A novel photochemical reaction of a mixed phosphonium iodonium ylide with phenylacetylene as a route to diphenyl-1λ5-phosphinoline

Full text of DOI:10.1007/s11172-010-0110-7

Russian Chemical Bulletin, International Edition, Vol. 59, No. 2, pp. 488, February, 2010
488
A novel photochemical reaction of a mixed phosphonium iodonium ylide
with phenylacetylene as a route to diphenylꢀ1λ5ꢀphosphinoline
E. D. Matveeva,a R. Gleiter,b and N. S. Zefirova
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: matveeva@org.chem.msu.ru
bInstitute of Organic Chemistry, Heidelberg University, Heidelberg, Germany.*
Fax: (0622) 154 4205. Eꢀmail: Rolf.Gleiter@oci.uniꢀheidelberg.de
3
117.45 (d, CHCPh, JC,P = 10.0 Hz); 124.57 (d, C arom.,
Earlier, we obtained mixed phosphonium iodonium
3JC,P = 11.5 Hz); 126.01 (d, C arom., JC,P = 7.6 Hz); 126.50
(s, C arom.); 127.61 (d, C arom., JC,P = 93.5 Hz); 128.46
(s, C arom.); 128.88 (s, C arom.); 129.14 (d, C arom., JC,P
= 13.0 Hz); 129.24 (s, C arom.); 130.00 (s, C arom.); 130.50
2
ylides1—4 and studied their reactivities. In the present work,
a novel photochemical reaction of ylide 1 with phenylꢀ
acetylene afforded phenyl 1,1,4ꢀtriphenylꢀ1λ5ꢀphosphinꢀ
olinꢀ2ꢀyl ketone (2). The structure of λ5ꢀphosphinoline 2
was confirmed by NMR spectroscopy and elemental analꢀ
ysis.
1
3
=
4
(s, C arom.); 132.05 (s, C arom.), 132.36 (d, C arom., JC,P
=
2
= 3.1 Hz); 133.80 (d, CH, JC,P = 6.9 Hz); 133.89 (d, C arom.,
2JC,P = 10.7 Hz); 133.99 (d, C arom., JC,P = 9.2 Hz); 141.14
3
(d, C arom., 3JC,P = 9.9 Hz); 142.01 (d, C arom., 2JC,P = 4.6 Hz);
143.32 (s, C arom.); 189.97 (d, CO, JC,P = 6.1 Hz). 31P NMR
2
(CDCl3), δ: 2.94. IR, ν/cm–1: 1580 (C=O), 1520 (C=C),
720—750, 1470 (Ar). Found (%): C, 85.24; H, 5.07. C34H25OP.
Calculated (%): C, 85.00; H, 5.21.
We are grateful to A. S. Pavlova for performing the
experimental work.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00611),
the Presidium of the Russian Academy of Sciences (Basic
Research Program No. 1), and the Division of Chemistry
and Materials Science of the Russian Academy of Sciencꢀ
es (Basic Research Program No. 9).
1H, 31P, and 13C NMR spectra were recorded on a Bruker
Avance 400 instrument (400 MHz) in CD2Cl2 and CDCl3 with
tetramethylsilane as the internal standard. IR spectra were reꢀ
corded on a URꢀ20 instrument in CCl4.
5
Phenyl 1,1,4ꢀtriphenylꢀ1λ ꢀphosphinolinꢀ2ꢀyl ketone (2).
Phenylacetylene (0.1 mL, 0.9 mmol) was added to a solution of
ylide 1 (0.3 g, 0.45 mmol) in anhydrous CH2Cl2. The reaction
mixture was stirred under argon, while being exposed to mercury
lamp radiation. The completion of the reaction was indicated by
the full consumption of ylide 1 (TLC). The reaction mixture was
concentrated in vacuo. The residue was dissolved in a minimum
amount of CH2Cl2 and separated by column chromatography on
Merck 60 silica gel (70—230 mesh ASTM). Liberated PhI
and the excess phenylacetylene were eluted with benzene and
the target phosphinoline was eluted with CH2Cl2 and then
CH2Cl2—MeOH (200 : 1). The yield of compound 2 was
0.11 g (50%).
1H NMR (CD2Cl2), δ: 7.12 (d, 1 H, CH, 3JP,H = 31.5 Hz);
7.10—7.13 (m, 1 H, H arom.); 7.23—7.27 (m, 1 H, H arom.);
7.35—7.43 (m, 10 H, H arom.); 7.52—7.65 (m, 8 H, H arom.);
7.84—7.90 (m, 4 H, H arom.). 13C NMR (CD2Cl2), δ: 74.30
(d, C(1), 1JC,P = 100.5 Hz); 111.35 (d, C arom., 1JC,P = 85.8 Hz);
References
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* Organischꢀchemisches Institut der Universität Heidelberg,
Received June 25, 2009,
Neuenheimer Feld 270 Dꢀ69120 Heidelberg, Deutschland.
in revised form October 7, 2009
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 478, February, 2010.
1066ꢀ5285/10/5902ꢀ0488 © 2010 Springer Science+Business Media, Inc.