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Current
Organic Chemistry
ISSN: 1385-2728
Current Organic
Chemistry
Volume 12, Number 1, January 2008
Contents
Special Issue on Organophosphorus Chemistry
Guest Editor: György Keglevich
Editorial Pp.
1
Phosphorylation of α-Haloimines:
P-C vs. P-N Bond Formation Pp. 2-24
Petro P. Onys’ko, Yuliya V. Rassukana and
Anatoly D. Sinitsa
[Abstract] [Purchase
Article]
Phosphorylation of Thiophenes Pp. 25-38
Sergei P. Ivonin, Andrey A. Tolmachev and Alexander
M. Pinchuk
[Abstract] [Purchase
Article]
Ring Closure Reactions in Heterocyclic Systems with
Implementation of Wittig and aza-Wittig Reactions
Pp. 39-58
György Hajós and Ildikó Nagy
[Abstract] [Purchase
Article]
Synthesis and Reactions of Stabilized Phosphorus Ylides†
Pp. 59-82
Ali Ramazani, Ali Reza Kazemizadeh, Ebrahim Ahmadi, Nader
Noshiranzadeh and Ali Souldozi
[Abstract] [Purchase
Article]
Aromaticity and Antiaromaticity of Four Membered P-Heterocycles
Pp. 83-96
Zoltán Mucsi and Imre G. Csizmadia
[Abstract] [Purchase
Article]
Abstracts
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Editorial
Organophosphorus chemistry continues to be a highly important
sector of organic chemistry, as shown by the numerous publications
in this field. The 17th International Conference on Phosphorus
Chemistry held in Xiamen (China) recently (http://icpc2007.xmu.edu.cn/)
highlighted some of the most significant and exciting trends.
The importance of this field is also acknowledged by the management
of Current Organic Chemistry by encouraging
me to put together the 3rd Organophosphorus Special Issue
that, like the previous two special issues, summarizes recent
results of some selected hot topics. The 10 articles are accommodated
in two parts.
This series of publications starts with organophosphorus supramolecular
chemistry, for which state-of-the-art progress in design and
application is presented for host molecules bearing phosphate,
phosphonate, phosphinate or phosphine oxide entities. The
P-heterocyclic field is represented by a paper on the synthesis
and conformation of 1,3,2-dioxa-, 1,3,2-oxaza-, and 1,3,2-diazaphosphorine
2-chalcogenides. This topic is also relevant from the point
of view of potential biological activity, an aspect that is
more directly involved in the next two articles. The first
of these discusses the possible reactivation of RBC cholinesterases
inhibited by paraoxon derivatives, while the other gives an
overview on the synthesis of ω-phosphinyl-α-amino
acids and their potential role as therapeutic agents.
Remaining with tetracoordinated P-compounds, the chemistry
of azidoalkyl-phosphonates, -phosphinates and -phosphine oxides,
as well as the phosphorylation of α-haloimines
and that of thiophenes is discussed. In the next section,
the use of Wittig- and aza-Wittig reactions in the synthesis
of heterocycles and the synthesis and utilization of stabilized
phosphorus ylides generated from triphenylphosphine and dialkyl
acetylenedicarboxylate are summarized. Finally, antiaromaticity,
a newly discovered phenomenon within the framework of organophosphorus
chemistry, is explored.
The 3. Organophosphorus Special Issue has been divided into
two parts published back to back. The five reviews included
in this issue (Part II) have been preceeded by five other
articles in Volume 11 (Part I). The previous papers are the
following:
Organophosphorus Supramolecular Chemistry. Part 2.
Organophosphorus Receptors
by Piotr Mlynarz, Ewa Rudzinska, Lukasz Berlicki and
Pawel Kafarski
6-Membered P-Heterocycles: Ring-Condensed 1,3,2-Diheterophosphorine
2-Chalcogenides
by Éva Frank and János Wölfling
Comparison of the Ability of Pyridinium Aldoximes
to Reactivate Human RBC Cholinesterases Inhibited by Ethyl-
and Methyl-Paraoxon
by Georg Petroianu and Huba Kalász
ω-Phosphinyl-α-amino
Acids: Synthesis, and Development Towards Use as Therapeutic
Agents
by Nick J. Wardle, S. W. Annie Bligh and Harry
R. Hudson
Synthesis and Reactivity of Azidoalkyl-Phosphonates,
-Phosphinates and -Phosphine Oxides
by Anna Gajda and Tadeusz Gajda
György Keglevich
Department of Organic Chemistry and technology
Budapest University of Technology and Economics
H-1521 Budapest
Hungary
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[Purchase
Article]
Phosphorylation of α-Haloimines:
P-C vs. P-N Bond Formation
Petro P. Onys’ko, Yuliya V. Rassukana and
Anatoly D. Sinitsa
The chemoselectivity of reactions between α-haloimines
– compounds containing a Hal-C-C=N-skeleton –
and nucleophilic phosphorus derivatives are discussed systematically.
The synthetic potentialities, as well as possible mechanistic
pathways of this currently developing field of organophosphorus
chemistry are considered. Phosphorylation of the α-haloimines
leads mainly to C- or N-phosphorylated compounds as the final
products, the selectivity being dependent on the type of halogen,
substituents at the imine carbon and nitrogen atoms, and on
the nature of phosphorus reagent. The main factors controlling
regio- and stereoselectivity are elucidated. A series of novel
theoretically and preparatively important transformations
have also been illustrated; i.e., new diad rearrangements
involving the N→C
and C→N
transfer of a sulfonyl or a phosphoryl group, the unusual
acylation of the electrophilic imine carbon atom by tervalent
phosphorus isocyanates, and others. Variety of transformations
is connected with the possible participation of C=N bond,
halogen atoms or N-substituents, in reactions involving the
Hal-C-C=N- arrangement. The use of haloimines as versatile
building blocks for synthesis of practically promising functionalized
aminophosphonates, bisphosphonates, and phosphorus analogs
of dehydro aminoacids, etc., is demonstrated.
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Phosphorylation of Thiophenes
Sergei P. Ivonin, Andrey A. Tolmachev and Alexander
M. Pinchuk
This review deals with synthetic methods, chemical transformations,
and some physical properties of thienyl- and benzothienyl
substituted phosphorus compounds bearing P-Het or P-CH2-Het
bonds.
The basic synthetic approaches to these compounds include
reactions of metalated thiophenes with phosphorus(III) and
(V) halides, phosphorylation of thiophenes in the presence
of a mild Lewis acid, use of halogenothiophenes in the Arbuzov
reaction, and phosphorylation of thiophenes with phosphorus(III)
halides in basic medium. Synthetic approaches to condensed
heterocyclic systems of novel types are also considered.
Investigation of chemical properties of phosphorylated thiophenes
has revealed that, despite the great similarity with phenyl
analogues, differences connected to the nature of the heterocycle
are observed. The tertiary phosphines bearing at least one
thienyl substituent are less active in quaternization and
oxidation reactions. At the same time, basic hydrolysis leading
to C-P bond cleavage is facilitated, as compared to benzene
derivatives.
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Article]
Ring Closure Reactions in Heterocyclic Systems with Implementation
of Wittig and aza-Wittig Reactions
György Hajós and Ildikó Nagy
Applications of Wittig and aza-Wittig reactions in various
cyclizations reported during the past ten years are reviewed.
The relevant literature is classified into two categories
according to these two main approaches and, in both sections,
the chemistry is exemplified according to the ring types synthesized.
The chemical examples include both intramolecular ring closures
and multistep procedures. Within the aza-Wittig reactions,
special attention is paid to those products that can undergo
electrocyclization to yield nitrogen heterocycles (e.g. pyridines
or pyrimidines). In most interesting cases, the reaction mechanism
of the transformations is discussed.
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Synthesis and Reactions of Stabilized Phosphorus Ylides†
Ali Ramazani, Ali Reza Kazemizadeh, Ebrahim Ahmadi, Nader
Noshiranzadeh and Ali Souldozi
Stabilized phosphorus ylides, versatile intermediates
in synthetic organic chemistry can be prepared by the novel
reaction of dialkyl acetylenedicarboxylates (DAAD), triphenylphosphine
(TPP) and acids such as phenols, imides, amides, enols, oximes
and alcohols. The reaction involves an intermediate formed
by the 1:1 conjugate addition reaction of the TPP to DAAD
and concomitant protonation of the intermediate by an acid
leads to vinyltriphenylphosphonium salts. The salts are unstable
intermediates and converted to stabilized phosphorus ylides
via Michael addition reaction. The stabilized phosphorus
ylides are able to take part in the normal intramolecular
Wittig reactions but they are not generally able to participate
in the normal intermolecular Wittig reactions. The intermolecular
Wittig reactions of the ylides are observed only with highly
electron-poor carbonyl groups such as indane-1,2,3-trione.
The ylides are converted to electron-poor alkenes via
elimination of TPP in solvent-free conditions. Almost all
of the final products are valuable families of compounds.
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Aromaticity and Antiaromaticity of Four-Membere P-Heterocycles
Zoltán Mucsi and Imre G. Csizmadia
The organophosphorus chemistry became the one of the
most rapidly developing and very important subdiscipline in
the organic and organometallic chemistry. This development
is providing exciting chemical structures, efficient metal
ligands and biologically important pharmacophores. In the
present review we first collected and discussed the four-membered
antiaromatic organic and inorganic compounds, containing phosphorous
atom in their ring, which were considered and prepared during
the past half a century.
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