Novel 3-cyanosubstituted 1,2-thiaphosphacyclanes: Synthesis and stereochemistry

Article abstract of DOI:10.1080/10426500212224

The facile synthetic route to 5- and 6-membered 3-cyano-2-oxo-1,2-thiaphosphacyclanes and 6-cyano-2-oxa-10+oxa(thia)-phosphabicyclo[4.4.0]-decane-1-oxides was elaborated via intramolecular S-alkylation in a series of ω-haloalkylsubstituted thiophosphorylacetonitriles. The compounds were used to prepare novel P(III)-containing bidentate ligands with definite stereochemistry. Diastereomeric transformations among 2-oxo-1,2-thiaphosphinanes were found and the mechanism of such transformations is suggested.

Full text of DOI:10.1080/10426500212224

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Novel 3-Cyanosubstituted 1,2-Thiaphosphacyclanes:
Synthesis and Stereochemistry
Irina Odinets a , Natalya Vinogradova a , Pavel Petrovskii a , Konstantin Lyssenko a & Tatyana
Mastryukova a
a A. N. Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences ,
Moscow, Russia
Published online: 27 Oct 2010.
To cite this article: Irina Odinets , Natalya Vinogradova , Pavel Petrovskii , Konstantin Lyssenko & Tatyana Mastryukova (2002)
Novel 3-Cyanosubstituted 1,2-Thiaphosphacyclanes: Synthesis and Stereochemistry, Phosphorus, Sulfur, and Silicon and the
Related Elements, 177:6-7, 1787-1791, DOI: 10.1080/10426500212224
To link to this article: http://dx.doi.org/10.1080/10426500212224
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:1787–1791
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290092884
NOVEL 3-CYANOSUBSTITUTED
1,2-THIAPHOSPHACYCLANES: SYNTHESIS
AND STEREOCHEMISTRY
Irina Odinets, Natalya Vinogradova, Pavel Petrovskii,
Konstantin Lyssenko, and Tatyana Mastryukova
A. N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, Moscow, Russia
(Received July 29, 2001; accepted December 25, 2001)
The facile synthetic route to 5- and 6-membered 3-cyano-2-oxo-1,2-
thiaphosphacyclanes and 6-cyano-2-oxa-10-oxa(thia)-phosphabicyclo
[4.4.0]-decane-1-oxides was elaborated via intramolecular S-alkylation
in a series of ω-haloalkylsubstituted thiophosphorylacetonitriles. The
compounds were used to prepare novel P(III)-containing bidentate
ligands with definite stereochemistry. Diastereomeric transformations
among 2-oxo-1,2-thiaphosphinanes were found and the mechanism of
such transformations is suggested.
Keywords: Intramolecular S-alkylation; 1,2-thiaphosphinanes;
1,2-thiaphospholanes; thiophosphorylacetonitriles
In spite of the fact, that functionalized 1,2-oxaphosphacyclanes are
rather well investigated and some of them have already found numer-
ous industrial applications, their nearest analogues having ring sulfur
atom were still unknown. Recently, one of us, with coworkers,1 demon-
strated that nonfunctionalized omega-haloalkyl-substituted thiophos-
phoryl compounds undergo intramolecular S-alkylation easily, yield-
ing either phosphacyclanium salts or 2-oxo-1,2-thiaphosphacyclanes
(thiolphostones). Unfortunately, the subsequent functionalization of
these compounds with the introduction of a substituent in the ring
was a rather problematic task. Nevertheless, it was evident that this
above reaction must be the general principle of 1,2- thiaphosphacyclane
structure formation. In other words, using different functionalized
This work was supported by the Russian Basic Research Foundation (grants 99-03-
33014; 00-15-97386).
Address correspondence to Irina Odinets, A. N. Nesmeyanov Institute of Organoele-
ment Compounds, Russian Academy of Sciences, Vavilova Str. 28, Moscow 119991,
Russia.
1787

1788
I. Odinets et al.
FIGURE 1 i: Br(CH2)3Cl, 50% aq. NaOH/CH2Cl2/cat. TEBA; ii: RHlg, 50%
aq. NaOH/CH2Cl2/cat. TEBA; iii: Hlg1(CH2)nHlg2, KOH/CH3CN/cat. TEBA;
iv: Br(CH2)3Cl, 50% aq. NaOH/without solvent/cat. TEBA.
thiophosphoryl compounds bearing omega-haloalkyl moiety as a start-
ing material, one could obtain a wide range of thiaphosphacyclanes of
interest. We realized this very simple and attractive idea with the exam-
ple of intramolecular S-alkylation in a series of ω-haloalkylsubstituted
thiophosphorylacetonitriles, wherein dual reactivity was practically ex-
cluded during intramolecular cyclization.
RESULTS AND DISCUSSION
The starting compounds 1–3 were obtained via alkylation of thiophos-
phorylacetonitriles under phase-transfer catalysis (PTC) conditions,
wherein usage of different PTC systems allows facile preparing of dif-
ferent haloalkylsubstituted derivatives with high selectivity and good
yields2,3 (Figure 1).
Naturally , an introduction of strong electron-withdrawing cyano
group decreases the tione sulfur nucleophilicity. That is why in some
cases we exchange Cl for I to increase the electrophilicity of a halogen
atom. Regardless of that, the compounds 10 with the diphenythio-
phosphoryl group transform to the corresponding phosphacyclanium
salts in CH3CN solution very slowly in comparison with their
nonfunctionalized analogues (Figure 2). The equlibrium position is
achived in about 6 months, but the amount of cyclic salt does not
exceed 15%.
FIGURE 2 R H, Me.

3-Cyanosubstituted 1,2-Thiaphosphacyclanes
1789
FIGURE 3 R1 = Me, OEt, OPr; Ph; R3 = H, Me, Et, Pr; 5, n = 2; 6, n = 3.
At the same time, in the case of at least one alkoxy group at the
phosphorus atom, the cyano group appears to facilitate the subsequent
dealkylation shifting and therefore the equlibrium position. So even
thiophosphorylacetonitrile derivatives 1–3 bearing a terminal chlorine
atom are thermally unstable and transform to the corresponding five-
and six-membered mono- and bicyclic thiolphostones 5–7 under distil-
6
lation in vacuo3 (Figure 3). Note that seven-membered cycles are not
formed by such a procedure. Naturally, for the corresponding iodine
derivatives 10–30, S-alkylation proceeds under much more mild con-
ditions and often with higher yields. Such modification could not be
used only in the case of thiophosphonate structure in the starting com-
pounds. The yields of the compounds obtained depend on the cycliza-
tion method in use, cyclic size, and the nature of alkyl group in the
alkoxy group at the phosphorus atom, which undergoes dealkylation as
well.
Compounds 5–7 were obtained as mixtures of cis and trans isomers
and were resolved into individual ones by fractional crystallization and
column chromatography. The structure of the starting compound and
the methods of cyclization specify the ratio of the isomers formed during
the cyclization. In 31P-NMR spectra the isomers have two closely located
signals where mutual disposition is constant in a variety of solvents in
use. This fact enables one to use 31P-NMR spectroscopy as a simple
and convenient method for monitoring the stereochemical composition
of the reaction mixtures and final products.

1790
I. Odinets et al.
Detailed x-ray investigation3 carried out for a variety of 3-cyano-
substituted 1,2-thiaphosphacyclanes 5–7 shows that in all compounds
under investigation the cyano group occupies the axial position. For
2-oxo-1,2- thiaphospholanes 5 the isomer having a downfield chem-
ical shift in 31P-NMR spectra is characterized by cis disposition of
P O and CN groups with identical configuration of chiral centers
(RP,RC), while the second isomer is the trans one with the opposite
configuration of asymmetric atoms (RP,SC). On the contrary, for 2-oxo-
1,2-thiaphosphinanes the diastereomer with a downfield shift in its
31P-NMR spectra is characterized by antiperiplanar disposition of cyano
group and phosphoryl oxygen atom (trans, RP,SC), while synclinal ar-
rangement of above mentioned groups (cis, RP,RC) corresponds to di-
astereomer with the smaller value P. And phosphabicyclodecane 7 fits
this dependence as well.
Diastereomeric transformations were found in a series of 2-oxo-1,2-
thiaphosphinanes 6. The crude products consisting of both isomers
transformed slowly to a preferred individual one, with substituent R1
at the phosphorus atom occuping the most advantageous position in the
view of general anomeric effect. Thus, there was obtained a cis isomer
with an axial OAlk group when R1 = OAlk and a trans isomer with an
axial phosphoryl oxygen when R1 = Alk. In benzene solutions the slow
opposite conversion of the preferred diastereomer to the equilibrium
mixture with initial statistical ratio of isomers was observed. Since such
transformations were not observed for the individual diastereomers of
3-alkyl-substituted 1,2-thiaphosphinanes 6 and 1,2-thiaphospholanes
5, we believe that the carbanion mechanism of such transformations
is realized.4,5 That is to say, diastereomer conversions proceed via the
dissociation of the 3-hydrogen atom, formation of a flat carbanion, and
subsequent hydrogen attachment, with the configuration inversion of
the asymmetric 3-carbon atom.
It was also shown that both isomers of 2-oxa-10-thia-phosphabi-
cyclodecane present conglomerates that undergo crystal-induced spon-
taneous resolution (recrystallyzation from benzene). Thus, we obtained
optically active crystals with rather high enantiomeric excess (ee 70%
for cis isomer and 40% for the trans one). The ratio of enantiomers was
estimated by 31P-NMR spectra using l-phenylethylamine as the shift
reagent.
The reduction of 3-cyano-2-oxo-1,2-thiaphosphacyclanes 5,6 by
HSiCl3 was used to prepare novel P(III)-containing bidentate lig-
ands with definite stereochemical configuration. The reaction proceeds
under mild conditions while retaining the cyano group, cyclic structure,
and configuration of the starting 2-oxoderivative. The complexes with
Co(II), Rh(III), Re(I), and Pd(II) were obtained and investigated.

3-Cyanosubstituted 1,2-Thiaphosphacyclanes
1791
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