Synthesis and properties of λ5-phosphinines and λ5- azaphosphinines

Article abstract of DOI:10.1080/10426500701764932

New accessible methods of synthesizing λ5-phosphines and 1,2-λ5-azaphosphinines by cyclocondensation of phosphorylated derivatives of linear enamines bearing at the α-position an electron-accepting substituent and a methyl group at the α-position was developed. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Synthesis and Properties
of λ5-Phosphinines and λ5-
Azaphosphinines
Aleksandr N. Kostyuk a , Yurii V. Svyashchenko a
Dmitrii M. Volochnyuk a , Dmitrii A. Sibgatulin a
Aleksandr M. Pinchuk a
,
&
a Institute of Organic Chemistry National Academy of
Sciences of Ukraine , Murmanska Str.5, Kyiv, 02094,
Ukraine
Published online: 20 Jun 2008.
To cite this article: Aleksandr N. Kostyuk , Yurii V. Svyashchenko , Dmitrii M.
Volochnyuk , Dmitrii A. Sibgatulin & Aleksandr M. Pinchuk (2008) Synthesis and
Properties of λ5-Phosphinines and λ5-Azaphosphinines, Phosphorus, Sulfur, and Silicon
and the Related Elements, 183:2-3, 558-560, DOI: 10.1080/10426500701764932
To link to this article: http://dx.doi.org/10.1080/10426500701764932
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Phosphorus, Sulfur, and Silicon, 183:558–560, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701764932
Synthesis and Properties of λ5-Phosphinines
and λ5-Azaphosphinines
Aleksandr N. Kostyuk, Yurii V. Svyashchenko,
Dmitrii M. Volochnyuk, Dmitrii A. Sibgatulin,
and Aleksandr M. Pinchuk
Institute of Organic Chemistry National Academy of Sciences
of Ukraine, Murmanska Str.5, Kyiv, 02094 Ukraine
New accessible methods of synthesizing λ5-phosphines and 1,2-λ5-azaphosphinines
by cyclocondensation of phosphorylated derivatives of linear enamines bearing at
the α-position an electron-accepting substituent and a methyl group at the α-position
was developed.
Keywords Phosphorylation; electrocyclization; λ5-phosphinines;1,2-λ5-azaphosphinines
INTRODUCTION
Development of a convenient synthetic procedure for phosphine 1 al-
lowed us to prepare it in gram scale batches. Phosphine 1 and other
trivalent phosphorus derivatives bearing the enamine residue were
readily alkylated with a set of alkyl bromides affording phosphonium
salts. In the reaction with DMFDMA these salts were transformed into
λ5-phosphinines.1 The phosphonium salts 2 were found to react dif-
ferently with bases. While the salts 2 upon treatment with aqueous
sodium hydroxide transformed into stable ylides 3, heating the salts
2 with a catalytic amount of triethylamine lead to cyclic phosphonium
salt 42 (Scheme 1).
We have investigated various reaction conditions under which both
the ylides 3 and the phosphonium salts 4 were converted into λ5-
phosphinines 5. Thus, we have found that heating ylides 3 neat at
150◦C in vacuo for 5 min resulted in the corresponding phosphinines 5
in moderate yields. Thus, one can conclude that ylide 3 undergoes ther-
mal cyclization leading to cyclic ylide 7 followed by dehydration thus
affording the final phosphinines 5 (Scheme 2).
Address correspondence to Aleksandr N. Kostyuk, Institute of Organic Chemistry
National Academy of Sciences of Ukraine, Murmanska Str.5, Kyiv, 02094 Ukraine.
E-mail: dov@fosfor.kiev.ua
558

λ5 - Phosphinines and λ5 -Azaphosphinines
559
SCHEME 1
SCHEME 2
SCHEME 3
SCHEME 4

560
A. N. Kostyuk et al.
The treatment of phosphonium salt 2 with DMFDMA gave phos-
phinine 9. Also, these compounds could be prepared by an alternative
method, namely by the reaction of dienamine 8 with bromoacetophe-
nones at room temperature (Scheme 3).
This approach was successfully applied for the synthesis of λ5-
azaphosphinines 10 (Scheme 4).
Thus, a novel approach to λ5-phosphinines and λ5-azaphosphinines
was proposed.
REFERENCES
[1] A. N. Kostyuk, Y. V. Svyaschenko, and D. M. Volochnyuk, Tertrahedron, 61, 9263
(2005).
[2] Y. V. Svyaschenko, A. N. Kostyuk, B. B. Barnych, and D. M. Volochnyuk, Tertrahe-
dron, 63, 5656 (2007).