (a) S. N. Arbuzova, L. Brandsma, N. K. Gusarova, and B. A. Trofimov, Recl. Trav.
Chim. Pays-Bas., 113, 575 (1994); (b) B. A. Trofimov, N. K. Gusarova, and L.
Brandsma, Main Group Chem. News, 4, 18 (1996).
[2] (a) B. A. Trofimov, L. Brandsma, S. N. Arbuzova, S. F Malysheva, and N. K. Gusarova,
Tetrahedron Lett., 35, 7647 (1994); (b) B. A. Trofimov, S. I. Shaikhudinova, V. I.
Dmitriev, K. V. Nepomnyashchikh, T. I. Kazantseva, and N. K. Gusarova, Zh. Ob-
shch. Khim., 70, 43 (2000); (c) N. K. Gusarova, S. I. Shaikhudinova, T. I. Kazantseva,
S. F. Malysheva, B. G. Sukhov, N. A. Belogorlova, V. I. Dmitriev, and B. A. Trofimov,
Zh. Obshch. Khim., 72, 399 (2002).
[3] B. A. Trofimov, S. N. Arbuzova, A. G. Mal’kina, N. K. Gusarova, S. F. Malysheva, M.
V. Nikitin, and T. I. Vakul’skaya, Mendeleev Commun., 163 (1999).
[4] (a) N. K. Gusarova, S. I. Shaikhudinova, S. N. Arbuzova, T. I. Vakul’skaya, B. G.
Sukhov, L. M. Sinegovskaya, M. V. Nikitin, A. G. Mal’kina, N. A. Chernysheva, and
B. A. Trofimov, Tetrahedron, 59,4789 (2003); (b) B. A. Trofimov, B. G. Sukhov, S.
F. Malysheva, N. A. Belogorlova, A. P. Tantsirev, L. N. Parshina, L. A. Oparina, S.
P. Tunik, and N. K. Gusarova, Tetrahedron Lett., 45, 9143 (2004); (c) T. Bunlak-
sananusorn and P. Knochel, J. Org. Chem., 69, 4595 (2004); (d) N. K. Gusarova, M.
V. Bogdanova, N. I. Ivanova, N. A. Chernysheva, B. G. Sukhov, L. M. Sinegovskaya,

Addition of Secondary Phosphine Sulfides to Acylacetylenes
1401
O. N. Kazheva, G. G. Alexandrov, O. A. D’yachenko, and B. A. Trofimov, Synthesis,
3103 (2005); (e) D. Leca, L. Fensterbank, E. Lacoˆte, and M. Malacria, Chem. Soc.
Rev., 34, 858 (2005); (f) A. F. Parsons, D. J. Sharpe, and P. Taylor, Synlett, 2981
(2005); (g) S. N. Arbuzova, N. K. Gusarova, and B. A. Trofimov, Arkivoc, 12 (2006);
(h) T. Hirai and L.-B. Han, Org. Lett., 9, 53 (2007).
[5] (a) R. K. Haynes, W. W.-L. Lam, and L.-L. Yeung, Tetrahedron Lett., 37, 4729, (1996);
(b) N. K. Gusarova, A. M. Reutskaya, N. I. Ivanova, A. S. Medvedeva, M. M. Demina,
P. S. Novopashin, A. V. Afonin, A. I. Albanov, and B. A. Trofimov, J. Organomet.
Chem., 659, 172 (2002).
[6] N. K. Gusarova, N. I. Ivanova, N. A. Konovalova, B. G. Sukhov, L. V. Baikalova, L.
M. Sinegovskaya, D. V. Pavlov, and B. A. Trofimov, Synthesis, 4159 (2006).
[7] 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., 183, (2005).
[8] J. I. Dickstein and S. I. Miller, in The Chemistry of the Carbon-Carbon Triple Bond,
S. Patai, Ed. (Wiley, Chichester, 1978), Chap. 19, pp. 813–955.
[9] Y. I. El’natanov and R. G. Kostyanovsky, Izv. Akad. Nauk SSSR, Ser. Khim., 382
(1988).
[10] S. Mori, E. Nakamura, and K. Morokuma, Organometallics, 23, 1081 (2004).
[11] (a) Asymmetric Catalysis in Organic Synthesis, R. Noyori, Ed. (Wiley, New York,
1994); (b) Comprehensive Asymmetric Catalysis, E. N. Jacobsen, A. Pfaltz, H. Ya-
mamoto, Eds.; Springer: Berlin, 1999; (c) Catalytic Asymmetric Synthesis, I. Ojima,
Ed. (VCH, Weinheim, 2000), 2nd ed.; (d) M. Arisawa and M.Yamaguchi, Adv. Synth.
Catal., 343, 27 (2001); (e) J. W. Faller, J. C. Wilt, and J. Parr, Org. Lett., 6, 1301
(2004); (f) D. Liu, Q. Dai, and X. Zhang, Tetrahedron, 61, 6460 (2005); (g) G. C. Fu,
Acc. Chem. Res., 39, 853 (2006); (h) Q. Dai, W. Gao, D. Liu, L. M. Kapes, and X.
Zhang, J. Org. Chem., 71, 3928 (2006); (i) D. K. Whelligan and C. Bolm, J. Org.
Chem., 71, 4609 (2006).
[12] (a) S. P. Gubin, N. A. Kataeva, and G. B. Khomutov, Izv. Akad. Nauk. Ser. Khim.,
811 (2005); (b) H. Liu, J. S. Owen, and A. P. Alivisatos, J. Am. Chem. Soc., 129, 305
(2007).