Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

Article abstract of DOI:10.1039/c6gc00903d

The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of diphenylphosphine to alkenes and alkynes, respectively, in the absence of a solvent and a catalyst. In the presence of elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.

Full text of DOI:10.1039/c6gc00903d

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Moglie, M. J.
González-Soria, I. Martín-García, G. Radivoy and F. Alonso, Green Chem., 2016, DOI:
10.1039/C6GC00903D.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/greenchem

Please do not adjust margins
Page 1 of 11
Green Chemistry
View Article Online
DOI: 10.1039/C6GC00903D
Journal Name
ARTICLE
Catalyst- and solvent-free hydrophosphination and
multicomponent hydrothiophosphination of alkenes and alkynes
Received 00th January 20xx,
Accepted 00th January 20xx
Yanina Mogliea,†, María José González-Soria,a Iris Martín-García,a Gabriel Radivoyb and Francisco
Alonso,a,*
DOI: 10.1039/x0xx00000x
The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal
catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of
diphenylphosphine to alkenes and alkynes, respectively, in the absence of solvent and catalyst. In the presence of
elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component
process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards
the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the
reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.
www.rsc.org/
Introduction
The deployment of phosphorus compounds in industry has
become widespread because of their manifold applications.1
Nowadays, many chemical, agrochemical and pharmaceutical
substances containing phosphorus are routinely produced to
control some natural or human-triggered processes and to
upgrade the quality of our lives. Research laboratories also
make extensive use of organophosphorus compounds,
particularly as ligands for homogeneous, heterogeneous and
asymmetric catalysis,2a-i but also as organocatalysts.2j,k Metal-
phosphine complexes with anticancer activity is another field
of recent interest aimed to develop substitutes of the current
platinum drugs.3 Phosphines can be synthesized using different
procedures (Scheme 1), such as (a) the displacement of a good
leaving group on a phosphine by an organometallic reagent
(eq. 1), (b) the reaction of a metal phosphide with an organic
electrophile (eq. 2), (c) the reduction of a phosphorus halide or
oxide (eq. 3), (d) from elemental phosphorus (eq. 4) and (e) by
phosphination (i.e., the metal-catalysed cross-coupling of aryl
halides or triflates with P–H bonds; eq. 5).4
Scheme 1. Some general methods for tertiary phosphine synthesis; M = metal, X =
leaving group; n = 2, m = 1 and n =1, m = 2.
straightforward approach to form C–P bonds from readily
accessible starting materials (Scheme 1, eq. 6);6 maximum
atom economy is attained with no by-product formation.
Closely related to phosphines are the phosphine sulfides,7 a
type of compounds with multiple applications in different
disciplines. Among others, phosphine sulfides have been
utilized in anion-selective electrodes,8 lanthanide extraction
from a nitrate medium,9 as sensor fluorescent materials for
metal ions of environmental concern,10 as anchor units for
single molecule junctions,11 in polymer chemistry,12 and as
ligands for gold,13 catalysis14 and asymmetric synthesis.15 Base-
promoted16 or free-radical17 initiated addition of secondary
phosphine sulfides to alkenes (or alkynes)7 are the most
practiced methods to prepare tertiary phosphine sulfides. The
reaction of secondary phosphine sulfides with carbonyl
Modern chemical research and production must advance on
the basis of sustainable and environmentally benign practices.5
In this vein, the hydrophosphination of unsaturated
compounds (i.e., alkenes and alkynes) appears as the most
a. Instituto de Síntesis Orgánica (ISO) and Departamento de Química Orgánica,
Facultad de Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain; E-
mail: falonso@ua.es
b. Departamento de Química, Instituto de Química del Sur (INQUISUR-CONICET),
Universidad Nacional del Sur, Avenida Alem 1253, 8000 Bahía Blanca, Argentina
†
Present address: Departamento de Química, Instituto de Química del Sur
(INQUISUR-CONICET), Universidad Nacional del Sur, Avenida Alem 1253, 8000
Bahía Blanca, Argentina
Electronic Supplementary Information (ESI) available: [experimental procedures,
compound characterisation, NMR spectra, kinetic graphics and X-ray data]. See
DOI: 10.1039/x0xx00000x
compounds can provide tertiary
-hydroxy phosphine
sulfides.7 The transformation of pre-formed tertiary
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 2 of 11
ARTICLE
Journal Name
phosphines into the corresponding sulfides can be readily sustainable production because of the use of non-reusable
View Article Online
DOI: 10.1039/C6GC00903D
accomplished by reaction with sulphur; in this case, however, precious metals or noxious solvents (e.g., benzene). In
hazardous solvents such as benzene, chloroform or addition, transition metals can accelerate the undesired
dichloromethane are required.7 More recently, Trofimov et al. phosphine oxidation to the phosphine oxide. Ideally, this
reported the one-pot synthesis of tertiary phosphine sulfides reaction should be conducted under metal-free and neutral
from styrenes, red phosphorus and elemental sulfur in a conditions, with the latter also preventing side-reactions and
superbasic system containing hydroquinone under microwave use of aqueous work-up (which can favour oxidation). To the
irradiation.18 In addition to these, transition-metal catalyzed best of our knowledge, Gaumont’s group was the first in
procedures have been recently published.19
reporting the uncatalysed hydrophosphination of alkenes:
On the other hand, both solvent-free reactions20 and catalyst- phosphane-borane complexes were added to inactivated
free organic synthesis21 notably simplify the reaction mixtures alkenes under neutral conditions and either conventional or
and experimental, at the same time that reduce the amount of microwave heating.32
waste which, in turn, depletes the environmental impact.
Following our recent discovery on the uncatalysed addition of
By virtue of our current interest on phosphorus chemistry,22 secondary phosphines to carbon-carbon double bonds under
we found out that tertiary phosphines can be obtained in a solvent-free conditions,22a we expanded this practice to the
very straightforward manner by addition of secondary addition of diphenylphosphine to a wide range of alkenes,
phosphines to carbon-carbon double bonds under solvent and including not only styrenes but
catalyst-free conditions.22a Moreover, under these conditions compounds and inactivated alkenes (Tables 1–3). All reactions
but in the presence of sulfur, -unsaturated carbonyl were executed under an inert atmosphere of argon.
compounds have been converted into the corresponding As regards styrenes, the simplest one (1a) reacted the fastest
-unsaturated carbonyl
-
substituted tertiary phosphine sulfide derivatives through a and in good yield. p-Halostyrenes (1b and 1c), p-methoxy- and
three-component approach (Scheme 2).22b Our intent is to p-acetoxystyrene (1d and 1e, respectively) behaved similarly in
present herein a comprehensive study on the substrate scope terms of yield (around 85%), with a shorter reaction time for
and mechanism of these environmentally friendly protocols, 2d. This hydrophosphination was also appropriate for vinyl
including the hydrophosphination and multicomponent pyridines (1f and 1g), permitting the synthesis of the P,N-
hydrothiophosphination of alkenes and alkynes.
bidentate ligand pyphos (2g), used in homogeneous transition-
metal catalysis.33 Other vinyl aromatics, such as 2-
vinylnaphthalene (1h) and 4-vinyl-1,1'-biphenyl (1i) were
transformed into the tertiary phosphines in high yields.
Furthermore, the standard conditions were also effectual for
the less reactive 1,1-disubstituted alkene isopropenyl benzene
(
1j). We must underline that all products 2a-2j were produced
with exclusive anti-Markovnikov regioselectivity.
We next explored the diphenylphosphine addition to
Scheme
2.
Solvent-
and
catalyst-free
hydrophosphination22a
and
-
hydrothiophosphination22b of alkenes; EWG = electron-withdrawing group.
unsaturated carbonyl and related compounds (Table 2). These
substrates can be considered more activated alkenes than the
aforesaid styrenes and, hence, more reactive under milder
conditions. Indeed, most of the starting alkenes (except 1l and
1q) experienced hydrophosphination at room temperature (7–
12 h); alternatively, the reaction times could be decreased (1–
3 h) by warming at 70 ºC with comparable yields (see 1k, 1n
and 1p). Diverse functional groups were compatible with these
conditions, whereby the synthesis of -diphenylphosphino
ketones (1k-1m), esters (1n and 1o), nitrile (1p), amides (1p
and 1q) and phosphonate (1s) was carried out in good yields;
products 2l and 2r were isolated as the phosphine oxides due
to easy oxidation of the phosphine precursors when exposed
to air. It is worth noting that the platinum-catalysed24 addition
of diphenylphosphine to acrylonitrile (1p) can instead be
effectuated in the absence of catalyst at room temperature.
Heteroatom-bonded vinyl compounds, such as N-
vinylphthalimide (1t), N-vinylpyrrolidin-2-one (1u) and phenyl
vinyl sulfide (1v) gave the expected diphenylphosphino(ethyl)
heteroatom products under the conventional conditions (70
ºC) (Table 3). Compound 2v is a P,S-bidentate ligand also
employed in catalysis.34 The usefulness of this protocol was
validated by its exploitation in the hydrophosphination of
Results and discussion
Alkene hydrophosphination
Originally, alkene hydrophosphination6 was induced by base
catalysis or radical activation to form the anti-Markovnikov
products,6c whereas the Markovnikov counterparts were
better obtained by acid treatment.23 More advantageous
were, however, the methodologies based on catalysis by
metal6 complexes, such as those of platinum,24 lanthanides,25
alkaline-earth metals,25e,f,26 nickel,27 palladium27 or iron.28 Of
particular
interest
is
the
catalytic
asymmetric
hydrophosphination of certain substrates which was achieved
by the use of chiral organopalladium(II) complexes.29 Not only
metal complexes but metal salts of copper30 or iron31 have
been also utilized as catalysts in alkene hydrophosphination.
With the exception of the Pd- and Ni-catalysed
hydrophosphination of vinyl ethers,27c,27d the aforementioned
methodologies afford the anti-Markovnikov products.
In spite of the higher selectivity reached by metal catalysis,
most of its applications in alkene hydrophosphination does not
meet some of the stringent criteria demanded for green and
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 11
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
Table 1 Hydrophosphination of styrenes.a
Table 2 Hydrophosphination of activated alkenes.a
View Article Online
DOI: 10.1039/C6GC00903D
Starting alkene
Product
Yield (%)b
Starting alkene
t/T
Product
Yield (%)b
a
b
Alkene 1 (0.5 mmol) and Ph2PH (0.5 mmol) at rt or 70 ºC under Ar. Isolated
yield.
susceptible to oxidation and were isolated as the phosphine
oxides 2x and 2y, respectively. It was gratifying to verify that
the hydrophosphination of (–)- -pinene (1z) followed an anti-
Markovnivov addition and involved the opening of the
cyclobutane ring to supply the enantiomerically pure p-menth-
1-ene derived phosphine oxide 2z. Unmistakable assignment
of the structure was done by X-ray crystallographic analysis
(Figure 1).35
a
Alkene 1 (0.5 mmol) and Ph2PH (0.5 mmol) at 70 ºC under Ar, 16 h (unless
otherwise stated). b Isolated yield. c Reaction time = 4 h. d Reaction time = 8 h.
inactivated alkenes such as allylbenzene (1x) and oct-1-ene
(
the trend displayed by all substrates in Tables 1–3. Still, the
tertiary phosphines originated from 1x and 1y were
1y). The anti-Markovnivov regioselectivity was consistent with
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 4 of 11
ARTICLE
Journal Name
Table 3 Hydrophosphination of Het-vinyl compounds and inactivated alkenes.a
View Article Online
DOI: 10.1039/C6GC00903D
Starting alkene
Product
Yield (%)b
Figure 1. X-ray crystallographic structure of phosphine oxide 2z.
depicted in Table 4.
A variety of electron-neutral, -rich and -deficient styrenes
underwent the hydrothiophosphination reaction at 70 ºC in
air; the corresponding products (3a, 3b, 3v, 3e and 3x) were
obtained in moderate-to-excellent isolated yields (Table 4).
Likewise, styrenes bearing N and S atoms, as well as
allylbenzene, were successfully converted into phosphine
sulfides (3f, 3g, 3m and 3n). It is worth noting that the process
was highly regioselective, giving rise in all cases to the anti-
Markovnikov products. The same conditions were applicable
to aliphatic substrates, such as oct-1-ene (1o) and 3,4-dihydro-
2H-pyran (1y). Despite the lack of regioselectivity observed for
oct-1-ene, both regioisomers (3o and 3o’) could be separated
by chromatography in reasonable yields, as a result of the
quantitative reaction conversion. In contrast, the
hydrothiophosphination of 3,4-dihydro-2H-pyran (1y) led to a
single regioisomer (3y), derived from the addition of P to the
-O carbon atom.
a Alkene 1 (0.5 mmol) and Ph2PH (0.5 mmol) at 70 ºC (1t-v) or 100 ºC (1x-z) under
Ar, 16-24 h. b Isolated yield.
Alkene hydrothiophosphination
Apart from the base-promoted16 and free-radical17 initiated
addition of secondary phosphine sulfides to alkenes, and
related to the title topic, is the recent synthesis of tertiary
phosphine sulfides by addition of secondary phosphine
sulfides to alkenes in the absence of solvent and catalyst.36
Reactions were performed at 80 ºC in an inert atmosphere to
give the anti-Markovnikov products.
Alkyne hydrophosphination
Comparatively, alkyne hydrophosphination has been much less
studied that alkene hydrophosphination. Beletskaya et al.
reported, for the first time, the hydrophosphination of alkynes
catalyzed by palladium and nickel complexes; interestingly,
depending on the metal used the - or -adduct was mainly
formed, with predominant syn addition.37 Other metal
complexes or salts (i.e., Yb, Pd, Ni, Cu, Ca, Fe and Y) have been
deployed for the same purpose with variable selectivity.25e,38
In our preliminary communication,22a we observed that
phenylacetylene could also undergo diphenylphosphine
addition under solvent- and catalyst-free conditions. A variety
In
a
previous study,22b we evidenced that alkene
hydrothiophosphination could be achieved through a three-
component approach involving the alkene, diphenylphosphine
and sulfur, under solvent- and catalyst-free conditions in air.
This is an advantageous strategy not only from the
environmental point of view, but also because circumvents the
preparation of the secondary phosphine sulfide, which is
generated in situ. Only
-unsaturated carbonyl compounds
were covered in that preliminary study; the results obtained
for other alkenes, either activated or not activated, are
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 11
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
Table 4 Alkene hydrothiophosphination.a
of alkynes has been subjected to this simple procedure to
produce vinylphosphines in a regio- and stereoselective
View Article Online
DOI: 10.1039/C6GC00903D
manner (Table 5).
Electron-neutral and -rich arylacetylenes reacted nicely with
diphenylphosphine at 70 ºC yielding the expected anti-
Starting alkene
Product
Yield (%)b
Markovnikov
alkenylphosphines
(
5a
-
5e)
as
Z
diastereoisomers.39 Converse behaviour was observed for
arylacetylenes bearing electron-withdrawing substituents (e.g.,
4f), which were reluctant to react under the same conditions.
When methyl(phenyl)acetylene (4g) was submitted to the
standard
reaction
conditions,
the
corresponding
vinylphosphine was formed as a 90:10 E/Z diastereomeric
mixture, with opposite regioselectivity to that reported with a
calcium complex.38d Besides arylacetylenes, aliphatic alkynes
also experienced hydrophosphination. The alkyl-chain alkyne
4h was converted into the phosphine 5h with a high degree of
stereocontrol (97:3 Z/E ratio), whereas the tertiary phosphines
resulting from the cyclohexyl derivatives 4i and 4j were prone
to rapid oxidation, being obtained as the phosphine oxides 5i
and 5j, respectively. A 60:40 Z/E ratio was recorded for 5i
,
though the major Z isomer could be isolated in moderate yield.
Different outcome arose for the hydroxyl derivative 5j, with
absolute control of both the regio- and the stereochemistry.
Alkyne hydrothiophosphination
Trofimov et al. have recently extended their addition of pre-
formed secondary phosphine sulfides to alkenes, under
catalyst- and solvent-free conditions, to alkynes, giving the
tertiary anti-Markovnikov alkenylphosphine sulfides with Z
stereochemistry.40 With a more straightforward approach in
hand, and based on our previously reported three-component
alkene
hydrothiophosphination,22b
the
hydrothiophosphination was undertaken for a series of alkynes
(Table 6). The standard reaction conditions, in air, were
applied to obtain alkenylphosphine sulfides in high yields from
diphenylphosphine, sulfur and phenylacetylenes bearing
electron-neutral, -donating and -withdrawing substituents (4a
-
4d and 4k). As occurred in the alkyne hydrophosphination, the
hydrothiophosphination of 4-trifluoromethyl(phenyl)acetylene
was troublesome, giving the expected product 6f in low yield.
The same conditions were suitable for aliphatic alkynes, either
linear-alkyl or cycloalkyl-substituted ones (4h and 4i).
It must be pointed out that all the alkenylphosphine sulfides
were synthesised as single anti-Markovnikov regioisomers and
Z
stereoisomers. The stereochemistry of the alkyne
hydrothiophosphination and, therefore, that of the alkyne
hydrophosphination was unequivocally established by X-ray
crystallographic analysis of alkenylphosphine sulfide 6a (Figure
2).41
Mechanistic aspects
Koenig et al. concluded that the radical or ionic mechanism of
addition of organophosphorus compounds containing a labile
P-H bond to alkenes and alkynes was dependent on the nature
of the unsaturated substrate (activated or inactivated), the
nature of the organophosphorus compound (with P-H, O=P-H
or S=P-H bonds) and the mode of activation (dry alkaline
a
Alkene 1 (0.5 mmol), Ph2PH (0.5 mmol) and S (0.5 mmol) at 70 ºC in air,
overnight. b Isolated yield. c Reaction at 120 ºC. d Reaction at 100 ºC.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 6 of 11
ARTICLE
Journal Name
Table 5 Alkyne hydrophosphination.a
Table 6 Alkyne hydrothiophosphination.a
View Article Online
DOI: 10.1039/C6GC00903D
Starting alkyne
Product
Yield (%)b
Starting alkyne
Product
Yield (%)b
a
Alkyne 4 (0.5 mmol), Ph2PH (0.5 mmol) and S (0.5 mmol) at 70 ºC in air,
overnight. b Isolated yield.
medium, alkaline medium/classical heating, US irradiation,
alkaline medium/US irradiation, radical initiator/classical
heating or photochemical irradiation).42
a
b
Alkyne 4 (0.5 mmol) and Ph2PH (0.5 mmol) at 70 ºC under argon, overnight.
Isolated yield. c As a 95:5 Z/E diastereomeric mixture. d GLC yield. e As a 90:10 E/Z
In order to get an insight into the reaction mechanism, the
f
g
diastereomeric mixture As a 97:3 Z/E diastereomeric mixture. Yield of the hydrophosphination of styrene was performed in the presence
major diastereoisomer, isolated from a 60:40 Z/E diastereomeric mixture.
of radical traps, such as cumene, TEMPO or 2,6-di-tert-
butylphenol [Scheme 3, eq. (1)]. All reactions proceeded
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 11
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
View Article Online
DOI: 10.1039/C6GC00903D
Scheme 5. Deuterium-labelling experiments in the hydrophosphination of 4i.
gave the Z -deuteriovinylphosphine oxide D1-5i with 80% D
incorporation. This essay ratifies the anti addition of the P–H
bond across the carbon-carbon triple bond which, apparently,
can involve some H/D scrambling (Scheme 5).
We also compared the rate of addition of Ph2PH to styrene at
70 ºC with that of Ph2PD (Figure 3). A kinetic isotopic effect
was manifested, which was especially dramatic in the range 0–
50 min (induction period for Ph2PD) and points to the cleavage
of the P–H bond as being the rate-determining step of the
reaction.
The effect of the stoichiometry of the reactants was also
investigated for the addition of diphenylphosphine to styrene,
in this case, in the range 10–60 min (Figure 4). It is clear that,
with respect to a 1:1 stoichiometric ratio, the excess of styrene
has a negligible effect on the formation of 2a, whereas an
excess of diphenylphosphine speeds up its formation (e.g., >5-
fold at 10 min by doubling the amount of diphenylphosphine).
This effect was expected to be more prominent at shorter
reaction times.44 Larger amounts of diphenylphosphine (e.g.,
1:3 ratio) were shown to be unproductive with respect to the
1:2 ratio, displaying a very similar trend.
Figure 2. X-ray crystallographic structure of phosphine sulfide 6a.
with >96% conversion and products derived from the radical
traps and diphenylphosphinyl radicals were not detected.
These results, together with the fact that the addition of
diphenylphosphine to hepta-1,6-diene did not yield the
corresponding cyclopentane derivative [Scheme 3, eq. (2)],43
point to a radical-free process. This hypothesis is consistent
with the Z to E isomerisation observed for alkenylphosphine
derivatives 5a and 5i under radical conditions (Scheme 4); that
is, the thermodynamic
E isomers, instead of the Z
counterparts, should be largely formed if the
hydrophosphination was driven by radicals. It must be
highlighted that E/Z equilibration did not occur when the
alkenyl phosphines 5a and 5i were subjected to prolonged
heating either in the absence or presence of iodine.
A series of deuterium-labelling experiments brought into view
additional evidence on the reaction course. The addition of
diphenylphosphine to deuterated cyclohexylacetylene D1-4i
0,25
2a
(mmol)
0,2
0,15
DPP{H}
DPP{D}
0,1
0,05
0
0
50
100
150
200
t (min)
Figure 3. Kinetic profiles for the reaction of styrene (1a) with protio- and
deuteriodiphenylphosphine, DPP{H} and DPP{D}, respectively, at 70 ºC under Ar.
Scheme 3. Experiments demonstrating the radical-free addition of diphenylphosphine
to alkenes.
0,6
2a
(mmol)
0,5
0,4
0,3
0,2
0,1
0
1a/DPP (1:1)
1a/DPP (2:1)
1a/DPP (3:1)
1a/DPP (1:2)
1a/DPP (1:3)
0
10
20
30
40
50
60
time (min)
Figure 4. Effect of the styrene (1a)/diphenylphosphine (DPP) ratio on the formation of
2a in the 10–60 min range, at 70 ºC under Ar. The amount of 2a is referred to the
limiting substrate.
Scheme 4. Radical-promoted Z/E isomerisation of alkenyl phosphine derivatives.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 8 of 11
ARTICLE
Journal Name
Considering the close electronegativities of P ( = 2.19) and H
= 2.20), in principle it might be presumed that the anti-
View Article Online
DOI: 10.1039/C6GC00903D
(
Markovnikov regioselectivity for the hydrophosphination
(particularly, that of inactivated substrates) is primarily
governed by steric rather than by electronic factors. In this
context, substrates leading to more sterically hindered
products, such as stilbene of diphenylacetylene, reacted
sluggishly with diphenylphosphine either in the presence or
absence of sulfur. A hydroboration-type model, in which the
B–H bond adds through a four-membered ring transition state
Scheme 7. Diphenylphosphine sulfide as intermediate in the three-component
synthesis of alkylphosphine sulfides.
Comparison with other catalysts
Although an array of effective catalysts has been designed for
the hydrophosphination of alkenes, some operating even at
room temperature, in practice, the results do not differ so
much from those attained in the absence of solvent and
catalyst (Table 7). Moreover, most of these results are based
on NMR conversions (instead of isolated yields) and small-
scale reactions performed in NMR tubes, what curtails the
potential scope of the method. By the same token, the usage
of an excess of the starting alkene in some of the methods has
a negative effect on the E-factor.
Similar comments can be extended to the hydrophosphination
of alkynes, in this case exemplified by the addition of
diphenylphosphine to phenylacetylene (Table 8). The vinyl
phosphine 5a can be obtained without catalyst and solvent,
not only in good isolated yield but in the highest E/Z
diastereoselectivity (entry 6). Taking into account different
parameters (catalyst, solvent, temperature, time, yield and
selectivity), together with the simplicity of the procedure, we
can state that this approach to the addition of the P–H bond to
alkenes and alkynes distinctly outperforms others based on
catalytic approaches.
must be disregarded because (a) the B–H bond ( = 2.04) is
B
more polarized than the P–H bond and this circumstance
works in the same direction as the steric factor in the former,
and (b) the hydroboration is syn whereas the
hydrophosphination is anti [Scheme 6, eq. (a)].
The above experiments and considerations lend weight to the
argument that the hydrophosphination reaction follows an
ionic pathway with anti addition, where the P and H atoms
come each from two different phosphine molecules. The
ability of tertiary phosphines to act as nucleophilic catalysts in
the addition to alkenes (especially, , -unsaturated carbonyl
compounds) is well known.45 Therefore, it seems reasonable to
propose that one phosphine molecule has a nucleophilic role,
by addition to the terminal carbon atom of the alkene, while a
second molecule behaves as the electrophilic partner through
its hydrogen atom [Scheme 6, eq. (b)].
With the proposed transition state model, electronic factors
also go into play as the negative charge density developed in
the transition state is especially stabilised at the benzylic
position (e.g., in the styrenes) as well as at the -position with
respect to heteroatoms (in Het-vinyl substrates) and carbonyl
groups (in , -unsaturated carbonyl compounds). In the case
Conclusions
of 3,4-dihydro-2H-pyran (1y), with a near symmetric carbon-
For decades, the addition of the P-H bond across multiple
carbon-carbon bonds has been associated with activation by
base, acid, radicals or metals. We have demonstrated that
tertiary phosphines can be readily prepared by thermal
treatment of secondary phosphines and alkenes in the
carbon double bond, electronic factors seem to prevail with
addition of the P atom to the most electrophilic -C atom
(Table 4). Further support for the interpretation made of the
hydrophosphination comes from the addition of Ph2PH to
-
pinene (1z): the formation of the ring-opened product 2z
(Table 3) seems more feasible if two molecules of
diphenylphosphine are implicated in the reaction.
Table 7 Addition of diphenylphosphine to styrene.
Concerning the three-component syntheses of alkyl and
alkenyl phosphine sulfides, we earlier confirmed that in situ
formation of diphenylphosphine sulfide comes off prior to the
addition (Scheme 7).22b
Entry
146
Catalyst (mol%)
t-BuOK (20)
Ni[P(OEt)3]4 (5)
Solvent
DMSO
C6H6
C6H6
dioxane-d8
MeCN
C6D6
T (ºC) Time (h) Yield (%)a
rt
130
75
100
60
25
60
60
rt
1
20
20
18–24
12
3
0.4
4
24
4
83
92
b
227b
326a Ca-amide complex (10)
64c (95)d
83
430
531
Cu(OTf)2·PhMe (10)
FeCl2 (30)
87e
625e
725f
825g
928
Ca-amide complex (2)
Ba-amide complex (2)
Yb(II) complex (1)
Fe(III) complex (0.5)
none
(100)d
(>96)d
(92)d
89
C6D6
C6D6
MeCNf
none
10
70
82g
a Isolated yield unless otherwise stated; conversion in parentheses. b 2.0 equiv. of
c
d
styrene; 1 equiv. of Et3N. Isolated yield of the phosphine oxide. Conversion
e
f
g
determined by NMR. Isolated as the borane complex. 1.82 equiv. of alkene.
This work.
Scheme 6. Mechanistic proposals for the hydrophosphination of carbon-carbon double
bonds following (a) a syn addition (hydroboration-type model) and (b) an anti addition.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 11
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
Table 8 Addition of diphenylphosphine to phenylacetylene.
Experimental
View Article Online
DOI: 10.1039/C6GC00903D
General procedure for the hydrophosphination of alkenes 1. All
reactions were performed using tubes in a multi-reactor
system under argon. Diphenylphosphine (0.5 mmol, 87 L) and
the alkene (1, 0.5 mmol) were stirred during the specified time
at room temperature, 70 or 100 ºC (Tables 1–3). The progress
of the reaction was monitored by TLC and/or GLC until total or
steady conversion was achieved. The resulting mixture was
dissolved in EtOAc (20 mL) followed by the addition of silica gel
and removal of the excess of solvent in vacuo. The reaction
crude absorbed on silicagel was subjected to column
chromatography (silica gel, hexane/EtOAc) to give the pure
Entry
137
Catalyst (mol%)
Pd(PPh3)4 (1.2)
Solvent
MeCN
T (ºC)
130
Time
18 h
Yield (%)a
95b
(86/14)
238a
325e
425e
538f
6
Yb-imine complex (5)
Ca-amide complex (5)
Yb-amide complex (5)
Y complex (2)
THF
C6D6
C6D6
C6D6
none
rt
5 min
38 h
38 h
72 h
10
>99c
(24/76)
78d
75
75
70
70
(76/24)
91d
(10/90)
100d
tertiary phosphines 2. The phosphine oxides 2x, 2y and 2z
were purified by preparative chromatography (silica gel,
hexane/EtOAc).
(42/58)
none
80e
(95/5)
General procedure for the hydrothiophosphination of alkenes
Z/E ratio in parenthesis. 31P NMR yield. GC yield of the phosphine oxide.
a
b
c
d
1
. All reactions were performed using tubes in a multi-reactor
system under air. Diphenylphosphine (0.5 mmol, 87 L), the
alkene ( , 0.5 mmol) and elemental sulfur (0.5 mmol, 16.0 mg)
Conversion determined by NMR. e This work; isolated yield.
1
absence of solvent and catalysts, under an inert atmosphere.
The method is applicable to -unsaturated carbonyl
were stirred at 70, 100 or 120 ºC overnight (Table 4). The
progress of the reaction was monitored by TLC and/or GLC
until total or steady conversion was achieved. The resulting
mixture was dissolved in EtOAc (20 mL) followed by the
addition of silica gel and removal of the excess of solvent in
vacuo. The reaction crude absorbed on silicagel was subjected
to column chromatography (silica gel, hexane/EtOAc) to give
the pure tertiary phosphine sulfides 3. Compounds 3b, 3e, 3n
and 3y were purified by preparative chromatography (silica
gel, hexane/EtOAc).
compounds, styrenes, N- and S-vinyl compounds, as well as
inactivated alkenes. The process is highly regioselective
producing the tertiary phosphines in an anti-Markovnikov
fashion. Alkynes undergo the same type of addition to furnish
anti-Markovnikov alkenyl phosphines with Z stereoselectivity.
Furthermore, by including elemental sulfur into the reaction
mixture in air, alkyl and alkenyl phosphine sulfides can be
readily synthesised through
a one-pot three-component
approach in a regio- and stereoselective manner. Compelling
experimental evidence suggests an ionic-type reaction
mechanism governed by steric and electronic effects different
from that of the alkene/alkyne hydroboration.
General procedure for the hydrophosphination of alkynes 4.
All reactions were performed using tubes in a multi-reactor
system under argon. Diphenylphosphine (0.5 mmol, 87 L) and
the alkyne (4, 0.5 mmol) were stirred at 70 ºC overnight (Table
These methods are in agreement with some of the twelve
principles introduced by Anastas et al.,5a namely: (a) waste is
prevented because of no by-product formation, (b) high atom
economy, as all the starting materials are incorporated into
the final products, (c) unnecessary use of solvents, (d) some
reactions proceed at room temperature and most of them at
70 ºC, (e) unnecessary derivatisation (the secondary phosphine
sulfides are generated in situ) and (f) neither stoichiometric
nor catalytic reagents are employed because the processes are
catalyst free. In addition to this, similar or better results are
obtained with respect to the catalytic methods.
5). The progress of the reaction was monitored by TLC and/or
GLC until total or steady conversion was achieved. The
resulting mixture was dissolved in EtOAc (20 mL) followed by
the addition of silica gel and removal of the excess of solvent
in vacuo. The reaction crude absorbed on silicagel was
subjected to column chromatography (silica gel,
hexane/EtOAc) to give the pure alkenyl phosphines 5.
General procedure for the hydrothiophosphination of alkynes
4. All reactions were performed using tubes in a multi-reactor
system under air. Diphenylphosphine (0.5 mmol, 87 L), the
alkyne (4, 0.5 mmol) and elemental sulfur (0.5 mmol, 16.0 mg)
In short, this study supports the statements by Sheldon that
“the best catalyst is no catalyst” and “the best solvent is no
solvent”.47
were stirred at 70 ºC overnight (Table 6). The progress of the
reaction was monitored by TLC and/or GLC until total or steady
conversion was achieved. The resulting mixture was dissolved
in EtOAc (20 mL) followed by the addition of silica gel and
removal of the excess of solvent in vacuo. The reaction crude
absorbed on silicagel was subjected to column
chromatography (silica gel, hexane/EtOAc) to give the pure
Acknowledgements
This work was generously supported by the Spanish Ministerio
de Economía y Competitividad (MINECO; CTQ2011-24151). Y.
M. and I. M.-G. acknowledge the Instituto de Síntesis Orgánica
(ISO) of the Universidad de Alicante for the grants. M. J. G.-S.
thanks the ISO and the Generalitat Valenciana (grant nº
APOTIP/2015/014) for financial support.
alkenyl phosphine sulfides 6.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 10 of 11
ARTICLE
Journal Name
15 (a) C. J. Chapman, C. G. Frost, M. P. Gill-Carey, G. Kociok-Köhn,
M. F. Mahon, A. S. Weller and M .C. Willis,ViTewetArratichleedOrnolinne:
Asymmetry, 2003, 14, 705–710; (b) E.DIOchI:i1k0a.w10a3,9/MC.6GSCuz0u0k9i0,3KD.
Yabu, M. Albert, M. Kanai and M. Shibasaki, J. Am. Chem. Soc.,
2004, 126, 11808–11809.
16 (a) S. R. Gilberston and X. Wang, J. Org. Chem., 1996, 61, 434–
435; (b) N. K. Gusarova, M. V. Bogdanova, N. I. Ivanova, N. A.
Chernysheva, B. G. Sukhov, L. M. Sinegovskaya, O. N. Kazheva,
G. G. Alexandrov, O. A. D’yachenko and B. A. Trofimov,
Synthesis, 2005, 3103–3106; (c) N. K. Gusarova, M. V.
Bogdanova, N. I. Ivanova, N. A. Chernysheva, A. A. Tatarinova
and B. A. Trofimov, Russ. J. Gen. Chem. 2006, 76, 1201–1204;
(d) N. K. Gusarova, S. F. Malysheva, N. A. Belogorlova, V. A.
Kuimov, I. A. Ushakov and B. A. Trofimov, Russ. Chem. Bull, Int.
Ed., 2009, 58, 234–237.
Notes and references
1
L. D. Quin, A Guide to Organophosphorus Chemistry, Wiley-
Interscience, New York, 2000.
2
For recent reviews and monographs, see: (a) Phosphorus
Ligands in Asymmetric Catalysis: Synthesis and Applications, ed.
A. Börner, Wiley-VCH, Weinheim, 2008; (b) P. E. Goudriann, P.
W. N. M. van Leeuwen, M.-N. Birkholz and J. N. H. Reek, Eur. J.
Org. Chem., 2008, 2939–2958; (c) S. Lühr, J. Holz and A. Börner,
ChemCatChem, 2011, 3, 1708–1730; (d) J. Wassenaar and J. N.
H. Reek, Org. Biomol. Chem., 2011, 9, 1704; (e) F. L. Lam, F. K.
Kwong and A. S. C. Chan, Top. Organomet. Chem., 2011, 36, 29–
66; (f) S. Lühr, J. Holz and A. Börner, ChemCatChem, 2011, 3,
1708–1730; (g) H. Fernández-Pérez, P. Etayo, A. Panossian and
A. Vidal-Ferran, Chem. Rev., 2011, 111, 2119–2176; (h)
Privileged Chiral Ligands and Catalysis, ed. Q.-L. Zhou, Wiley-
VCH, Weinheim, 2011; (i) Phosphorus(III) Ligands in
Homogeneous Catalysis: Design and Synthesis, ed. P. C. J. Kamer
and P. W. N. M. van Leeuwen, John Wiley & Sons, Chichester,
2012; (j) Y. C. Fan and O. Kwon, Chem. Commun., 2013, 49,
11588–11619; (k) Y. Xiao, H. Guo and O. Kwon, Aldrichim. Acta,
2016, 49, 3–13.
17 (a) A. F. Parsons, D. J. Sharpe, P. Taylor, Synlett, 2005, 2981–
2983; (b) N. K. Gusarova, M. V. Bogdanova, N. I. Ivanova, N. A.
Chernysheva, S. V. Yas’ko, V. G. Samoilov, S. M. Markosyan and
B. A. Trofimov, Russ. J. Gen. Chem., 2006, 76, 1514–1515; (c) B.
A. Trofimov, S. F. Malysheva, N. K. Gusarova, N. A. Belogorlova,
S. F. Vasilevsky, V. B. Kobychev, B. G. Sukhov, I. A. Ushakov,
Mendeleev Commun., 2007, 17, 181–182; (d) L. A. Oparina, S. F.
Malysheva, N. K. Gusarova, N. A. Belogorlova, O. V. Vysotskaya,
A. V. Stepanov, A. I. Albanov and B. A. Trofimov, Synthesis,
2009, 3427–3432; (e) N. A. Chernysheva, S. V. Yas’ko, N. K.
Gusarova, A. A. Tatarinova, L. V. Klyba, B. A. Trofimov,
Mendeleev. Commun., 2010, 20, 346–347. (f) N. K. Gusarova, S.
F. Malysheva, N. A. Belogorlova, L. N. Parshina and B. A.
Trofimov, Synthesis, 2011, 1777–1782.
3
4
A. A. Nazarov and P. J. Dyson, in Phosphorus Compounds,
Advanced Tools in Catalysis and Materials Science, Catalysis by
Metal Complexes, ed. M. Peruzzini and L. Gonsalvi, Springer,
Dordrecht, 2011, ch. 13, vol. 37.
For reviews, see: (a) I. P. Beletskaya and M. A. Kazankova, Russ.
J. Org. Chem., 2002, 38, 1391–1430; (b) M. L. Clarke and J. M. J.
Williams, in Organophosphorus Reagents. A Practical Approach
in Chemistry, ed. P. J. Murphy, Oxford University Press, Oxford,
2004, ch. 2; (c) Hey-Hawkins and A. A. Karasik, in Science of
Synthesis, ed. F. Mathey, Georg Thieme Verlag, Stuttgart, 2009,
vol. 42, p. 71–108; (d) B. A. Trofimov and N. K. Gusarova,
Mendeleev Commun., 2009, 19, 295–302; (e) D. S. Glueck, Top.
Organomet. Chem., 2010, 31, 65–100.
18 V. A. Kuimov, S. F. Malysheva, N. K. Gusarova, A. O. Korocheva
and B. A. Trofimov, J. Sulfur Chem., 2014, 35, 137–144.
19 (a) M. Arisawa, M. Yamaguchi, Tetrahedron Lett., 2009, 50, 45–
47; (b) M. Hayashi, T. Matsuura, I. Tanaka, H. Ohta and Y.
Watanabe, Org. Lett., 2013, 15, 628–631.
20 (a) K. Tanaka and F. Toda, Chem. Rev., 2000, 100, 1025–1074;
(b) K. Tanaka and F. Toda, Solvent-free Organic Synthesis, Wiley-
VCH, Weinheim, 2003.
5
6
(a) P. Anastas and N. Eghbali, Chem. Soc. Rev., 2010, 39, 301–
312; for reviews on organophosphorus compounds and Green
Chemistry, see: (b) I. L. Odinets and E. V. Matveeva, Russ. Chem.
Rev., 2012, 81, 221–238; (c) G. Keglevich and I. Greiner, Curr.
Green Chem., 2014, 1, 2–16.
For reviews, see: (a) C. Baillie and J. Xiao, Curr. Org. Chem.,
2003, 7, 477–514; (b) F. Alonso, I. P. Beletskaya and M. Yus,
Chem. Rev., 2004, 104, 3079–3159; (c) O. Delacroix and A. C.
Gaumont, Curr. Org. Chem., 2005, 9, 1851–1882; (d) S. A.
Pullarkat and P.-H. Leung, Top. Organomet. Chem., 2013, 43,
145–166; (e) V. Koshti, S. Gaikwad and S. H. Chikkali, Coord.
Chem. Rev., 2014, 265, 52–73.
21 Review: G. Brahmachari and B. Banerjee, Curr. Green Chem.,
2015, 2, 274–305.
22 (a) F. Alonso, Y. Moglie, G. Radivoy and M. Yus, Green Chem.,
2012, 14, 2699–2702; (b) F. Alonso and Y. Moglie, Curr. Green
Chem., 2014, 1, 87–93; (c) V. Gutiérrez, E. Mascaró, F. Alonso, Y.
Moglie and G. Radivoy, RSC Adv., 2015, 5, 65739–65744; (d) Y.
Moglie, E. Mascaró, V. Gutiérrez, F. Alonso, G. Radivoy, J. Org.
Chem., 2016, 81, 1813–1818.
23 (a) M. C. Hoff and P. Hill, J. Org. Chem., 1959, 24, 356–359; (b)
B. D. Dombek, J. Org. Chem., 1978, 43, 3408–3409.
7
8
9
N. L. Kilah and S. B. Wild, in Science of Synthesis; ed. F. Mathey,
Georg Thieme Verlag, Stuttgart, 2009, vol. 42, p. 595–632.
A. Florido, L. G. Bachas, M. Valiente and I. Villaescusa, Analyst,
1994, 119, 2421–2425.
24 (a) D. K. Wicht, I. V. Kourkine, B. M. Lew, J. Mulei Nthenge and
D. S. Glueck, J. Am. Chem. Soc., 1997, 119, 5039–5040; (b) D. K.
Wicht, I. V. Kourkine, I. Kovacik and D. S. Glueck,
Organometallics, 1999, 18, 5381–5394; (c) C. Scriban, I. Kovacik
and D. S. Glueck, Organometallics, 2005, 24, 4871–4874; (d) I.
Kovacik, C. Scriban and D. S. Glueck, Organometallics, 2006, 25,
536–539; (e) C. Scriban, D. S. Glueck, L. N. Zakharov, W. Scott
Kassel, A. G. DiPasquale, J. A. Golen and A. L. Rheingold;
Organometallics, 2006, 25, 5757–5767.
25 (a) M. R. Douglass and T. J. Marks, J. Am. Chem. Soc., 2000, 122,
1824–1825; (b) M. R. Douglass, C. L. Stern and T. J. Marks, J. Am.
Chem. Soc., 2001, 123, 10221–10238; (c) K. Takaki, M. Takeda,
G. Koshoji, T. Shishido and K. Takehira, Tetrahedron Lett., 2001,
42, 6357–6360; (d) A. Motta, I. L. Fragalà and T. J. Marks,
Organometallics, 2005, 24, 4995–5003; (e) H. Hu and C. Cui,
Organometallics, 2012, 31, 1208–1211.; (f) B. Liu, T. Roisnel, J.-
F. Carpentier and Y. Sarazin, Chem. Eur. J., 2013, 19, 13445–
13462; (g) I. V. Basalov, S. C. Rosca, D. M. Lyubov, A. N.
Selikhov, G. K. Fukin, Y. Sarazin, J.-F. Carpentier and A. A.
Trifonov, Inorg. Chem., 2014, 53, 1654–1661.
Q. Jia, Q. Shang and W. Zhou, Ind. Eng. Chem. Res., 2004, 43,
6703–6707.
10 M. Castillo and I. A. Rivero, ARKIVOC, 2003, xi, 193–202.
11 A. Fukazawa, M. Kiguchi, S. Tange, Y. Ichihashi, Q. Zhao, T.
Takahashi, T. Konishi, K. Murakoshi, Y. Tsuji, A. Staykov, K.
Yoshizawa and S. Yamaguchi, Chem. Lett., 2011, 40, 174–176.
12 (a) T. Eto, H. Nakajima and H. Kobayashi, JP Patent 2002265759,
2002; (b) A. Jallouli, Y. Turshani, S. Wanigatunga and M.
Rickwood, WO Patent 2004085447, 2004.
13 (a) M. Preisenberger, A. Bauer and H. Schmidbaur, Chem.
Ber./Recueil, 1997, 130, 955–958; (b) S. Ahmad, A. A. Isab, H. P.
Perzanowski, M. Sakhawat Hussain and M. Naseem Akhtar,
Transition Met. Chem., 2002, 27, 177–183; (c) A. T. Breshears, A.
C. Behrle, C. L. Barnes, C. H. Laber, G. A Baker and J. R.
Walensky, Polyhedron, 2015, 100, 333–343.
14 (a) N. K. Skvortsov, V. N. Spevak, L. V. Pashnova and V. K.
Bel’skii, Russ. J. Gen. Chem., 1997, 67, 487; (b) M. Hayashi, H.
Takezaki, Y. Hashimoto, K. Takaoki and K. Saigo, Tetrahedron
Lett., 1998, 39, 7529–7532; (c) M. Hayashi, Y. Hashimoto, Y.
Yamamoto, J. Usuki and K. Saigo, Angew. Chem. Int. Ed., 2000,
39, 631–633.
26 (a) M. R. Crimmin, A. G. M. Barret, M. S. Hill, P. B. Hitchcock and
P. A. Procopiu, Organometallics, 2007, 26, 2953–2956; (b) S.-C.
Rosca, T. Roisnel, V. Dorcet, J.-F. Carpentier and Y. Sarazin,
Organometallics, 2014, 33, 5630–5642.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 11
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
27 (a) M. O. Shulyupin, M. A. Kazankova and I. P. Beletskaya, Org. 42 D. Semenzin, G. Etemad-Moghadam, D. Albouy, O. Diallo and M.
View Article Online
Lett., 2002, 4, 761–763; (b) M. A. Kazankova, M. O. Shulyupin, A.
Koenig, J. Org. Chem., 1997, 62, 2414–2D4O22I:.10.1039/C6GC00903D
A. Borisenko and I. P. Beletskaya, Russ. J. Org. Chem., 2002, 38, 43 (a) C. M. Jessop, A. F. Parsons, A. Routledgea and D. Irvine,
1479–1484; For the Pd- and Ni-catalysed hydrophosphination of
vinyl ethers, see: (c) M. A. Kazankova, M. O. Shulyupin and I. P.
Beletskaya, Synlett, 2003, 2155–2158; (d) M. O. Shulyupin, I. G.
Tetrahedron Lett., 2003, 44, 479–483; (b) viewpoint: A. N.
Hancock and C. H. Schiesser, Chem. Commun., 2013, 49, 9892–
9895.
Trostyanskaya, M. A. Kazankova and I. P. Beletskaya, Russ. J. 44 A near second-order kinetics with respect to Ph2PH has been
Org. Chem., 2006, 42, 17–22.
determined (i.e., 1.7 order). However, to obtain accurate kinetic
data at very short reaction times has been troublesome and,
therefore, not very reliable. This is in part due to the fact that
the amounts of diphenylphosphine oxide and the oxidised
product formed while handling the samples for gas
chromatography analysis can mask the results.
28 K. J. Gallager, R. L. Webster, Chem. Commun., 2014, 50, 12109–
12111.
29 (a) W.-C. Yeo, L. Tang, B. Yan, S.-Y. Tee, L. L. Koh, G.-K. Tan and
P.-H. Leung, Organometallics, 2005, 24, 5581–5585; (b) Y.
Zhang, L. Tang, S. A. Pullarkat, F. Liu, Y. Li and P.-H. Leung, J.
Organomet. Chem., 2009, 694, 3500–3505; (c) Y. Huang, S. A. 45 Encyclopedia of Reagents for Organic Synthesis, ed. L. A.
Pullarkat, Y. Li and P.-H. Leung, Chem. Commun., 2010, 46,
6950–6952; (d) Y. Huang, S. A. Pullarkat, M. Yuan, Y. Ding, Y. Li
Paquette, John Wiley & Sons, Chichester, 1995, vol. 4, p. 2234–
2236.
and P.-H. Leung, Organometallics, 2010, 29, 536–542; (e) C. Xu, 46 T. Bunlaksananusorn and P. Knochel, Tetrahedron Lett., 2002,
G. J. H. Kennard, F. Hennersdorf, Y. Li, S. A. Pullarkat and P.-H.
Leung, Organometallics, 2012, 31, 3022–3026.
30 A. Leyva-Pérez, J. A. Vidal-Moya, J. R. Cabrero-Antonino, S. S. Al-
43, 5817–5819. According to Corma et al.,30 the corresponding
phosphine oxide was the major product isolated under those
conditions.
Deyab, S. I. Al-Resayes and A. Corma, J. Organomet. Chem., 47 R. A. Sheldon, Chem. Commun., 2008, 3352–3365.
2011, 696, 362–367.
31 (a) M. Taillefer, L. Routaboul and A. C. Gaumont, FR Patent,
2965809, 2012, (b) L. Routaboul, F. Toulgoat, J. Gatignol, J.-F.
Lohier, B. Norah, O. Delacroix, C. Alayrac, M. Taillefer and A.-C.
Gaumond, Chem. Eur. J., 2013, 19, 8760–8764.
32 (a) D. Mimeau, O. Delacroix and A.-C. Gaumont, Chem.
Commun., 2003, 2928–2929; (b) D. Mimeau, O. Delacroix, B.
Join and A.-C. Gaumont, C. R. Chimie, 2004, 7, 845–854.
33 See, for instance: R. L. Rogers, J. L. Moore and T. Rovis, Angew.
Chem., Int. Ed., 2007, 46, 9301–9304.
34 See, for instance: C. Pisano, A. Mezzetti and G. Consiglio,
Organometallics, 1992, 11, 20–22.
35 CCDC 1468810 (2z) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif (see the Supplementary
Information).
36 (a) S. F. Malysheva, N. K. Gusarova, A. V. Artem’ev, N. A.
Belogorlova, A. I. Albanov, T. N. Borodina, V. I. Smirnov and B. A.
Trofimov, Eur. J. Org. Chem., 2014, 2516–2521; (b) N. K.
Gurasova, N. A. Chernysheva, S. V. Yas’ko and B. A Trofimov, J.
Sulfur. Chem. 2015, 36, 526–534.
37 M. A. Kazankova, I. V. Efimova, A. N. Kochetkov, V. V. Afanas’ev
and I. P. Beletskaya, Russ. J. Org. Chem., 2002, 38, 1465–1474.
38 (a) Yb: K. Takaki, G. Koshoji, K. Komeyama, M. Takeda, T.
Shishido, A. Kitani and K. Takehira, J. Org. Chem., 2003, 68,
6554–6565; (b) Pd and Ni: B. Join, D. Mimeau, O. Delacroix and
A.-C. Gaumont, Chem. Commun., 2006, 3249–3251; (c) Cu: A.
Kondoh, H. Yorimitsu and K. Oshima, J. Am. Chem. Soc., 2007,
129, 4099–4104; (d) Ca: T. M. A. Al-Shboul, V. K. Pálfi, L. Yu, R.
Kretschmer, K. Wimmer, R. Fischer, H. Görls and M. Reiher, M.
Westerhausen, J. Organomet. Chem., 2011, 696, 216–227; (e)
Fe: M. Kamitami, M. Itazaki, C. Tamiya and H. Nakazawa, J. Am.
Chem. Soc., 2012, 134, 11932–11935; (f) Y: A. A. Kissel, T. V.
Mahrova, D. M. Lyubov, A. V. Cherkasov, G. K. Fukin, A. A.
Trifonov, I. Del Rosal and L. Maron, Dalton Trans., 2015, 44,
12137–12148.
39 The first attempt of diphenylphosphine addition to
phenylacetylene reported by us at 70 ºC in the absence of
solvent and catalyst gave a 90:10 Z/E diastereomeric ratio.22a
Any further experiment conducted with the same starting
materials has led to Z/E ratios of about 95:5.
40 A. V. Artem-ev, S. F. Malysheva, N. K. Gusarova, N. A.
Belogorlova, V. A. Shagun, A. I. Albanov and B. A. Trofimov,
Synthesis, 2015, 47, 263–271.
41 CCDC 1437629 (6a) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif (see the Supplementary
Information)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
Please do not adjust margins