UV-mediated hydrophosphinylation of unactivated alkenes with phosphinates under batch and flow conditions

Article abstract of DOI:10.1039/c7ra12977g

A UV-mediated hydrophosphinylation of unactivated alkenes with H-phosphinates and hypophosphorous acid under radical free conditions is presented. The reaction affords selectively a large number of structurally diverse organophosphorous compounds in moderate to good yields under mild reaction conditions in the presence of an organic sensitizer as catalyst irradiated by UV-A LEDs. Furthermore, the high yielding hydrophosphinylation in continuous flow is disclosed.

Full text of DOI:10.1039/c7ra12977g

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PAPER
UV-mediated hydrophosphinylation of unactivated
alkenes with phosphinates under batch and flow
conditions†
Cite this: RSC Adv., 2018, 8, 8385
*
Fabien Gelat, Maxime Roger, Christophe Penverne, Ahmed Mazzad,
*
Christian Rolando
and Laetitia Chausset-Boissarie
¨
A UV-mediated hydrophosphinylation of unactivated alkenes with H-phosphinates and hypophosphorous
acid under radical free conditions is presented. The reaction affords selectively a large number of
structurally diverse organophosphorous compounds in moderate to good yields under mild reaction
conditions in the presence of an organic sensitizer as catalyst irradiated by UV-A LEDs. Furthermore, the
high yielding hydrophosphinylation in continuous flow is disclosed.
Received 1st December 2017
Accepted 18th February 2018
DOI: 10.1039/c7ra12977g
rsc.li/rsc-advances
always preferred in term of sustainability and environmental
benignity. Alternatively, pioneering work from the group of
Dondoni8 demonstrated that P(O)-centered radical can be
generated from H-phosphonates under UV-A irradiation, in the
presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) as
photoinitiator, and added to alkene functionalized carbohy-
Introduction
Organophosphorus compounds have attracted much attention
due to their wide range of applications in materials, catalysis,
natural bioactive products and pharmaceuticals.1 In particular,
phosphinates (P(O)(OR)R1R2, R1/R2 ¼ hydrogen and/or carbon)
have been the target of numerous synthetic efforts as they are
versatile precursors to organophosphorus compounds and
represent a sustainable alternative to the use of phosphorous
trichloride.2 Indeed, phosphinates can be considered as the
synthetic equivalents of phosphorous trichloride with several
advantages in terms of stability and toxicity. In this regard, the
development of efficient and selective methodologies for the
preparation and functionalization of phosphinates (P(O)(OR)H2)
and H-phosphinates (P(O)(OR)R1H) has been extensively studied,
mostly by the group of Montchamp.2,3 Hydrophosphinylation of
unactivated alkenes is one of these routes that provide a direct
access to functionalized organophosphorous compounds.4 This
atom economical process has been reported to proceed via
transition metal catalysis,5 or radical activation (Scheme 1a and
b).6 Despite the signicant progress in this chemistry, these
transformations suffer from some drawbacks like the relatively
harsh conditions, narrow substrates scopes and costly catalytic
system thus limiting their chemical and pharmaceutical appli-
cations. Recently, Lakhdar and co-workers reported a hydro-
phosphinylation of unactivated alkenes with ethyl and butyl
phosphinates under photocatalytic conditions (Scheme 1c),7
even though diphenyl iodonium triate which acted as sacricial
oxidant is not a heavy metal, the use of catalytic quantity is
drates. However, the reaction requires the use of a large excess of
9
´
phosphonates (100 eq.). Mathe and coworkers then extended
this free radical hydrophosphonylation to activated and unac-
tivated alkenes, similar reaction with hypophosphorous acid and
H-phosphinates derivatives10 have not been studied previously.
In this context, we envisaged that continuous-ow systems in
combination with a sensitizer irradiated by UV-A LEDs (l ¼ 365
`
´
USR 3290, MSAP, Miniaturisation pour la Synthese l'Analyse et la Proteomique and FR
`
´
2638, Institut Eugene-Michel Chevreul, Universite de Lille, F-59000 Lille, France.
E-mail: Laetitia.chausset-boissarie@univ-lille1.fr; Fabien.gelat@univ-lille1.fr
† Electronic supplementary information (ESI) available: Copies of 1H and 13C
NMR spectral data. See DOI: 10.1039/c7ra12977g
Scheme 1 Hydrophosphinylation of phosphinates with unactivated
alkenes.
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Table 1 Optimization of the reaction conditionsa
nm) would result in a signicant enhancement of the reaction.
Over the last decade, interest has grown for ow chemistry based
on microuidic technology in particular towards large-scale
application due to its signicant improvement over traditional
batch reactors concerning reduced consumption of chemicals,
solvents and time together with enhanced yields, selectivity and
control over reaction conditions. An easy scale up is also one of the
characteristic of photo-reactions which are conducted in micro-
reactors. In batch reactors, light penetration through the reaction
media is limited which restrains the efficiency of photochemical
processes. This drawback can be overcome with continuous
microow reactors since their small optical lengths improve
sample irradiation and also enhance heat and mass transfer.11
Therefore, in view of the growing demand to develop efficient,
mild and sustainable methods to access phosphinates and as
a continuation of our interest in photocatalyzed processes,12 we
herein report an original UV-mediated hydrophosphinylation of
unactivated alkenes with hypophosphorous acid and less reactive
H-phosphinates derivatives under batch and ow conditions.
Entry Photoinitiator
Equivalent Solvent Time (h) Yieldb (%)
1
2
3
4
5
6
7
8
4,40-DMBPc
4,40-DMBP
4,40-DMBP
4,40-DMBP
4,40-DMBP
4,40-DMBP
4,40-DMBP
4,40-DMBP
—
4,40-DMBP
4,40-DMBP
Thioxantone
4-MAPf
1
1
1
1
MeCN
EtOAc
DMF
3
3
3
3
3
3
5
17
5
5
5
5
5
5
5
16
42
46
52
69
70
72
84
86
10
—
DMSO
AcOH
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
1
0.5
0.1
0.05
—
0.1
0.1
0.1
0.1
9
10d
11e
12
13
14
15
16
5
76
19
77
32
79 (76)i
Benzophenone 0.1
Results and discussion
Hydrophosphinylation of unactivated alkenes with H-
DMPAg
DIBPh
0.1
0.1
phosphinates under batch conditions
a
Reaction condition: 1a (0.3 mmol, 1 equiv.), 2a (0.3 mmol, 1 equiv.),
photoinitiator (x equiv.), solvent ([0.1 M]), under nitrogen and UV-A
Initially, the hydrophosphinylation of relatively challenging H-
phosphinate (1a) with octene (2a) in equimolar amounts in the
presence of a photoinitiator under UV-A irradiation was selected
as a model to investigate the reaction. The use of one equivalent
of 4,40-dimethoxybenzophenone (4,40-DMBP) was found to be
effective furnishing 3a aer stirring in acetonitrile under an
ambient inert atmosphere for 3 h (Table 1, entry 1, 42%). An
investigation of solvents showed that the reaction efficiency was
further enhanced when performed in DMSO (Table 1, entry 4,
69%) or acetic acid6b,13 (entry 5, 70%) as previously observed for
radical process with H-phosphinates, whereas moderate yields
were obtained with ethyl acetate (entry 2, 46%) or DMF (entry 3,
52%). Importantly a very low catalyst loading could promote the
reaction yield up to 84% (entries 6 and 7). Moreover, the loading
could be further decreased but a prolonged reaction time was
required (Table 1, entry 8, 86%). Interestingly, the photo-
initiator DMPA (2,2-dimethoxy-2-phenylacetophenone) was not
efficient in our case since the phosphorylated product was
formed in a moderate yield (Table 1, entry 15, 32%). Further-
more, none of the common photoinitiators (thioxantone, 4-
methoxyacetophenone, benzophenone) exhibited a better cata-
lytic effect (Table 1, entries 12–14). Control experiments
revealed that the photoinitiator, inert conditions and light were
essential for this reaction (Table 1, entries 9–11). It is note-
worthy that using a 4,40-DMBP derivative functionalized with an
ionic liquid moiety14 (4,40-(2-(1-methylimidazolium)ethoxy)
benzophenone dibromide, DIBP) as photosensitizer led to the
same conversions as previously observed furnishing an excel-
lent way to simplify the purication procedure by simple
washing of the reaction media thus improving the synthetic
efficiency by avoiding chromatography (Table 1, entry 16).
The generality of the method was investigated, with the
scope of the reaction being explored with respect to the H-
LED irradiation (l
¼
365
ꢀ
15 nm, 230 mW cmꢁ2
) at room
temperature. Derived from 31P crude NMR spectra on integration of
b
c
all formed species. 4,40-DMBP
¼
4,40-dimethoxybenzophenone.
d
e
f
Without irradiation. Under ambient atmosphere. 4-MAP ¼ 4-
g
methoxyacetophenone.
DMPA
¼
2,2-dimethoxy-2-
h
phenylacetophenone. DIBP ¼ 4,40-(2-(1-methylimidazolium)ethoxy)
benzophenone dibromide. i The isolated yield is shown in parentheses.
phosphinate component, and the results are summarized in
Table 2. Various P(O)–H compounds were employed to react
with 1-octene 2a giving the corresponding 3a–g with isolated
yields ranging from 30 to 76% (Table 2, entries 1–7). As ex-
pected, in all of the cases the anti Markovnikov product was
observed. The reaction is not limited to H-phosphinate esters as
H-phosphinate acid 1b could also deliver the desired product
with a good yield (entry 2, 64%) in contrast to H-phosphinate
acid 1c whose corresponding phosphinate acid product 3c was
difficult to obtain in high purity (entry 3, 30%). However, H-
phosphinate including unactivated alkyl and benzyl derivatives
reacted successfully regardless of the ester chosen (Table 2,
entries 4–6). When using (hydroxymethyl)-H-phosphinate ester,
which was reported to have several application,15 the branched
product 3g was obtained with a signicant yield of 75% (Table 2,
entry 7). To further evaluate the substrate scope, a series of
alkenes were tested with H-phosphinate 1a (Table 2, entries 8–
12). The reaction with allyl benzene gave the corresponding
product 3h with 48% of yield (Table 2, entry 8). Interestingly, 1a
reacted with hindered alkene giving 3i with a modest yield of
27% (Table 2, entry 9). Note that halogens like Br and alcohol
groups were well tolerated which indicates a potential for
further functionalization (Table 2, entries 10–12).
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Although the detailed reaction mechanism is unclear, based
on literature precedents6i,16 all these results could be well
explained by a radical chain mechanism as depicted in Scheme
2. Upon irradiation, the excited state of the photoinitiator17
abstracts a proton from H-phosphinates to form the phosphoryl
radical18 which adds to the terminal carbon of the alkenes. The
carbon centered radical can then abstract a proton from H-
phosphinate 1 to regenerate the phosphoryl radical.
Table 2 Hydrophosphinylation of alkenes with H-phosphinatesa 1
Entry H-Phosphinate 1 Alkene 2
Product 3
Yield (%)
76
Hydrophosphinylation of unactivated alkenes with H-
phosphinates under ow conditions
1
2
1-Octene 2a
With the successful results for the hydrophosphinylation under
batch conditions, the reaction was then performed under
continuous ow to further improve its efficiency in a shorter
amount of time. The continuous ow hydrophosphinylation
was performed using a continuous ow microuidic system
composed of a high pressure syringe pump delivering the
homogeneous reaction mixture at specic ow rates to
1-Octene 2a
1-Octene 2a
1-Octene 2a
1-Octene 2a
1-Octene 2a
64
30b
73
71
51
3
a
commercially available microreactor (Mikroglas Dwell
Device® microreactor from Invenios Europe, Langen, Germany)
irradiated by HP UV-A lamp. This microreactor is made up of
Foturan® glass that is transparent up to 300 nm allowing to
work at a wide range of wavelengths (UV-A & visible).
We were delighted to nd that H-phoshinate derivatives (3a,
b, k) could be obtained with 4,40-DMBP as photoinitiator within
a shorter reaction time than in batch (30 min vs. 5 h), indicating
the importance of the short light path length provided by the
microreactor, with slightly higher isolated yield, highlighting
the potentials of this process (Scheme 3). This results offer the
possibility to conduct the reaction on large scale without
erosion of the yields.
4
5
6c
7
1-Octene 2a
75
48
27
Hydrophosphinylation of unactivated alkenes with
hypophosphorous acid under batch conditions
8
To further demonstrate the utility of our protocol, we sought to
test its potential for the hydrophosphinylation of various
9c
10
38
56
11c
12c
69
a
Reaction condition: all reactions unless specied were carried out
using 1 (0.3 mmol, 1 equiv.), 2 (0.3 mmol, 1 eq.), DIBP (0.1 equiv.) in
DMSO ([0.1 M]) under nitrogen and UV-A LED irradiation (l ¼ 365 ꢀ
15 nm, 230 mW cmꢁ2) at room temperature for 16 h, isolated yield.
b
Derived from 31P crude NMR spectra on integration of all formed
species. c (0.5 equiv.) of DIBP.
Scheme
2 Proposed reaction mechanism for the photoinduced
hydrophosphinylation of unactivated alkenes with H-phosphinates.
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2 : 1 molar ratio of hypophosphorous acid–alkenes was
necessary to obtain a high conversion without the formation of
the disubstituted by-product. However despite the observed
high conversions, isolated yields were modest due to difficult
purications. In all of the cases, the reaction was chemo-
selective where only mono substituted phosphinates were
observed. As for H-phosphinate, the reaction proceeded well
with terminal (1c–h) and cyclic alkenes (1j). Hindered alkenes
delivered the desired compounds like 1i with a moderate yield
of 31%, which is still higher than that obtained with H-phos-
phinate ester. H-Phosphinate acid 1k however was difficult to
obtain in high purity. Similar to the rst reaction assessed, the
reaction tolerates functional groups such as amines or alco-
hols (1l–n) but the obtained H-phosphinate acids were not
isolated. Although the scope of this reaction seems to be
limited, H-phosphinate acids could be easily esteried19 in situ
and therefore the resulting procedure offers signicant
synthetic advantages.
Scheme 3 Hydrophosphinylation of alkenes with H-phosphinates 1
under batch and flow conditions. (a) Reactions conditions in batch: 1
(0.3 mmol, 1 equiv.), 2 (0.3 mmol, 1 eq.), 4,40-DMPB (0.1 equiv.) in
DMSO ([0.1 M]) under nitrogen and UV-A LED irradiation (l ¼ 365 ꢀ
15 nm, 230 mW cmꢁ2) at room temperature, 5 h, isolated yield. (b)
Reaction conditions in continuous flow: 1 (0.3 mmol, 1 equiv.), 2
(0.3 mmol, 1 equiv.), 4,40-DMPB (0.1 equiv.) in DMSO ([0.1 M]) under
nitrogen and UV-A LED irradiation (l ¼ 365 ꢀ 15 nm, 230 mW cmꢁ2
)
with Dwell device manufactured by Mikroglass Chemtech Mainz,
Germany with a rectangular shape of dimensions 115 mm ꢂ 2 mm ꢂ
0.5 mm as photo-microreactor, at room temperature for 30 min of
residence time, isolated yield.
Experimental section
General information
All reagents were purchased from commercial suppliers (Strem
Chemicals Inc., Sigma-Aldrich or Alfa Aesar) and were used
without further purication. Thin-layer chromatography (TLC)
was performed on Silica gel 60 F254 plates (Merck) and visual-
ized under UV (254 nm) or by staining with potassium
permanganate or phosphomolybdic acid. Column chromatog-
raphy was performed with 63–200 mesh silica gel. NMR spectra
were recorded on a Bruker AVANCE 300 spectrometer at 300
MHz (75 MHz). Chemical shis are reported in parts per million
relative to solvent signal and coupling constants are reported in
hertz (Hz). High-resolution mass spectra (HRMS) were per-
formed on a Thermo LTQ Orbitrap mass spectrometer using
nanoESI ionization. H-Phosphinates derivatives 1 and 4,40-(2-(1-
methylimidazolium)ethoxy)benzophenone dibromide (DIBP)14
were prepared according to the reported procedure. The illu-
mination was performed by UV-A LEDs (365 nm, irradiance ¼
alkenes with hypophosphorous acid to form the previous
precursor H-phosphinate acid (Scheme 4).
A slight modication of the previous batch conditions (see
Table 1, ESI†) allowed us to obtain the corresponding H-
phosphinates 1 with 31P NMR yield ranging from 49 to 96%. A
230 mW cmꢁ2
) Omnicure® AC475 model from Lumen
Dynamics (Excelitas Technologies, Waltham, MA, USA). Note
that the irradiance was measured at the surface of the reactor
using a radiometer.
General procedure A for the hydrophosphinylation with H-
phosphinate 1 derivatives under batch conditions
A solution of a selected H-phosphinate 1 (0.3 mmol, 1 equiv.), an
alkene 2 (0.3 mmol, 1 equiv.) and DIPB (0.03–0.15 mmol, 10–
50 mol%) in degazed DMSO (1.5 mL) was irradiated under
365 nm and N2 for 16 h. Ethyl acetate (30 mL) was added and the
reaction mixture was washed with saturated solution of
NaHCO3 (2 ꢂ 15 mL) and brine (2 ꢂ 15 mL). The organic layer
was dried over MgSO4, ltered and concentrated under reduce
pressure. The residue was then puried by ash chromatog-
raphy on silica gel if necessary to afford the corresponding
organophosphorous compound.
Scheme 4 Hydrophosphinylation of alkenes with hypophosphorous
acid. All reactions (unless otherwise specified) were carried out using
H3PO2 (0.3 mmol, 2 equiv.), 2 (0.15 mmol, 1 equiv.), DMPA (0.2 equiv.)
in DMSO ([0.1 M]) under UV-A LED irradiation (l ¼ 365 ꢀ 15 nm, 230
mW cmꢁ2) at room temperature for 16 h. aDerived from 31P crude NMR
spectra on integration of all formed species. bIsolated yield.
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removed under reduce pressure to afford the desired pure
compound 3b (51.8 mg, 0.19 mmol, 64%). 31P NMR (121 MHz,
CDCl3): d ¼ 45.8 (s); 1H NMR (300 MHz, CDCl3): d ¼ 11.65 (br s,
1H), 7.72–7.58 (m, 2H), 7.45–7.24 (m, 3H), 1.83–1.64 (m, 2H),
1.46–1.26 (m, 2H), 1.24–1.03 (m, 10H), 0.78 (t, J ¼ 6.7 Hz, 3H);
13C NMR (75 MHz, CDCl3): d ¼ 132.5 (d, JPC ¼ 127 Hz), 131.9,
131.2 (d, JPCCC ¼ 9.4 Hz, 2C), 128.4 (d, JPCC ¼ 11.4 Hz, 2C), 31.9,
30.8 (d, JPCC ¼ 16.3 Hz), 30.6 (d, JPC ¼ 98.7 Hz), 29.2 (2C), 22.7,
21.8 (d, JPCCC ¼ 2.6 Hz), 14.2; HRMS (ESI) m/z calcd for
C14H24O2P ([M + H]+) 255.1508, found 255.1507.
Octyl octylphosphinic acid (3c). A solution of Octyl phos-
phinic acid5b 1c (53.5 mg, 0.3 mmol, 1 equiv.), 1-octene 2a
(33.6 mg, 0.3 mmol, 1 equiv.) and DIPB (6.7 mg, 0.03 mmol,
10 mol%) in degazed DMSO (3 mL) was irradiated under 365 nm
and argon for 16 h. Ethyl acetate (30 mL) was added and the
reaction mixture was washed with brine (3 ꢂ 15 mL). To the
organic layer was added a 0.03 M solution of sodium bicar-
bonate (30 mL, 1 mmol). The aqueous layer was washed with
ethyl acetate (2 ꢂ 15 mL), acidied with 1 M HCl (2 mL, 2 mmol)
and extracted with ethyl acetate (30 mL). The last ethyl acetate
General procedure B for the hydrophosphinylation with
hypophosphorous acid
To a 50% aqueous solution of hypophosphorous acid (79.2 mg,
0.6 mmol, 2 equiv.) in DMSO (3 mL) was added an alkene 2
(0.3 mmol, 1 equiv.), 4,40-DMPA (15.5 mg, 0.06 mmol, 20 mol%).
The reaction mixture was irradiated under 365 nm and ambient
atmosphere for 16 h. Ethyl acetate (30 mL) was added and the
organic layer was washed with brine (3 ꢂ 15 mL). To the organic
layer a 0.03 M solution of NaHCO3 (30 mL, 1 mmol) was added.
The aqueous layer was washed with ethyl acetate (2 ꢂ 15 mL),
acidied with 1 M HCl (2 mL, 2 mmol), saturated with NaCl and
extracted with ethyl acetate (30 mL). The last ethyl acetate layer
was dried over Na2SO4, ltered and concentrated under reduce
pressure. The residue was then puried by ash chromatog-
raphy on silica gel using 9 : 1 : 0.5 DCM–MeOH–AcOH as the
eluant to afford the desired pure H-phosphinate acid 1.
Hydrophosphinylation of cyclohexyl phenyl-H-phosphinate 1a
under ow condition
A solution of a cyclohexyl phenyl-H-phosphinate20 1a (67.2 mg, layer was dried over Na2SO4, ltered and the solvent was
0.3 mmol, 1 equiv.), 1-octene 2a (33.6 mg, 0.3 mmol, 1 equiv.) removed under reduce pressure to afford compound 3c with
and 10 mol% of 4,40-dimethoxybenzophenone (7.2 mg) in impurities (51.8 mg, 0.19 mmol, derived from 31P NMR spectra
degazed DMSO (1.5 mL) was pumped through the Mikroglas on integration of all formed species). All attempts to purify the
Dwell Device reactor (Vint ¼ 1.15 mL) at 38.33 mL minꢁ1, resi- compound were unfruitful. 31P NMR (121 MHz, CDCl3): d ¼
dence time of 30 min and irradiated by UV-A LEDs. Ethyl acetate 56.5 (s).
(30 mL) was added to the collected reaction mixture and the
Cyclohexyl dioctylphosphinate (3d). Following the general
reaction mixture was washed with saturated solution of procedure A, using cyclohexyl octyl-H-phosphinate20 1d (78 mg,
NaHCO3 (2 ꢂ 15 mL) and brine (2 ꢂ 15 mL). To the organic 0.3 mmol, 1 equiv.), 1-octene 2a (33.6 mg, 0.3 mmol, 1 equiv.)
layer was dried over MgSO4, ltered and the solvent was and 10 mol% of catalyst (17.8 mg) affords 3d (81.2 mg,
removed under reduce pressure to afford 3a (85.6 mg, 0.22 mmol, 73%) as a colorless oil. 31P NMR (121 MHz, CDCl3):
0.25 mmol, 85%) as a colorless oil.
d ¼ 56.5 (s); 1H NMR (300 MHz, CDCl3): d ¼ 4.41–4.27 (m, 1H),
Cyclohexyl octyl(phenyl)phosphinate (3a). Following the 1.92–1.81 (m, 2H), 1.74–1.41 (m, 12H), 1.40–1.17 (m, 24H), 0.85
general procedure A, using cyclohexyl phenyl-H-phosphinate 1a (t, J ¼ 6.7 Hz, 6H); 13C NMR (75 MHz, CDCl3): d ¼ 73.2 (d, JPOC
(67.2 mg, 0.3 mmol, 1 equiv.), 1-octene (33.6 mg, 0.3 mmol, 1 6.8 Hz), 34.4 (d, JPOCC ¼ 4.3 Hz, 2C), 31.9 (2C), 31.0 (d, JPCC
¼
¼
equiv.) and 10 mol% of catalyst (17.8 mg) affords 3a (76.6 mg, 15.1 Hz, 2C), 29.2 (2C), 29.2 (2C), 28.9 (d, JPC ¼ 89.9 Hz, 2C),
0.23 mmol, 76%) as a colorless oil. 31P NMR (121 MHz, CDCl3): 25.4, 23.9 (2C), 22.7 (2C), 22.1 (d, JPCCC ¼ 3.9 Hz, 2C), 14.2 (2C);
d ¼ 43.5 (s); 1H NMR (300 MHz, CDCl3): d ¼ 7.81–7.72 (m, 2H), HRMS (ESI) m/z calcd for C22H46O2P ([M + H]+) 373.3229, found
7.55–7.39 (m, 3H), 4.30–4.16 (m, 1H), 2.06–2.11 (m, 24H), 0.83 (t, 373.3227.
J ¼ 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3): d ¼ 132.3 (d, JPC
¼
Butyl dioctylphosphinate (3e). Following the general proce-
122 Hz), 132.0 (d, JPCCCC ¼ 2.7 Hz), 131.7 (d, JPCCC ¼ 9.7 Hz, 2C), dure A, using butyl octyl-H-phosphinate5d 1e (70.3 mg,
128.5 (d, JPCC ¼ 12.2 Hz, 2C), 74.3 (d, JPOC ¼ 6.8 Hz), 34.4 (d, 0.3 mmol, 1 equiv.), 1-octene 2a (33.6 mg, 0.3 mmol, 1 equiv.)
JPOCC ¼ 2.9 Hz), 33.8 (d, JPOCC ¼ 4.3 Hz), 31.9, 31.0 (d, JPCC ¼ 16.0 and 10 mol% of catalyst (17.8 mg) affords 3e (74 mg, 0.21 mmol,
Hz), 30.4 (d, JPC ¼ 101 Hz), 29.1 (2C), 25.3, 23.8, 23.8, 22.7, 21.8 71%) as a colorless oil. 31P NMR (121 MHz, CDCl3): d ¼ 57.6 (s);
(d, JPCCC ¼ 3.7 Hz), 14.2. HRMS (ESI) m/z calcd for C20H34O2P 1H NMR (300 MHz, CDCl3): d ¼ 3.92 (q, J ¼ 6.7 Hz, 2H), 1.71–
([M + H]+) 337.2290, found 337.2289.
1.19 (m, 32H), 0.89 (t, J ¼ 7.4 Hz, 3H), 0.84 (t, J ¼ 6.7 Hz, 6H); 13
C
Octyl phenylphosphinic acid (3b). A solution of phenyl NMR (75 MHz, CDCl3): d ¼ 63.7 (d, JPOC ¼ 6.9 Hz), 32.9 (d, JPOCC
phosphinic acid 1b (47.4 mg, 0.3 mmol, 1 equiv.), 1-octene 2a ¼ 5.8 Hz), 31.9 (2C), 31.0 (d, JPCC ¼ 15.0 Hz, 2C), 29.2 (2C), 29.1
(33.6 mg, 0.3 mmol, 1 equiv.) and DIPB (6.7 mg, 0.03 mmol, (2C), 28.0 (d, JPC ¼ 89.6 Hz, 2C), 22.7 (2C), 22.0 (d, JPCCC
¼
10 mol%) in degazed DMSO (3 mL) under N2 was irradiated 3.9 Hz, 2C), 18.9, 14.1 (2C), 13.7. HRMS (ESI) m/z calcd for
under 365 nm for 15 h. Ethyl acetate (30 mL) was added and the
C
20H44O2P ([M + H]+) 347.3073, found 347.3073.
reaction mixture was washed with brine (3 ꢂ 15 mL). To the
Butyl benzyl(octyl)phosphinate (3f). Following the general
organic layer was added a 0.03 M solution of sodium bicar- procedure A, using butyl benzyl-H-phosphinate4a 1f (63.6 mg,
bonate (30 mL, 1 mmol). The aqueous layer was washed with 0.3 mmol, 1 equiv.), 1-octene 2a (33.6 mg, 0.3 mmol, 1 equiv.)
ethyl acetate (2 ꢂ 15 mL), acidied with 1 M HCl (2 mL, 2 mmol) and 50 mol% of catalyst (89 mg) affords 3f (49.6 mg, 0.15 mmol,
and extracted with ethyl acetate (30 mL). The last ethyl acetate 51%) as a colorless oil. 31P NMR (121 MHz, CDCl3): d ¼ 52.9 (s);
layer was dried over Na2SO4, ltered and the solvent was 1H NMR (300 MHz, CDCl3): d ¼ 7.28–7.16 (m, 5H), 3.96–3.76 (m,
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2H), 3.06 (d, JPCH ¼ 16.7 Hz, 2H), 1.60–1.39 (m, 6H), 1.35–1.13 ene 2c (22.1 mg, 0.3 mmol, 1 equiv.) and 50 mol% of catalyst
(m, 12H), 0.84 (t, J ¼ 7.3 Hz, 3H), 0.80 (t, J ¼ 6.7 Hz, 3H); 13C (89 mg) affords 3i (24 mg, 0.08 mmol, 27%) as a colorless oil
NMR (75 MHz, CDCl3): d ¼ 132.2 (d, JPCC ¼ 7.2 Hz), 129.8 (d, (mixture 1 : 1 of the both diastereoisomers). 31P NMR (121 MHz,
1
JPCCC ¼ 5.6 Hz, 2C), 128.8 (d, JPCCCC ¼ 2.7 Hz, 2C), 126.9 (d, CDCl3): d ¼ 42.7 (s), 46.3 (s); H NMR (300 MHz, CDCl3): d ¼
JPCCCCC ¼ 3.2 Hz), 64.3 (d, JPOC ¼ 6.9 Hz), 36.5 (d, JPC ¼ 84.0 Hz), 7.76–7.66 (m, 2H), 7.49–7.34 (m, 3H), 4.26–4.10 (m, 1H), 2.31–
32.9 (d, JPOCC ¼ 5.8 Hz), 31.9, 30.9 (d, JPCC ¼ 15.2 Hz), 29.2, 29.1, 1.48 (m, 7H), 1.42–1.03 (8H), 0.96–0.79 (m, 6H); 13C NMR (75
27.6 (d, JPC ¼ 92.5 Hz), 22.8, 21.8 (d, JPCCC ¼ 4.3 Hz), 18.9, 14.2, MHz, CDCl3): d ¼ 132.3 (d, JPCC ¼ 5.1 Hz, 2 ꢂ 0.5C), 132.2 (d,
13.4. HRMS (ESI) m/z calcd for C19H34O2P ([M + H]+) 325.2290, JPCC ¼ 5.2 Hz, 2 ꢂ 0.5C), 131.9 (d, JPCCCC ¼ 2.2 Hz, 0.5C), 131.9
found 325.2289.
(d, JPCCCC ¼ 2.2 Hz, 0.5C), 128.5 (d, JPCCC ¼ 3.2 Hz, 2 ꢂ 0.5C),
Cyclohexyl hydroxymethyl(octyl)phosphinate (3g). To a solu- 128.3 (d, JPCCC ¼ 3.1 Hz, 2 ꢂ 0.5C), 74.2 (d, JPOC ¼ 7.2 Hz, 0.5C),
tion of hypophosphorous acid (6.3 g, 48 mmol, 1 equiv.) was 74.0 (d, JPOC ¼ 7.1 Hz, 0.5C), 39.6 (d, JPC ¼ 100 Hz 2 ꢂ 0.5C), 34.4
added paraformaldehyde (1.575 g, 52.5 mmol, 1.1 equiv.) and (d, JPOCC ¼ 2.4 Hz, 0.5C), 34.4 (d, JPOCC ¼ 2.3 Hz, 0.5C), 33.8 (d,
the reaction mixture was stirred under N2 for 24 h. Then, JPOCC ¼ 1.9 Hz, 0.5C), 33.8 (d, JPOCC ¼ 1.9 Hz, 0.5C), 26.8 (d,
cyclohexanol (10 mL, 96 mmol, 2 equiv.) and toluene (85 mL) JPCCC ¼ 2.8 Hz, 0.5C), 26.1 (0.5C), 25.4 (2 ꢂ 0.5C), 23.8 (2 ꢂ
were added and the solution was reuxed for 16 h under Ar 0.5C), 23.7 (2 ꢂ 0.5C), 22.6 (d, JPCC ¼ 6.1 Hz, 0.5C), 22.4 (d, JPCC
using a Dean-Stark apparatus. During the reaction, the forma- ¼ 8.7 Hz, 0.5C), 18.3 (d, JPCC ¼ 3.2 Hz, 0.5C), 17.7 (d, JPCCC
¼
tion of a gel occurred. The reaction mixture was cooled to room 2.2 Hz, 0.5C), 7.7 (0.5C), 6.9 (d, JPCC ¼ 4.6 Hz, 0.5C) (1 signal
temperature and transferred into another round bottom ask to missing); HRMS (ESI) m/z calcd for C17H28O2P ([M + H]+)
remove the gel and concentrated under vaccum to afford the 295.1821, found 295.1819.
desired hydroxymethyl-H-phosphinate 1g (9.4 g, 57% purity,
Cyclohexyl
(5-bromopentyl)(phenyl)phosphinate
(3j).
30.1 mmol, 63%) which was used without any further purica- Following the general procedure A, using cyclohexyl phenyl-H-
tion for the next step.21 A solution of compound 1g (93.7 mg, phosphinate 1a (67.2 mg, 0.3 mmol, 1 equiv.), 5-bromo-1-
0.3 mmol, 1 equiv.), 1-octene 2a (50.4 mg, 0.45 mmol, 1.5 equiv.) pentene 2d (46.6 mg, 0.3 mmol, 1 equiv.) and 10 mol% of
and DIPB (17.5 mg, 0.03 mmol, 10 mol%) in degazed DMSO (3 catalyst (17.8 mg) affords 3j (43 mg, 0.12 mmol, 38%) as
mL) under N2 was irradiated under 365 nm for 16 h. Ethyl a colorless oil. 31P NMR (121 MHz, CDCl3): d ¼ 42.7 (s); 1H NMR
acetate (30 mL) was added and the reaction mixture was washed (300 MHz, CDCl3): d ¼ 7.82–7.72 (m, 2H), 7.56–7.39 (m, 3H),
with saturated solution of NaHCO3 (2 ꢂ 15 mL) and brine (2 ꢂ 4.31–4.18 (m, 1H), 3.34 (t, J ¼ 6.8 Hz, 2H), 2.06–1.11 (m, 18H);
15 mL). The organic layer was dried over MgSO4, ltered and the 13C NMR (75 MHz, CDCl3): d ¼ 132.2 (d, JPC ¼ 123 Hz), 132.1 (d,
solvent was removed under reduce pressure. The residue was JPCCCC ¼ 2.7 Hz), 131.7 (d, JPCCC ¼ 9.7 Hz, 2C), 128.6 (d, JPCC
¼
puried on a column of silica gel to afford the desired pure 12.3 Hz, 2C), 74.5 (d, JPOC ¼ 6.7 Hz), 34.5 (d, JPOCC ¼ 2.9 Hz), 33.8
desired H-phosphinate 3g (65.2 mg, 0.23 mmol, 75%). 31P NMR (d, JPOCC ¼ 4.4 Hz), 33.5, 32.4, 30.3 (d, JPC ¼ 101 Hz), 29.3 (d, JPCC
(121 MHz, CDCl3): d ¼ 52.9 (s); 1H NMR (300 MHz, CDCl3): d ¼ ¼ 15.7 Hz), 25.3, 23.8, 23.8, 21.2 (d, JPCCC ¼ 3.6 Hz); HRMS (ESI)
4.82 (s br, 1H), 4.43–4.28 (m, 1H), 3.87–3.70 (m, 2H), 1.92–1.14 m/z calcd for C17H27BrO2P ([M + H]+) 372.0854, found.
(m, 24H), 0.84 (d, J ¼ 6.6 Hz, 3H); 13C NMR (75 MHz, CDCl3): d ¼
Cyclohexyl
phenyl(3-hydroxypropyl)phosphinate
(3k).
74.4 (d, JPOC ¼ 7.2 Hz), 59.3 (d, JPC ¼ 104.4 Hz), 34.3 (d, JPOCC
¼
Following the general procedure A, using cyclohexyl phenyl-H-
3.2 Hz), 34.2 (d, JPOCC ¼ 3.3 Hz), 31.9, 31.0 (d, JPCC ¼ 14.9 Hz), phosphinate 1a (67.2 mg, 0.3 mmol, 1 equiv.), allyl alcohol 2e
29.2 (2C), 26.5 (d, JPC ¼ 89.6 Hz), 25.2, 23.8 (2C), 22.7, 21.5 (d, (17.4 mg, 0.3 mmol, 1 equiv.) and 50 mol% of catalyst (89 mg)
JPCCC ¼ 4.2 Hz), 14.2; HRMS (ESI) m/z calcd for C15H32O3P ([M + affords 3k (47.0 mg, 0.168 mmol, 56%) as a colorless oil. 31P
H]+) 291.2083, found 291.2080.
Cyclohexyl
NMR (121 MHz, CDCl3): d ¼ 44.9 (s); 1H NMR (300 MHz, CDCl3):
phenyl(3-phenylpropyl)phosphinate
(3h). d ¼ 7.84–7.72 (m, 2H), 7.58–7.40 (m, 3H), 4.32–4.18 (m, 1H),
Following the general procedure A, using cyclohexyl phenyl-H- 3.63–3.70 (m, 2H), 2.12–1.12 (m, 15H); 13C NMR (75 MHz,
phosphinate 1a (67.2 mg, 0.3 mmol, 1 equiv.), allylbenzene 2b CDCl3): d ¼ 132.3 (d, JPCCCC ¼ 2.6 Hz), 131.7 (d, JPCCC ¼ 9.9 Hz,
(35.4 mg, 0.3 mmol, 1 equiv.) and 50 mol% of catalyst (89 mg) 2C), 131.6 (d, JPC ¼ 123.9 Hz), 128.7 (d, JPCC ¼ 12.4 Hz, 2C), 74.9
affords 3h (48.3 mg, 0.14 mmol, 48%) as a colorless oil. 31P NMR (d, JPOC ¼ 6.7 Hz), 62.8 (d, JPCC ¼ 11.0 Hz), 34.4 (d, JPOCC ¼ 2.7
(121 MHz, CDCl3): d ¼ 43.0 (s); 1H NMR (300 MHz, CDCl3): d ¼ Hz), 33.8 (d, JPOCC ¼ 4.3 Hz), 27.9 (d, JPC ¼ 101.3 Hz), 25.4 (d,
7.74–7.64 (m, 2H), 7.49–7.33 (m, 3H), 7.21–7.00 (m, 5H), 4.24– JPCCC ¼ 3.8 Hz), 25.2, 23.7, 14.3; HRMS (ESI) m/z calcd for
4.09 (m, 1H), 2.66–2.49 (m, 2H), 1.98–1.04 (m, 14H); 13C NMR
(75 MHz, CDCl3): d ¼ 141.2, 132.1 (d, JPC ¼ 123 Hz), 132.0 (d,
C
15H24O3P ([M + H]+) 283.1457, found 283.1455.
Cyclohexyl (4-hydroxybutyl) (phenyl) phosphinate (3l).
JPCCCC ¼ 2.7 Hz), 131.6 (d, JPCCC ¼ 9.8 Hz, 2C), 128.5 (2C), 128.5 Following the general procedure A, using cyclohexyl phenyl-H-
(d, JPCC ¼ 12.2 Hz, 2C), 128.4 (2C), 126.0, 74.4 (d, JPOC ¼ 6.7 Hz), phosphinate 1a (67.2 mg, 0.3 mmol, 1 equiv.), 3-buten-1-ol 2f
36.6 (d, JPCC ¼ 16.0 Hz), 34.4 (d, JPOCC ¼ 2.9 Hz), 33.7 (d, JPOCC
4.4 Hz), 29.8 (d, JPC ¼ 101 Hz), 25.2, 23.7, 23.7, 23.5 (d, JPCCC
¼
¼
(21.6 mg, 0.3 mmol, 1 equiv.) and 50 mol% of catalyst (89 mg)
affords 3l (61 mg, 0.207 mmol, 69%) as a colorless oil. 31P NMR
3.2 Hz); HRMS (ESI) m/z calcd for C21H28O2P ([M + H]+) (121 MHz, CDCl3): d ¼ 43.4 (s); 1H NMR (300 MHz, CDCl3): d ¼
342.1749, found 426.0564.
7.81–7.72 (m, 2H), 7.58–7.41 (m, 3H), 4.30–4.16 (m, 1H), 3.65–
Cyclohexyl (3-methylbutan-2-yl)(phenyl)phosphinate (3i). 3.57 (m, 2H), 2.06–1.13 (m, 17H); 13C NMR (75 MHz, CDCl3): d ¼
Following the general procedure A, using cyclohexyl phenyl-H- 132.2 (d, JPCCCC ¼ 2.6 Hz), 132.0 (d, JPC ¼ 123.0 Hz), 131.7 (d,
phosphinate 1a (67.2 mg, 0.3 mmol, 1 equiv.), 2-methylbut-2- JPCCC ¼ 9.8 Hz, 2C), 128.6 (d, JPCC ¼ 12.3 Hz, 2C), 74.6 (d, JPOC
¼
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6.8 Hz), 62.0, 34.5 (d, JPOCC ¼ 2.8 Hz), 33.8 (d, JPOCC ¼ 4.4 Hz), alternative for the preparation and functionalization of P(O)–H
33.5 (d, JPCC ¼ 14 Hz), 29.8 (d, JPC ¼ 101 Hz), 25.3, 23.8, 18.2 (d, bonds. This reaction can be carried out using an ionic liquid
JPCCC ¼ 3.6 Hz) (1 signal missing); HRMS (ESI) m/z calcd for soluble photosensitizer while maintaining good yield. Further-
C
16H26O3P ([M + H]+) 297.1614, found 297.1612.
more, the reaction with hypophosphorous acid is disclosed for
Octyl phosphinic acid (1c). Following the general procedure the rst time. Finally, a continuous ow hydrophosphinylation
B, using 50% aqueous solution of hypophosphorous acid was also reported which allowed faster reaction time with high
(79.2 mg, 0.6 mmol, 2 equiv.), 1-octene 2a (33.6 mg, 0.3 mmol, 1 yields, highlighting the potential of our methodology for rapid
equiv.) and 20 mol% of catalyst (15.5 mg, 0.06 mmol) affords 1b scale up and in-line synthesis. Taking into account the
(29 mg, 0.165 mmol, 55%) as a colorless oil. 31P NMR (121 MHz, simplicity of our reaction conditions we believe this procedure
CDCl3): d ¼ 37.7 (d, JPH ¼ 544 Hz); 1H NMR (300 MHz, CDCl3): will be appealing for further chemical and pharmaceutical
d ¼ 12.53 (br s, 1H), 7.11 (d, JPH ¼ 544 Hz, 1H), 1.85–1.71 (m, applications.
2H), 1.70–1.53 (m, 2H), 1.49–1.24 (m, 10H), 0.91 (t, J ¼ 6.7 Hz,
3H); 13C NMR (75 MHz, CDCl3): d ¼ 31.9, 30.5 (d, JPCC ¼ 16 Hz),
Conflicts of interest
29.4 (d, JPC ¼ 94 Hz), 29.2, 29.1, 22.7, 20.5 (d, JPCCC ¼ 2.7 Hz),
14.2; HRMS (ESI) m/z calcd for C8H20O2P ([M + H]+) 179.1195, There are no conicts to declare.
found 179.1190.
3-Phenylpropyl phosphinic acid (1h). Following the general
procedure B, using 50% aqueous solution of hypophosphorous
Acknowledgements
acid (79.2 mg, 0.6 mmol, 2 equiv.), allylbenzene 2b (35.4 mg, The authors gratefully acknowledge the NMR and Mass Spec-
0.3 mmol, 1 equiv.) and 20 mol% of catalyst (15.5 mg, 0.06 trometry facilities funded by the European Community (FEDER)
´
mmol) affords 1h (34.7 mg, 0.189 mmol, 63%) as a colorless oil. and Region Haut de France (France), the CNRS, and the Uni-
31P NMR (121 MHz, CDCl3): d ¼ 34.2 (d, JPH ¼ 541 Hz); 1H NMR versite de Lille, Sciences et Technologies. The authors thank Dr
´
(300 MHz, CDCl3): d ¼ 7.32–7.24 (m, 2H), 7.23–7.10 (m, 3H), Nassim El Achi for her help with editing this manuscript.
7.07 (d, JPH ¼ 541 Hz, 1H), 2.76–2.63 (m, 2H), 2.02–1.62 (m, 4H);
13C NMR (75 MHz, CDCl3): d ¼ 140.9, 128.6 (4C), 126.4, 36.4 (d,
Notes and references
JPCC ¼ 16 Hz), 28.8 (d, JPC ¼ 94 Hz), 22.4 (d, JPCCC ¼ 2.9 Hz);
HRMS (ESI) m/z calcd for C9H14O2P ([M + H]+) 185.0725, found
185.0720.
1 (a) L. D. Quin, A Guide to Organophosphorous Chemistry,
Wiley Interscience, New York, 2000; (b) New Aspects in
Phosphorous Chemistry, ed. J.-P. Majoral, Springer, Berlin,
2002–2005, vol. 1–5; (c) D. E. C. Corbridge, in Phosphorus:
Chemistry, Biochemistry and Technology; CRC Press:
London, edn 6, 2013.
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3 For selected reviews see:(a) O. Berger and J.-L. Montchamp,
Beilstein J. Org. Chem., 2014, 10, 732; (b) N. Z. Kiss and
G. Keglevich, Curr. Org. Chem., 2014, 18, 2673; (c)
J.-L. Montchamp, Top. Curr. Chem., 2015, 361, 217.
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3601; (b) X.-Q. Pan, J.-P. Zou, W.-B. Yi and W. Zhang,
Tetrahedron, 2015, 71, 7481.
1,2-Dimethylpropyl phosphinic acid (1i). Following the
general procedure B, using 50% aqueous solution of hypo-
phosphorous acid (79.2 mg, 0.6 mmol, 2 equiv.), 2-methylbut-2-
ene 2c (21 mg, 0.3 mmol, 1 equiv.) and 20 mol% of catalyst
(15.5 mg, 0.06 mmol) affords 1i (12.6 mg, 0.09 mmol, 31%) as
a colorless oil. 31P NMR (121 MHz, CDCl3): d ¼ 44.0 (d, JPH ¼ 534
Hz); 1H NMR (300 MHz, CDCl3): d ¼ 8.90 (br s, 1H), 7.01 (d, JPH
¼ 534 Hz, 1H), 2.22–2.04 (m, 1H), 1.72–1.54 (m, 1H), 1.18–0.95
(m, 9H); 13C NMR (75 MHz, CDCl3): d ¼ 39.5 (d, JPC ¼ 94 Hz),
27.1, 21.6 (d, JPCC ¼ 12 Hz), 19.0 (d, JPCC ¼ 5.9 Hz), 7.3; HRMS
(ESI) m/z calcd for C5H14O2P ([M + H]+) 137.0725, found
137.0720.
´
Cyclohexyl phosphinic acid (1j). Following the general
procedure B, using 50% aqueous solution of hypophosphorous
acid (79.2 mg, 0.6 mmol, 2 equiv.), cyclohexene (21 mg,
0.3 mmol, 1 equiv.) and 20 mol% of catalyst (15.5 mg, 0.06
mmol) affords 1k (21.7 mg, 0.147 mmol, 49%) as a colorless oil.
31P NMR (121 MHz, CDCl3): d ¼ 42.8 (d, JPH ¼ 537 Hz); 1H NMR
(300 MHz, CDCl3): d ¼ 6.82 (d, JPH ¼ 537 Hz, 1H), 2.01–1.54 (m,
6H), 1.39–1.14 (m, 5H); 13C NMR (75 MHz, CDCl3): d ¼ 37.6 (d,
JPC ¼ 95 Hz), 26.0 (2C), 25.8, 24.0 (2C); HRMS (ESI) m/z calcd for
C6H14O2P ([M + H]+) 149.0725, found 149.0720.
5 (a) C. Petit, F. Fecourt and J.-L. Montchamp, Adv. Synth.
Catal., 2011, 353, 1883; (b) S. Deprele and
J.-L. Montchamp, J. Am. Chem. Soc., 2002, 124, 9386; (c)
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Org. Chem., 2013, 78, 6599.
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Gen. Chem., 1980, 50, 1416; (b) S. Deprele and
J.-L. Montchamp, J. Org. Chem., 2001, 66, 6745; (c)
O. Dubert, A. Gautier, E. Condamine and S. R. Piettre, Org.
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Conclusions
In conclusion, we developed an efficient UV-mediated hydro-
phosphinylation of unactivated alkenes with H-phosphinate
under free radical conditions giving a straightforward access to
a wide range of phosphorous compounds providing a metal free
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(b) G. Porter and P. Suppan, Faraday Trans., 1965, 61, 1664;
(c) J. Lalevee, F. Morlet-Savary, M. A. Tehfe, B. Graff and
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a
´
´
M. Marazzi, S. Mai, D. Roca-Sanjuan, M. l. G. Delcey,
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R. Lindh, L. Gonzalez and A. Monari, J. Phys. Chem. Lett.,
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Z. J. Garlets, J. D. Nguyen and C. R. J. Stephenson, Isr. J.
Chem., 2014, 54, 351; (b) Y. H. Su, N. J. W. Straathof,
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´
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and C. Rolando, New J. Chem., 2016, 40, 9460; (b) N. El 643, 154.
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chromatography failed or conducted in a very low yield.
Purity was determined by 31P NMR on a sample by mixing
it with phenylphosphinic acid as a standard.
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8392 | RSC Adv., 2018, 8, 8385–8392
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