An Eco-Friendly and Efficient Photoinduced Coupling of Alkenes and Alkynes with H-Phosphinates and Other P(O)H Derivatives Under Free-Radical Conditions

Article abstract of DOI:10.1002/ejoc.201700584

An efficient method for the synthesis of organophosphorus compounds from alkenes or alkynes and P(O)H compounds under neutral and free-radical conditions was developed. The reaction takes place without solvent, at room temperature, open to the air, using

Full text of DOI:10.1002/ejoc.201700584

A Journal of
Accepted Article
Title: An eco-friendly and efficient photoinduced coupling of alkenes
and alkynes with H-phosphinates and other P(O)H derivatives
under free-radical conditions
Authors: Pierre-Yves Geant, Jean-Pierre Uttaro, Suzanne Peyrottes,
and Christophe Mathe
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201700584
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10.1002/ejoc.201700584
European Journal of Organic Chemistry
FULL PAPER
An eco-friendly and efficient photoinduced coupling of alkenes
and alkynes with H-phosphinates and other P(O)H derivatives
under free-radical conditions
Pierre-Yves Geant,[a] Jean-Pierre Uttaro,[a] Suzanne Peyrottes[a] and Christophe Mathé*[a]
Abstract:
An
efficient method
for the synthesis of
organophosphorus compounds from alkenes or alkynes and P(O)H
compounds was developed under neutral and free-radical conditions.
This methodology can be achieved without solvent, at room
temperature in an open air system, using only 0.1 equiv. of 2,2-
dimethoxy-2-phenylacetophenone (DPAP) as photoinitiator and an
equimolar ratio of unsaturated compound and P(O)H derivative.
Additionally, the reaction can also proceed under sunlight irradiation,
giving to this methodology a very respectful approach to the
environment.
Results and Discussion
As a model reaction, we studied the hydrophosphinylation of
vinylcyclohexane
1
with ethylphenylphosphinate
2
using
previously reported conditions for the corresponding
hydrophosphonylation reaction (Equation 1).[11a]
Introduction
The study and the synthesis of organophosphorus compounds[1]
have been largely developed in recent decades due to their wide
range of applications. These latter can be used in organic
Scheme
1.
Hydrophosphinylation
of
vinylcyclohexane
with
ethylphenylphosphinate
.
synthesis as reagents[2] ligands for transition metal catalysts and
3]
organocatalysts[2d,
and also as building blocks for
pharmaceutical, agricultural and material chemistry.[4] As a result,
significant progresses have been made to generate C-P bonds.
Nevertheless, the development of highly selective and
environmentally friendly synthetic methods is still relevant. In this
context, the direct addition of P(O)-H bonds to carbon-carbon
unsaturated bonds is the most attractive and atom-economical
approach for the synthesis of organophosphorus compounds.[5]
The first attempt was carried out with 0.25 mmol of
vinylcyclohexane, 0.5 equiv. of 2,2-dimethoxy-2-
phenylacetophenone (DPAP) as a photoinitiator under UV-A
irradiation. In our previous study, the hydrophosphonylation
reaction was performed in presence of 100 equiv. of H-
phosphonate under solvent-free conditions. In the case of the
hydrophosphinylation reaction, the amount of H-phosphinate
required may be lower as Montchamp and co-workers have
shown that H-phosphinates are most reactive that H-
phosphonates.[14] In this regard, we studied, in the first set of
assays, the reaction time and the amount of H-phosphinate
needed to accomplish the hydrophosphinylation reaction with
good yields (Table 1). A first attempt was accomplished using
only 10 equiv. of ethylphenylphosphinate (entry 1). Under these
conditions, after 30 min, the desired adduct was obtained in 73%
yield, confirming that H-phosphinates are more reactive than H-
phosphonates. As expected, a total anti-Markovnikov selectivity
was observed. The increase of the reaction time to 1 h led to the
formation of the phosphinate adduct in 90% yield (entry 2). As a
result of these assays, next experiments were carried out with a
reaction time of 1 h. The equivalent of H-phosphinates can be
reduced to 5 without lowering the yield (entry 3). Nevertheless,
when the equivalents of H-phosphinate were lowered to 2 or 1.1
equiv., the reaction yield decreased to 78% and 70%
respectively (entry 4 and 5). In this case, a longer reaction time
(2 h) did not permit to increase the yield (entry 6).
This addition can be achieved in the presence of radical
7]
initiators,[6] bases,[6b,
transition metals[8] and/or under
thermal,[1a, 9] microwaves[9d, 10] or photochemical activation.[9d, 11]
Among them, the free radical additions represent one of the
most versatile way to create a C-P bond.[5a, 5c, 5d, 12] In addition,
the use of phosphinates or H-phosphinates as synthesis
reagents is an eco-friendly alternative to phosphorus trichloride,
this intermediate being commonly used in organophosphorus
synthesis.[13] In our continuous investigations on the C-P bond
formation via free radical processes,[11a] we started exploring the
hydrophosphinylation reaction with alkenes or alkynes under
photochemical activation. We report herein an atom-economical,
and highly efficient synthesis of organophosphorus compounds
taking place under mild neutral and green conditions.
[a]
Institut des Biomolécules Max Mousseron (IBMM), UMR 5247,
Université de Montpellier, CNRS, ENSCM, cc 1705, Site Triolet,
Place Eugène Bataillon, 34095 Montpellier cedex 5, France.
E-mail: christophe.mathe@umontpellier.fr
Supporting information for this article is given via a link at the end of
the document
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10.1002/ejoc.201700584
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Table 1. Optimization of the amount of ethylphenylphosphinate 2 required to
Table 3. Influence of the light source to equation 1.[a]
equation 1.
Entry
Light source
UV-A 60 w
Sunlight
Time (h)
Yield[b] (%)
Entry
2 (equiv.)
Time (h)
Yield[b] (%)
1
2
3
1
4
8
90
62
79
1
2
3
4
5
6
10
10
5
0.5
1
73
90
90
78
70
69
Sunlight
1
[a] Reaction conditions: vinylcyclohexane (0.25 mmol), ethylphenylphosphinate
(5 equiv.), DPAP (0.5 equiv.), no solvent.
chromatography.
[b]
After purification by column
2
1
1.1
1
The scale-up of the reaction was also examined and results are
summarized in table 4. In the optimized conditions (i.e. 5 equiv.
of H-phosphinate, 0.5 equiv. of DPAP and 1 h under UV-A
irradiation) the yield of the reaction remains excellent, using 0.25,
1.25 or 2.5 mmol of vinylcyclohexane (entry 1 to 3). In order to
limit waste management, especially for larger scale, and in
accordance with the tests carried out to determine the amounts
of photoinitiator and/or H-phosphinate required for the reaction
(Tables 1 & 2), the amount of DPAP was reduced to 0.1 equiv.
while the reaction time was fixed at 2 h (entry 4). Under these
conditions, the yield obtained remains similar to the one
observed in entries 1 to 3. Then, the reaction has been
attempted with 2 equiv. of ethylphenylphosphinate and 0.1 equiv.
of DPAP (entry 5). Surprisingly, under these conditions the
observed yield remains similar to the one described with 5 equiv.
of H-phosphinate (86% versus 89%). This result prompted us to
examine the scale-up of the reaction on the basis of a 1:1
stoichiometry between the H-phosphinate and the alkene (entry
6) and the phosphinate adduct was obtained in 83% yield. This
scale-up having been made under the same experimental
conditions than the initial reaction with 0.25 mmol of
vinylcyclohexane, it appears evident that the yield is dependent
on the amount of material involved along with the equipment
used in this work. This unexpected result allowed us to
significantly reduce chemicals and waste.
1.1
2
[a] Reaction conditions: vinylcyclohexane (0.25 mmol), DPAP (0.5 equiv.), no
solvent, under UV-A irradiation (365 nm, 60 w). [b] After purification by column
chromatography.
In the second set of assays, we have studied the influence of the
amount of the photoinitiator on the hydrophosphinylation
reaction (Table 2). In entry 1, 5 equiv. of H-phosphinate, a
reaction time of 1 h and 0.5 equiv. of DPAP were used and
under these conditions the yield of the reaction was 90%. As can
be seen in entry 2 and 3, the yield decreased when the amount
of photoinitiator was reduced (86% with 0.2 equiv. of DPAP and
76% whit 0.1 equiv. of DPAP). Nevertheless, an excellent yield
(91%) was restored by increasing the reaction time to 2 h (entry
4), and no reaction took place in the absence of a photoinitiator
(entry 5). Thus, hydrophosphinylation can be carried out using
either 0.5 equiv. or 0.1 equiv. of the photoinitiator but requires a
longer reaction time (2 h versus 1 h) in the second case. For the
next assays, we chose to use 0.5 equiv. of DPAP in order to
reduce the reaction time.
Table 2. Optimization of the amount of DPAP required to equation 1.[a]
Entry
DPAP (equiv.)
Time (h)
Yield [b] (%)
Table 4. Reaction scale-up.[a]
1
2
3
4
5
0.5
0.2
0.1
0.1
-
1
1
1
2
1
90
86
76
91
-
1
2
DPAP
(equiv.)
Time
(h)
Entry
Yield[b] (%)
(mmol)
(equiv.)
1
2
3
4
5
6
0.25
1.25
2.5
5
5
5
5
2
1
0.5
0.5
0.5
0.1
0.1
0.1
1
1
1
2
2
2
90
87
90
89
86
83
2.5
[a] Reaction conditions: vinylcyclohexane (0.25 mmol), ethylphenylphosphinate
(5 equiv.), no solvent, under UV-A irradiation (365 nm, 60 w).
purification by column chromatography.
[b]
After
2.5
The influence of the light source has also been considered with
the aim to save energy and resource. As depicted in table 3, the
hydrophosphinylation reaction can be carried out under sunlight
irradiation without excessively increasing the reaction time, and
gave the desired phosphinate in 62% yield after 4 h (entry 2)
and 79% yield after 8 h (entry 3) versus 90% yield after 1 h
under UV-A irradiation (entry 1).
2.5
[a] Reaction conditions: no solvent under UV-A irradiation (365 nm, 60 w). [b]
After purification by column chromatography.
Then, we explored the scope of the reaction with diverse
unsaturated carbon-carbon bonds (Table 5). For this study, our
standard conditions (i.e. 1 equiv. of unsaturated compound, 5
equiv. of H-phosphinate, 0.5 equiv. of DPAP under UV-A
irradiation for 1 h) were used. The reaction proceeded efficiently
with most of the substrates tested, giving rise to the
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10.1002/ejoc.201700584
European Journal of Organic Chemistry
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corresponding phosphinate in good to excellent yields and anti-
Markovnikov selectivity was exclusively observed for terminal C-
in the case of styrene, probably due to polymerization reaction.
Electron-rich olefins were also examined (entries 10 and 11) and
gave the corresponding phosphinate in good yields (87 and
85 %). Conversely, no reaction was observed with electron-poor
C-C double bonds (entries 12 and 13). Allyl acetate was
successfully converted into the corresponding phosphinate
(entry 14). Racemic allylglycine (entry 15) do not react under
C
double bonds. Entries 1, 2 and 3 gave the desired
phosphinates, respectively, with 90%, 75% and 81% yields.
Under these conditions, allylsilane (entry 4) also led to the
corresponding phosphinate in high yield (91%). Then endo and
exo-cyclic double bonds were examined (entries 5 and 6) and
the best reactivity was observed for the compound with an endo-
cyclic double bond (96% versus 76%). Internal alkene has also
been investigated using oct-2-ene (entry 7). In this case, the
formation of an inseparable mixture of 4 isomers (regio and
diastereoisomers) was observed in excellent yield (98%).
Hydrophosphonylation of 1,6-heptadiene (entry 8) proceeded via
cyclisation, affording the five-membered ring compound in good
yield (85%). In this case, an inseparable mixture of cis and
trans-isomers was obtained in 4.3/1 ratio. No reaction occurred
these
conditions
while
N-Boc-allylglycine
gave
the
corresponding phosphinate in 75% yield (entry 16). Finally,
some alkynes were also examined. If non activated alkynes
gave the desired phosphinate in moderate yield (entries 17 to
19), conjugate alkynes such as phenylacetylene or 4-
ethynylanisole gave
a
complex mixture of inseparable
compounds (entries 20 and 21).
Table 5. Hydrophosphinylation of various alkenes and alkynes with ethylphenylphosphinate.[a]
Entry
Alkene/Alkyne
Time (h)
Product
E/Z ratio[b]
Yield[c] (%)
90
1
1
-
2
3
1
1
-
-
75
81
4
5
1
1
-
-
91
76
6
7
1
1
-
-
96
98
8
9
1
1
-
-
85
-
-
10
1
-
87
11
12
1
1
-
-
85
-
-
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10.1002/ejoc.201700584
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13
1
1
-
-
-
-
-
14
15
86
1
1
-
-
-
16
17
75
1
56/44
69
18
19
20
21
1
1
1
1
66/34
62/38
-
67
52
-
-
-
-
[a] Reaction conditions: alkene or alkyne (0.25mmol), ethylphenylphosphinate (5 equiv.), DPAP (0.5 equiv.) no solvent under UV-A irradiation (365 nm, 60 w). [b]
Determined by 1H-NMR of the crude reaction mixture. [c] After purification by column chromatography.
Table 6. Influence of the solvent to equation 1.[a]
The scope of the reaction was finally extended to various
commercially available organophosphorus compounds including
a dialkylphosphine oxide and an alkylphosphinic acid. As these
compounds, unlike ethylphenylphosphinate, are solids and not
liquid the use of a solvent was required to accomplish the
hydrophosphinylation reaction (under solvent-free conditions no
reaction was observed due to the heterogeneity of the reaction
mixture). In this respect, several solvents were screened using
vinylcyclohexane as alkene and under our standards conditions
(Table 6). When using cyclohexane (entry 2) and DMF (entry 6)
the hydrophosphinylation adduct was obtained in yields
comparable to the one without solvent (entry 1). As alcohols are
often considered as environmentally friendly solvents,[15]
methanol (entry 7) and isopropanol (entry 8) were investigated,
the latter leading to a slightly better yield (81% versus 83%).
Water was also tested, and gave the desired phosphinate in
good yield (entry 10). An excellent yield can be restored with
isopropanol or water (entries 9 and 11) by increasing the
reaction time to 2 h.
Entry
Solvent
Time (h)
Yield[b] (%)
1
2
-
1
1
1
1
1
1
1
1
2
1
2
90
86
52
35
70
89
81
83
91
77
89
cHex
Toluene
CH2Cl2
THF
3
4
5
6
DMF
7
MeOH
iPrOH
iPrOH
H2O
8
9
10
11
H2O
[
a] Reaction conditions: vinylcyclohexane (0.25 mmol), ethylphenylphosphinate
(5 equiv.), DPAP (0.5 equiv.) under UV-A irradiation (365 nm, 60 w) and 0.5
mL of solvent. [b] After purification by column chromatography.
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10.1002/ejoc.201700584
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Overall these results shown that the hydrophosphinylation may
be achieved efficiently in many different solvents. Aprotic and
apolar solvents such as cyclohexane, aprotic and polar solvents
such as DMF, or protic and polar solvents such as simple
alcohols or water giving the possibility to use the appropriate
solvent depending of the nature of the unsaturated compounds
In our case, the study of various organophosphorus reagents
was achieved using either DMF, isopropanol or water. In order
to be able to compare the different assays, all experiments were
performed using a reaction time of 2 hours. The results of this
study are summarized in Table 7. In the case of 9,10-dihydro-9-
oxa-10-phosphaphenanthrene 10-oxide (DOPO, entry 1) or
diphenylphosphine oxide (entry 3) the best yields were obtained
for both isopropanol and DMF. The phenylphosphonic acid
(entry 2) gave the best results using water as solvent (98%),
whereas significantly lower yields were observed for DMF and
isopropanol.
and/or
the
H-phosphinates
employed.
Recently,
hydrophosphinylation of unactivated alkenes with diaryl
phosphine oxide initiated by commercially available organic dye
under visible light photoirradiation was reported.[11b] These
results demonstrate the power of visible-light photocatalysis to
generate C-P bond formation however with longer reaction time.
Table 7. Scope of the vinylcyclohexane with various H-P(O) derivatives.[a]
Entry
H-P(O)
Solvent
DMF
Time (h)
2
Product
Yield[b] (%)
81
1
i-PrOH
H2O
2
2
2
83
56
86
DMF
2
3
i-PrOH
2
2
66
98
H2O
DMF
i-PrOH
H2O
2
2
2
97
95
72
[a] Reaction conditions: vinylcyclohexane (0.25 mmol), H-P(O) derivatives (5 eq.), DPAP (0.5eq.) under UV-A irradiation (365 nm, 60 w), 0.5 mL of solvent, 2
hours. [b] After purification by column chromatography.
ESI Mass and High Resolution Mass spectra were recorded in the
positive or negative-ion mode on a Micromass Q-TOF. Thin-layer
Conclusions
chromatography was performed on pre-coated aluminum sheets of Silica
60 F254 (Merck, Art. 5554), visualization of products being accomplished
by UV absorbance and by charring with anisaldehyde solution, Dittmer
reagent or KMnO4 (solution in ethanol) and heating. Chromatography
was performed on Merck Silica gel 60 (230–400 mesh ASTM).
In summary, we have developed an efficient photoinduced
coupling of alkenes and alkynes with H-phosphinates and other
P(O)H derivatives under neutral and free-radical conditions. This
reaction can be performed in solvent-free conditions with only
0.1 equiv. of photoinitiator. Depending of the nature of the
substrate and/or P(O)H reagents, the hydrophosphinylation
reaction can be achieved in different types of solvents including
green solvents such as isopropanol or water. Moreover, on large
scale (2.5 mmol) the reaction can be carried out under
stoichiometric conditions while maintaining good yields, reducing
thereby chemical wastes to a minimum. Finally, considering
energy and resource saving, our methodology may be
performed under sunlight photoirradiation while increasing in this
case the reaction time.
General procedure A: The appropriate alkene/alkyne (0.25 mmol, 1
equiv.) and ethyl-phenylphosphinate (1.25 mmol, 5 equiv.) were placed in
a glass vial (diameter: 1 cm; wall thickness: 0.65 mm). DPAP (0.125
mmol, 0.5 equiv.) was added and the reaction mixture was stirred under
UV activation (UV-A lamp, λmax = 365 nm, 4 x 15 w tubes; vial located
2.5 cm away from the lamp) for the indicated time. The solution was then
diluted with EtOAc (10 mL) and washed with aqueous 10% KOH (5x5
mL). The organic phase was dried (MgSO4), concentrated and
purification by flash chromatography on silica gel (CH2Cl2/MeOH)
afforded the corresponding phosphonate.
Experimental Section
General procedure B: Vinylcyclohexane (0.25 mmol,
1 eq), the
appropriate P(O)H derivative (1.25 mmol, 5 equiv.) and the indicated
solvent (0.5 mL) were placed in a glass vial (diameter: 1 cm; wall
thickness: 0.65 mm). DPAP (0.125 mmol, 0.5 equiv.) was added and the
reaction mixture was stirred under UV activation (UV-A lamp, λmax = 365
nm, 4 x 15 w tubes; vial located 2.5 cm away from the lamp) for the
indicated time. The mixture was concentrated and treated by I2 (2 eq) in
General conditions: 1H, 31P and 13C NMR spectra were recorded at
ambient temperature on a Bruker Avance III HD 400 MHz. Chemical
shifts (δ) are quoted in parts per million (ppm) referenced to the residual
solvent peak (CDCl3 fixed at 7.26 ppm and 77.16 ppm) relative to
tetramethylsilane (TMS). Coupling constants, J, are reported in Hertz.
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10.1002/ejoc.201700584
European Journal of Organic Chemistry
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pyridine/H2O (98/2 v/v, 10 mL/mmol) for 15 min. Excess I2 was
neutralised (aq. sat. Na2S2O3), the mixture was diluted (CH2Cl2) washed
with water and concentrated. Purification by flash chromatography on
silica gel (CH2Cl2/MeOH) afforded the corresponding phosphonate.
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Keywords:
Hydrophosphinylation;
Organophosphorus
compound; UV or sunlight irradiation; Photochemistry; radical
reaction.
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This article is protected by copyright. All rights reserved.

10.1002/ejoc.201700584
European Journal of Organic Chemistry
FULL PAPER
Entry for the Table of Contents
FULL PAPER
Hydrophosphinylation;
Organophosphorus compound
Pierre-Yves Geant, Jean-Pierre Uttaro,
Suzanne Peyrottes and Christophe
Mathé*
Page No. – Page No.
Text for Table of Contents
An
eco-friendly
and
efficient
photoinduced coupling of alkenes
and alkynes with H-phosphinates and
other P(O)H derivatives under free-
radical conditions
A green and efficient hydrophosphinylation of various alkenes/alkynes is reported using DPAP as photoinitiator under UV
and/or sunlight irradiation
This article is protected by copyright. All rights reserved.