Facile non-catalyzed synthesis of tertiary phosphine sulfides by regioselective addition of secondary phosphine sulfides to alkenes

Article abstract of DOI:10.1002/ejoc.201301786

An atom-economic green synthesis of tertiary phsophine sulfides has been developed based on catalyst- and solvent-free addition of secondary phosphine sulfides to diverse terminal and internal alkenes (hept-1-ene, cyclohexene, styrenes, allyl alcohol, vin

Full text of DOI:10.1002/ejoc.201301786

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FULL PAPER
DOI: 10.1002/ejoc.201301786
Facile Non-Catalyzed Synthesis of Tertiary Phosphine Sulfides by
Regioselective Addition of Secondary Phosphine Sulfides to Alkenes
Svetlana F. Malysheva,[a] Nina K. Gusarova,[a] Alexander V. Artem’ev,[a]
Nataliya A. Belogorlova,[a] Alexander I. Albanov,[a] Tatyana N. Borodina,[a]
Vladimir I. Smirnov,[a] and Boris A. Trofimov*[a]
Keywords: Synthetic methods / Green chemistry / Alkenes / Phosphorylation / Regioselectivity
An atom-economic green synthesis of tertiary phsophine
sulfides has been developed based on catalyst- and solvent-
free addition of secondary phosphine sulfides to diverse ter-
minal and internal alkenes (hept-1-ene, cyclohexene, styr-
enes, allyl alcohol, vinyl ethers, vinyl sulfides, vinyltrimethyl-
silane, 1-vinylimidazoles, vinyl acetate). The reaction pro-
ceeds under mild conditions (80 °C, without solvent, 4–45 h)
to afford chemo- and regioselectively the corresponding anti-
Markovnikov adducts in excellent to quantitative yields (50–
99%).
Introduction
The tertiary phosphine sulfides continue to attract sig- of initiators such as AIBN or in Et3B/O2 systems, this reac-
nificant attention from researchers. Currently, these impor- tion proceeds in an anti-Markovnikov manner to give rise
tant organophosphorus compounds find widespread appli- to diverse tertiary phosphine sulfides, as a rule, in high
cation as extractants for noble metals and radionuclides,[1] yields.[9] A variety of electron-rich (vinyl ethers,[13] vinyl
excellent ligands and pre-ligands for metal complex cata- sulfides,[14] vinyl selenides[15] and tellurides,[16] styrene,[17] 1-
lysts,[2] efficient precursors and capping agents for the prep- vinylimadazoles,[18] diketene[19]) and electron-poor (methyl
aration of metal sulfide nanoparticles[3] as well as reagents methacrylate, acrylonitrile, acrylamide and N-phenylmale-
for organic synthesis.[4] In addition, tertiary phosphine sulf- imide)[17] alkenes can serve as unsaturated substrates. Sub-
ides have been offered as modifiers for rubbers and resins,[5] sequently, this approach has been extended to the synthesis
chemical sensitizers in photographic materials,[6] additives of branched di-,[20] tri-[21] and tetraphosphine sulfides[22]
to lubricating oils, and as electrolytes.[7]
from the corresponding alkenes.
A number of synthetically useful reactions leading to ter-
tiary phosphine sulfides have been described.[8] However,
from the viewpoint of green chemistry, the most ideal route
to tertiary phosphine sulfides is direct atom-economic ad-
dition of secondary phosphine sulfides across the C=C
bonds of alkenes. Usually, activation of the P–H bonds
within secondary phosphine sulfides in the above process
requires the utilization of strong basic catalysts or radical
initiators.[9] For instance, the nucleophilic addition of sec-
ondary phosphine sulfides to vinyl sulfoxides[10] or vinyl
sulfones (including divinyl sulfoxide and -sulfone[11] as well
as 2-sulfolene[12]) has been carried out in the presence of
KOH (50–100 mol-%, THF) to give anti-Markovnikov ad-
ducts in high yields. The radical addition of secondary
phosphine sulfides to alkenes has received significantly
greater attention. Upon UV-irradiation or in the presence
In addition, there is a series of studies devoted to transi-
tion metal-catalyzed (Pd, Ni, Fe, Cu, etc.) additions of vari-
ous P–H addends (mainly, H-phosphonates, secondary
phosphines and their oxides) to C=C and CϵC bonds.[23]
Although these reactions afford the target adducts in good
yields, the application of expensive noble metal-based cata-
lytic systems is necessary.
The main disadvantage of the aforementioned methodol-
ogy for the synthesis of tertiary phosphine sulfides is the
application of basic and free-radical conditions, which are
often not compatible with the functionalized molecules. In
addition, harmful organic solvents (e.g. THF, 1,4-dioxane)
and free-radical initiators (e.g. toxic AIBN or pyrophoric
Et3B) or metal-based catalysts are required for the above
reactions. Avoiding the use of the catalysts, initiators and
solvents in syntheses of tertiary phosphine sulfides is highly
desirable also from an environmental safety viewpoint. An
uncatalyzed solvent-free protocol meets the modern
requirements of green chemistry.[24] In line with this think-
ing, the regioselective addition of secondary phosphine-
boranes and H-phosphinates to alkenes[25] or alkynes[26] in
the absence of solvents and catalysts has been ac-
complished.
[a] A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences,
1 Favorsky Str., 664033 Irkutsk, Russian Federation
E-mail: boris_trofimov@irioch.irk.ru
http://www.irkinstchem.ru
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201301786.
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B. A. Trofimov et al.
FULL PAPER
In this paper we report the facile and convenient green
Eventually, using the example of secondary phosphine
route toward tertiary phosphine sulfides based on the ad- sulfide 1 and vinyl sulfide 17, we discovered that the reac-
dition of secondary phosphine sulfides to alkenes, proceed- tion proceeds also at room temperature. However, even af-
ing under catalyst- and solvent-free conditions.
ter a long reaction time (72 h), the conversion of the initial
compounds is only 60%.
Regarding the mechanism of this non-catalyzed addition,
at the moment it is difficult to draw reliable conclusions.
Using the example of phosphine sulfide 3 and its reaction
with alkene 17 (Table 1, Entry 14), we have shown that the
addition reaction proceeds in the dark with the same effi-
ciency as in the presence of light. Furthermore, the addition
of a radical inhibitor such as TEMPO and hydroquinone
(5–10 mol-%) does not affect the reaction course. It is quite
possible that different reaction mechanisms are specific for
each alkene group. So, it is known that the styrenes,[9] vinyl
sulfides[9,27] and 1-vinylimidazoles[28] react with H-phos-
phines and H-phosphine chalcogenides not only under the
conditions of radical initiation but also in the presence of
basic catalysts to afford the anti-Markovnikov adducts,
whereas the reactions of nucleophilic addition of PH-ad-
dends to alkenes 7–10 and vinyl ethers have not been de-
scribed.
Results and Discussion
Serendipitously, we found that secondary phosphine sulf-
ide 1, without any catalyst and solvent, easily (80 °C, 44 h,
inert atmosphere) adds to styrene to give tertiary phosphine
sulfide 2 in 89% yield (Scheme 1). Remarkably, the reaction
proceeds strictly regioselectively as an anti-Markovnikov
addition; no alternative isomer has been detectable in the
reaction mixture on the basis of H and 31P NMR studies.
The equimolar ratio of reactants is close to optimal al-
though excess styrene does not affect the course of the reac-
tion.
1
The synthetic utility and efficiency of the disclosed pro-
tocol is further demonstrated by the fact that alkynes can
also react with secondary phosphine sulfides under catalyst-
and solvent-free conditions. For example, phenylacetylene
adds phosphine sulfide 3 chemo-, regio- and stereoselec-
tively at 80 °C (5 h) to produce corresponding anti-Markov-
nikov adduct 22 in 94% isolated yield with a Z/E ratio of
95:5.
Scheme 1. Addition of secondary phosphine sulfide 1 to styrene
under catalyst- and solvent-free conditions.
The synthesized products were fully characterized by 1H,
13C, 31P NMR and IR spectroscopy. Moreover, molecular
To extend the application and demonstrate a substrate structures of phosphine sulfides 2 and 21h were established
scope for this efficient protocol, we have tested the reaction by single-crystal X-ray diffraction analysis (Figure 1, Fig-
of diverse secondary phosphine sulfides with a series of alk- ure 2).[29]
enes. As seen in Table 1, various terminal and internal alk-
enes (including functionalized ones) successfully participate
in the reaction to give only anti-Markovnikov adducts in
50–99% yields. The product yields depend upon the elec-
tronic and steric properties of the alkenes. Expectedly, ter-
minal alkenes appeared to be more reactive than internal
ones. For example, the reaction of diphenylphosphine sulf-
ide (3) with hept-1-ene (7) or allyl alcohol (10) for 12 h pro-
vided desired products in 70–84% isolated yields (Table 1,
Entries 1 and 4), whereas cyclohexene (8) or β-propylstyr-
ene (9) showed lower reactivity under the same conditions
(Table 1, Entries 2 and 3). Among the terminal alkenes,
vinyl ethers (Table 1, Entries 6–9), vinyl sulfides (Table 1,
Entries 10–16) and vinyltrimethylsilane (Table 1, Entry 17)
displayed higher reactivity than 1-vinylimidazoles (Table 1,
Entries 18 and 19), not to mention styrene (Scheme 1) and
4-tert-butoxystyrene (Table 1, Entry 5). It should be noted
that the reactive functional groups, (e.g. OH, SiMe3, OAc
and imidazole) within alkenes 10, 14, 18–20 tolerate the re-
action conditions. Among the secondary phosphine sulf-
ides, diphenylphosphine sulfide (3) is the most reactive (cf.
Table 1, Entry 14 with Entries 12 and 13) presumably due
to the lower energy necessary for P–H bond cleavage.
Figure 1. ORTEP plot of the phosphine sulfide 2 at 25% thermal
ellipsoid probability.
2
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Facile Non-Catalyzed Synthesis of Tertiary Phosphine Sulfides
Table 1. Synthesis of tertiary phosphine sulfides 21a–s.[a]
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FULL PAPER
Table 1. (Continued).
[a] Reaction conditions: secondary phosphine sulfides 1, 3–6 (1 mmol), alkenes 7–20 (1 mmol), 80 °C, inert atmosphere, stirring. [b] Yields
based on 31P NMR spectra of the crude reaction mixture. [c] Isolated yields. [d] Yields refer to experiments carried out in dark conditions.
with sodium metal in toluene (110 °C, 1 h) furnishes to
phosphine 23 in 90% yield (Scheme 2).
Conclusions
To summarize, a facile, green and high-yielding protocol
for the addition of secondary phosphine sulfides to a series
of alkenes under mild catalyst- and solvent-free conditions
has been developed. The reaction selectively proceeds in an
anti-Markovnikov fashion to form tertiary phosphine sulf-
ides bearing diverse functional groups. These products are
promising ligands for the construction of metal complexes,
prospective metal extracting agents and building blocks in
organic synthesis.
Figure 2. ORTEP plot of the phosphine sulfide 21h at 25% thermal
ellipsoid probability.
The synthesized tertiary phosphine sulfides can be suc-
cessfully converted into the corresponding phosphines. We
found that reduction of phosphine sulfide 21f by treatment
Experimental Section
General: All reactions were carried out under an argon atmosphere.
Secondary phosphine sulfides 1, 3–6 were synthesized by oxidation
of the corresponding phosphines with powdered sulfur. The initial
phosphines were prepared from the corresponding styrenes or 2-
vinylfurane and red phosphorus as described in the literature.[30]
Diphenylphosphine was purchased from Aldrich. Hept-1-ene, cy-
clohexene, styrene, 4-tert-buthoxystyrene, allyl alcohol, vinyltri-
methylsilane and vinyl acetate are all commercially available prod-
ucts (Aldrich, Alfa Aesar). Vinyl ethers 12, 13, vinyl sulfides 15–17
Scheme 2. Reduction of phosphine sulfide 21f with sodium.
4
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Facile Non-Catalyzed Synthesis of Tertiary Phosphine Sulfides
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Received: November 30, 2013
Published Online: ᭿
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Facile Non-Catalyzed Synthesis of Tertiary Phosphine Sulfides
Green Synthesis
S. F. Malysheva, N. K. Gusarova,
A. V. Artem’ev, N. A. Belogorlova,
A. I. Albanov, T. N. Borodina,
V. I. Smirnov, B. A. Trofimov* .......... 1–7
Facile Non-Catalyzed Synthesis of Tertiary
Phosphine Sulfides by Regioselective Ad-
dition of Secondary Phosphine Sulfides to
Alkenes
Secondary phosphine sulfides easily add to
diverse terminal and internal alkenes (hept-
1-ene, cyclohexene, styrenes, allyl alcohol,
vinyl ethers, vinyl sulfides, vinyltrimethyl-
silane, 1-vinylimidazoles, vinyl acetate) un-
der catalyst- and solvent-free conditions at
80 °C (4–44 h) to afford the corresponding
anti-Markovnikov adducts in good to ex-
cellent yields (50–99%).
Keywords: Synthetic methods
/ Green
chemistry / Alkenes / Phosphorylation /
Regioselectivity
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