Tin-catalyzed hydrophosphination of alkenes

Article abstract of DOI:10.1039/c5dt04272k

Simple tin derivatives, Cp?₂SnCl₂ (1) and Ph₂SnCl₂ (2), catalyze the hydrophosphination of alkene substrates with diphenylphosphine. Competitive dehydrocoupling to give Ph₄P₂ was observed, but this side reaction can be mitigated when the catalysis is conducted under an H₂ atmosphere. Efforts to prepare stable tin bis(phosphido) compounds commonly resulted in decomposition to Ph₄P₂. Lewis acidic inorganic tin compounds do not show dehydrocoupling reactivity. It was found that the Lewis acid, B(C₆F₅)₃, is able to engage in the hydrophosphination of alkenes, but it is poorly effective under the conditions tested.

Full text of DOI:10.1039/c5dt04272k

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Tin‐Catalyzed Hydrophosphination of Alkenes
John P. W. Stelmach, Christine A. Bange, and Rory Waterman*
Received 00th January 20xx,
Accepted 00th January 20xx
Simple tin derivatives, Cp*2SnCl2 (1) and Ph2SnCl2 (2), catalyze the hydrophosphination of alkene substrates with
diphenylphosphine. Competitive dehydrocoupling to give Ph4P2 was observed, but this side reaction can be mitigated
when the catalysis is conducted under an H2 atmosphere. Efforts to prepare stable tin bis(phosphido) compounds
commonly resulted in decomposition to Ph4P2. Lewis acidic inorganic tin compounds do not show dehydrocoupling
reactivity. It was found that the Lewis acid, B(C6F5)3, is able to engage in the hydrophosphination of styrene, but it is poorly
effective under the conditions tested.
DOI: 10.1039/x0xx00000x
www.rsc.org/
new type of hydrophosphination catalyst.
Introduction
Main group catalysis has grown explosively over the last
decade, driven by three main areas of interest: Frustrated Lewis
pairs (FLP),1-3 s-block metals,4, 5 and p-block elements. Though
there have been tremendous advances in p-block systems that
engage in transition-metal–like reactivity,6-9 non-Lewis acid
catalysis10 (e.g., redox or cooperative) from p-block elements
has lagged behind developments with s-block metals and FLP
systems.11-14 As part of broader studies of dehydrocoupling
1
Results and discussion
Hydrophosphination catalysis
Catalytic hydrophosphination reactions of
1
with alkene
reactions of phosphine substrates,15-17 we have investigated tin
substrates and Ph2PH were sluggish under conditions by which
alkenes were reacted with primary phosphines and 1 18
Moreover, the reactions were poorly selective for
hydrophosphination products. In most reactions,
dehydrocoupling of Ph2PH to Ph4P2 and H2 was the dominant
process (Scheme 1). From our perspective, this is an unusual
19
compound catalysts,18,
originally reported by Wright and
.
coworkers.20 In the course of those studies, it was found that
Cp*2SnCl2 ( ) is an active catalyst for the hydrophosphination
of alkene substrates (eqn 1).18 That study surveyed the
hydrophosphination reactivity of with primary phosphines
1
1
because that substrate type has been of increased interest in
recent years as compared to historical interest.18, 21-29 Herein,
we report investigation of tin compounds as catalysts for
hydrophosphination catalysis, focusing on a more classical
diphenylphosphine substrate, Ph2PH, with efforts to expand the
utility of this catalyst class. Hydrophosphination is a ubiquitous
metal-catalyzed route to P–C bonds,30-37 and new catalysts that
may relieve pressure on diminishing coinage metals often used
in this reaction are of merit. Initial investigation of
observation.
Zirconium
compounds
affect
catalytic
hydrophosphination, and those reactions are much more
favorable than dehydrocoupling, regardless of whether a
primary or secondary phosphine substrate is used.21, 26, 38, 39
In the reactions catalyzed by 1, some conversion to the anti-
Markovnikov product was seen at longer reaction times. These
products were observed when monitoring the reactions in
closed, J-Young type NMR tubes. The observation of hydrogen
1
in the H NMR spectrum led to the hypothesis that competitive
hydrophosphination catalyzed by
1 involved primary phosphine
dehydrocoupling could be inhibited by an atmosphere of
hydrogen during the reaction. Therefore, new conditions were
devised.
substrates.18 The most pervasive phosphine substrate in this
catalysis is Ph2PH.30-37 Thus, hydrophosphination reactions
with this substrate were investigated to better compare tin
catalysis with that of transition metals and gain insight into this
For these reactions, NMR tubes were charged with alkene
substrate, one equivalent of Ph2PH, and 10 mole % of
1 in
benzene-d6 solution. After degassing, the system was backfilled
with H2 gas, and reactions were conducted at 65 °C. As
hypothesized, reactions run under one atmosphere of H2 were
successful at catalytic hydrophosphination (Table 1).
Department of Chemistry, University of Vermont, Cook Physical Sciences Building,
Burlington, Vermont, 05405, USA, E‐mail: rory.waterman@uvm.edu; Fax: +1 802
656‐8705; Tel: +1 802 656 0278.
Electronic Supplementary Information (ESI) available: Representative spectra of
reactions (pdf) See DOI: 10.1039/x0xx00000x
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entry 4) and withdrawing (Table 1, entries 2,3) substituents in
View Article Online
DOI: 10.1039/C5DT04272K
the para position. Hydrophosphination of styrene substrates,
among others, has become more common with lanthanide
catalysts, and the conditions (temperature, length of reaction)
are comparable to recent work with those systems.29, 40, 41
Despite the observation of successful hydrophosphination
catalysis, there are three unsavory features of
1 as a catalyst.
The conversions to hydrophosphination products are modest at
elevated temperatures, the reaction displays substantial
competitive dehydrocoupling of phosphine substrate, and to
achieve these optimal conversions, reactions need to be run
under an atmosphere of hydrogen. Substantial improvements in
hydrophosphination reactivity were achieved through catalyst
modification for calcium compounds.42-45 This precedent gives
impetus to pursue further the development of these tin catalysts
because Hill’s original calcium catalyzed hydrophosphination
of styrene proceeded with similar conversion under comparable
conditions and reaction time.42 That precedent further suggests
that modification of the cyclopentadienyl ligand would be the
route to promote more productive reactivity. In all catalysis
runs, however, the formation of pentamethylcyclopentadiene
Scheme
1
.
Change in product distribution for
hydrophosphination catalysis with
1.
Table 1. Catalytic hydrophosphination reactions with Ph2PH using 10 mol % of
Cp*2SnCl2 (1).
products (%)a
substrate
styrene
conversion hydrophosphination (Ph2P)2
1
2
84
91
76
82
82
85
4
8
4‐bromo‐styrene
4‐CF3‐styrene
4‐methyl‐styrene
phenyl acetylene
2‐vinyl pyridine
acrylonitrile
7
3
93
5
4
90
5
was observed. Furthermore, reaction of
1 with two equivalents
5
39
15
22
14
12
13
10
of Ph2PH resulted in the formation of Ph4P2 and
1
pentamethylcyclopentadiene, as observed by 31P{1H} and H
6
100
100
35
78
86
29
68
0
NMR spectroscopy. A colorless precipitate also formed, which
is attributed to tin decomposition products. This stoichiometric
reaction is consistent with the catalytic reactions, where
pentamethylcyclopentadiene is also observed. The net
protonation of the Cp* ligand, suggests that this ligand may be
unimportant in the catalysis. Thus, a new strategy was
employed. A search for more convenient precursors and greater
understanding of the reaction was undertaken.
7
8
vinyl ether
9
ethyl acrylate
1‐hexene
81
10
10
Reactions were heated at 65 °C for 18 hours under an H2 atmosphere. The
conversion of products was measured by the relative integration of the
respective resonances by 31P{1H} NMR spectroscopy.
Using the same conditions as those for reactions with
Ph2SnCl2 ( ) was tested for hydrophosphination activity (eqn 2
and Table 2). Catalysis with compound is attractive because it
1,
2
a Some unidentified phosphorus‐containing products were also observed.
2
is a commercially available stannane. Under these conditions,
styrene derivatives and phenylacetylene were not converted to
hydrophosphination products. Activated alkenes (Table 2,
It is important to note that competitive dehydrocoupling
remained prevalent but was relegated to less than 15%
conversion in most cases. For hydrophosphination catalysis
entries 1, 2 and 4) showed similar reactivity with
2 as with 1.
with
1 using primary phosphine substrates, some competitive
Despite the inertness of styrene substrates to this catalyst, better
and more selective hydrophosphination of ethyl vinyl ether was
dehydrocoupling was observed, but for receptive unsaturated
substrates, the dehydrocoupling products were minor.18
observed in reactions with
2 (Table 2, entry 3).
Trends from substrates are mixed. Styrene derivatives and
Michael acceptors were the most effective substrates.
Unactivated alkenes exhibited poor reactivity. For example,
only 29% of ethyl vinyl ether was converted to
hydrophosphination product over an 18 hour reaction time
(Table 1, entry 8), and 1-hexene was not converted at all under
the reaction conditions (Table 1, entry 10). Surprisingly, less
than catalytic conversion to the vinyl phosphine product was
observed with phenylacetylene as the unsaturated substrate
(Table 1, entry 5). With some of the other limitations in this
catalysis, alkynes were not further pursued until better
understanding and more optimized catalysts could be found.
The styrene substrates did not appear to reflect a strong
electronic preference. While run in parallel, conversions were
not systematically affected by either electron donating (Table 1,
2
The oxidation state of tin appears to be important. Reactions
using catalytic Cp*2Sn ( ) failed to produce appreciable
hydrophosphination of styrene, acrylonitrile, or 2-vinyl
pyridine. The lack of hydrophosphination catalysis with is
consistent with prior reports in which displays no catalytic
dehydrocoupling behavior. Comparison of the reactivities of
, and in the dehydrocoupling of Ph2PH, revealed no
conversion by
substantially more active catalyst for dehydrocoupling than is
(Table 3).18 Compound
3
3
3
1
,
2
3
3
and confirmed the prior observation that
1
is
2
3
does engage in some
dehydrocoupling, but this is scarcely catalytic under the
2 | Dalton Trans., 2015, 00, 1‐3
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reaction conditions. Thus, dehydrocoupling reactivity provides Stoichiometric reactions
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DOI: 10.1039/C5DT04272K
course predictor about the activity of these tin compounds with
respect to hydrophosphination.
An effort was made to prepare and isolate tin derivatives that
may be relevant to the catalysis. A potential candidate
intermediate, Ph2Sn(PPh2)2 has been reported.47,
48
Efforts to
with
Table 2. Catalytic hydrophosphination reactions with Ph2PH using 10 mol % of Ph2SnCl2
(2).
prepare Cp*2Sn(PPh2)2 by metathesis of
1
diphenylphosphide anion (Ph2PLi) met with substantial
formation of Ph4P2 (Scheme 2), consistent with prior reports of
products (%)
substrate
2‐vinyl pyridine
acrylonitrile
vinyl ether
conversion a
hydrophosphination
(Ph2P)2
stoichiometric dehydrocoupling of phosphines mediated by tin
49
reagents and BuLi.20,
In our hands, efforts to prepare
1
2
3
4
92
60
52
98
71
60
52
93
3
0
0
5
Ph2Sn(PPh2)2 by salt metathesis resulted in significant
formation of Ph4P2 and limited amounts of the desired product.
Reaction of
2 with Ph2PH and 1,8-diazabicycloundec-7-ene
ethyl acrylate
(DBU) also afforded Ph4P2. Interestingly, attempted preparation
of Sn–P bonds has been observed to result in the formation of
Sn–Sn products rather than those with P–P bonds.48
Reactions were run at 65 °C for 18 hours under an H2 atmosphere. The
conversion of products was measured by the relative integration of the
respective resonances by 31P{1H} NMR spectroscopy.
a Percent of Ph2PH consumed as measured by 31P{1H} NMR spectroscopy.
Based on the dehydrocoupling reactivity, compound
should not need hydrogen atmosphere
2
for
a
Scheme 2. Stoichiometric reactions of
1 and 2 targeted at
hydrophosphination. Indeed this is the case, and the
hydrophosphination of 2-vinyl pyridine proceeds smoothly
under the same conditions (vide supra) without a hydrogen
atmosphere to give the hydrophosphination product in 82%
yield (eqn 3).
R2Sn(PPh2)2 products largely give Ph4P2.
Lewis acids
The remarkable chemistry of Lewis acid and FLP systems
raises the possibility that Lewis acidic tin may be catalyzing the
reaction. The stoichiometric hydrophosphination of alkenes
was reported recently by Erker.50 Indeed, Stephan and co‐
workers demonstrated P–H bond activation to generate a
stabilized phosphenium (i.e., hydride abstraction) using Lewis
acids, chemistry which was leveraged into catalytic phosphine
dehydrocoupling and hydrogenation.51 Therefore, simple tin
chloride compounds were screened. Reactions in which each
tin(II) chloride and tin(IV) chloride were used as a catalyst (10
mol %) failed to give appreciable hydrophosphination of
styrene when applying the same conditions used for the
organometallic tin derivatives.
3
Measurement of the kinetic isotope effect for the
hydrophosphination of styrene using
1 gave KIE = 3.1(3). The
value was obtained by an internal competition between an
equivalent excess of Ph2PH and Ph2PD, and the ratio of
products (1‐diphenylphosphino‐2‐phenylethane and 1‐
diphenylphosphino‐2‐phenylethane‐d1) was measured to give
the KIE value (eqn 4). This is a large value, which demonstrates
substantial P–H/D cleavage in the turnover limiting step. The
The possibility of Lewis acid‐mediated hydrophosphination
could not be ignored, and B(C6F5)3, a more potent Lewis acid,
was also tested. Treatment of an equimolar mix of styrene and
Ph2PH with B(C6F5)3 in benzene‐d6 solution gave no detectable
formation of the hydrophosphination product at 65 °C.
However, reactions run at high temperatures gave
hydrophosphination products. Thus, heating an equimolar mix
of styrene and Ph2PH with B(C6F5)3 in benzene‐d6 solution to
100 °C resulted in about one turnover to give 1‐
diphenylphosphino‐2‐phenylethane after 12 hours (eqn 5),
and further heating resulted in catalysis. While Lewis acid
catalyzed hydrophosphination appears to be possible based on
these results, it is inefficient under these conditions. It is likely
that better Lewis acid catalysts can be identified to promote
this transformation.
magnitude is similar to that seen for
‐bond metathesis
reactions,46 which may explain why the catalysis is only
operant for the higher oxidation state tin compounds.
4
Table 3. Comparison of dehydrocoupling activity of Ph2PH using 10 mol
compounds 1, 2, and 3, respectively.
% of
cmpd.
Ph4P2
13 a
0
Cp*2SnCl2 (1)
Ph2SnCl2 (2)
Cp*2Sn (3)
2
Reactions were run at 65 °C for 18 hours. The conversion to Ph4P2 was calculated
based on relative integration in 31P{1H} NMR spectra.
5
a Extended reaction times improve conversion to product, see reference 18.
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Table 4. Catalytic hydrophosphination reactions with Ph2PH using 10 mol % of B(C6F5)3
Table 5. Quantities of reagents (mg) for hydrophosphination catalysis with 1.
View Article Online
DOI: 10.1039/C5DT04272K
and control reactions in the absence of borane.
substrate
styrene, 29.6
4‐methyl styrene, 33.4
4‐bromo styrene, 52.7
4‐trifluromethyl styrene, 50.1
acrylonitrile, 28.8
PPh2H
53.2
53.5
51.4
53.7
74.5
74.5
52.5
46.5
53.5
1
product a
products (%)a
52
12.9
12.9
13.1
13.2
18.4
18.4
13.1
11.5
13.1
52
b
substrate
4‐bromo‐styrene
4‐CF3‐styrene
4‐methyl‐styrene
2‐vinyl pyridine
acrylonitrile
conversion hydrophosphination (Ph2P)2
1
2
3
5
6
7
8
31 (29)
42 (36)
20 (23)
84 (56)
67 (15)
57 (8)
24 (27)
33 (34)
16 (23)
77 (15)
58 (15)
52 (8)
7 (0)
8 (0)
4 (0)
2 (0)
5 (0)
5 (0)
3 (0)
c
53, 54
53
phenyl acetylene, 45.1
2‐vinyl pyridine, 23.2
ethyl vinyl ether, 19.3
ethyl acrylate, 27.5
52
55
53
a
vinyl ether
Reference to spectroscopic characterization of the anticipated product of
hydrophosphination catalysis.
ethyl acrylate
82 (23)
72 (23)
b Selected data: 31P{1H} NMR: δ = –15.4; GCMS (EI): m/z = 369.4, 367.8
c Selected data: 31P{1H} NMR: δ = –15.8; GCMS (EI): m/z = 357.5
Reactions were heated at 65 °C for 18 hours under an H2 atmosphere. The
conversion of products was measured by the relative integration of the
respective resonances by 31P{1H} NMR spectroscopy.
Table 6. Quantities of reagents (mg) for hydrophosphination catalysis with 2.
a
Values are for the catalytic runs, and values in parentheses are for control
reactions in the absence of added borane.
substrate
acrylonitrile, 27.1
2‐vinyl pyridine, 28.2
ethyl vinyl ether, 24.8
ethyl acrylate, 35.1
PPh2H
95.2
52.0
58.5
63.4
2
17.2
9.2
10.5
11.5
Extension of that initial observation to the substrates
screened throughout this study show that styrene derivatives
are poorly hydrophospinated by this Lewis acid (Table 4,
entries 1–3). Michael acceptors show moderate activity as
substrates (Table 4, entries 5–8). These results are highly
preliminary, but in this proof of concept series, Lewis acids
appear to be potentially viable hydrophosphination catalysts.
Dehydrocoupling reactions
Reactions were conducted in PTFE‐valved NMR tubes. One
equivalent of diphenylphosphine and 10 mol % of pre‐catalyst
were dissolved in 0.4 mL of benzene‐d6 (Table 6). The resulting
solution was added to the NMR tube. Initial H and 31P{1H}
1
NMR spectra were obtained. The NMR tube was then heated
to 65 °C and data collected again periodically until 18 hours of
reaction time was reached. Experiments were halted at this
Experimental Section
General considerations
All manipulations were performed with rigorous exclusion of time because 18 hours was the typical length of
air and water by means described in prior publications.18 All hydrophosphination run with these compounds.
NMR spectra were collected at 25 °C in benzene‐d6 on a Bruker
a
Table 7. Reagents for the attempted catalytic dehydrocoupling of Ph2PH (mg).
Ascend 500 MHz NMR spectrometer and referenced internally
to solvent residual resonances or to external phosphoric acid
(85%).
Catalytic hydrophosphination reactions using R2SnCl2 (R = Cp*, 1; R
= Ph, 2)
compound
Cp*2SnCl2 (1)
Ph2SnCl2 (2)
Cp*2Sn (3)
amount
18.7
8.2
Ph2PH
74.5
45.3
15.7
75.1
Reaction of Cp*2SnCl2 with Ph2PH
All reactions were conducted in J‐Young type
polytetrafluroethylene (PTFE)‐valved NMR tubes. A mixture of
one equiv. of unsaturated substrate, one equiv. of phosphine,
A scintillation vial equipped with a magnetic stir bar was
charged with 30.1 mg (0.065 mmol) of Cp*2SnCl2 and 5 mL of
diethyl ether. Slowly 25.8 mg (0.139 mmol, 2.1 equiv) of neat
Ph2PH was added. The contents of the reaction were stirred at
23 °C for 18 h to give 90% conversion to Ph4P2 by 31P NMR
spectroscopy.
and 10 mol % of
1 or 2 were then dissolved in 0.4 mL of
benzene‐d6 (Table 4 and 5, respectively). The resulting solution
was transferred to an NMR tube. The nitrogen atmosphere
was removed from the J‐Young PTFE‐valved NMR tube via a
freeze‐pump‐thaw cycle, and the tube was backfilled with a
positive pressure of H2 gas. The headspace was evacuated and
backfilled again to ensure a pure H2 atmosphere. Initial 1H and
31P NMR spectra were then collected. The solution was then
heated to 65 °C, and NMR spectra collected periodically with a
final spectrum at 18 hours reaction time. In all reactions, the
yellow initial solution gradually lost its color upon heating and
formation of a colorless precipitate was observed during the
course of the reaction.
Reaction of Cp*2SnCl2 with Ph2PLi
A scintillation vial equipped with a magnetic stir bar was
charged with 45.9 mg (0.247 mmol) of Ph2PH. The reaction
was given 5 mL of ether, cooled to –30 °C, and treated with
0.16 mL of a 1.6 M BuLi solution in hexanes. This was allowed
to warm to 23 °C and stirred for 30 min. The reaction contents
were cooled to ‐30 ̊C and slowly given 54.0 mg (0.117 mmol) of
Cp*2SnCl2. The contents of the reaction were stirred at 23 °C
for 18 h to give quantitative conversion to Ph4P2 by 31P NMR
spectroscopy.
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Reaction of Ph2SnCl2 with Ph2PLi
Overall, there is a clear potential for growth and iVmiewprAortvicelemOnelinnet
with these tin‐catalyzed reactions.
DOI: 10.1039/C5DT04272K
A scintillation vial was given 47.8 mg (0.257 mmol) of Ph2PH, a
magnetic stir bar, and 5 mL of diethyl ether. The contents were
Though not the focus of this work, evidence for Lewis acid
catalyzed hydrophosphination has been discovered. This
catalysis is poorly efficient as compared to the tin catalysis
reported herein as well as hydroamination catalysis using
B(C6F5)3.56 This preliminary discovery suggests that Lewis acid
or FLP catalysis may be an area of growth in
hydrophosphination, and like these tin compounds, may be a
route to alleviate pressure on coinage metals in this kind of
catalysis.
cooled to ‐30
̊
solution in hexanes. This was allowed to warm to 23
̊
stirred for 30 min. The reaction contents were cooled to –30 °C
followed by slow addition of 44.0 mg (0.127 mmol) of
Ph2SnCl2. The contents of the reaction were stirred at 23 °C for
18 h to give 46% conversion to Ph4P2 by 31P NMR spectroscopy.
Reaction of Ph2SnCl2 with Ph2PH and DBU
A flask was charged with 46.6 mg (0.136 mmol) of Ph2SnCl2, 5
mL of dichloromethane, and 53.4 mg (0.350 mmol, 2.57 equiv.)
of DBU. Dropwise, 54.3 mg (0.292 mmol) of Ph2PH were
added. The contents were refluxed for 22 h. The volatiles were
removed under reduced pressure to yield a complicated
mixture of products including Ph4P2 by 31P NMR spectroscopy.
A second run at ambient temperature provided similar results.
Catalytic hydrophosphination of styrene using B(C6F5)3
Acknowledgements
This work was supported by the U.S. National Science
Foundation (NSF) and acknowledgment is made to the Donors
of the American Chemical Society Petroleum Research Fund
for support of this research (CHE‐1265608 and 54820‐ND3 to
RW). The NMR spectrometer used in this work was purchased
with NSF support (CHE‐1126265).
A J‐Young NMR tube was charged with 2.9 mg (0.0057 mmol)
of B(C6F5)3, 7.9 mg (0.076 mmol) of styrene, and 0.50 mL of
benzene‐d6. Finally, 15.8 mg (.085 mmol) of Ph2PH was added.
The reaction was heated at 65 °C or 100 °C and monitored by
31P NMR spectroscopy. For styrene, No dehydrocoupling
products were observed and after at least 6 hours, measurable
quantities of Ph2PCH2CH2Ph were observed. Reactions with all
other substrates (Table 4) were conducted similarly. In those
reactions, only runs at 100 °C were made.
Notes and references
1.
2.
D. W. Stephan, Dalton Trans., 2009, 3129‐3136.
D. W. Stephan, J. Am. Chem. Soc., 2015, 137, 10018‐
10032.
3.
4.
D. W. Stephan and G. Erker, Angew. Chem. Int. Ed., 2015,
54, 6400‐6441.
M. R. Crimmin and M. S. Hill, Top. Organomet. Chem.,
Kinetic isotope effect measurement
2013, 45, 191‐241.
S. Harder, Chem. Rev., 2010, 110, 3852‐3876.
P. P. Power, Nature, 2010, 463, 171‐177.
P. P. Power, Chem. Rec., 2012, 12, 238‐255.
M. Soleilhavoup and G. Bertrand, Acc. Chem. Res., 2015,
48, 256‐266.
A J‐Young NMR tube was charged with Cp*2SnCl2 (2.8 mg,
0.0061 mmol), styrene (8.1 mg, 0.078 mmol), and 0.50 mL of
benzene‐d6. A mixture of 17.5 mg of Ph2PH and 17.8 mg of
Ph2PD was then added. The contents were heated to 65 °C for
18 h, and the relative integration of the methylene resonances
was compared.
5.
6.
7.
8.
9.
D. Martin, M. Melaimi, M. Soleilhavoup and G. Bertrand,
Organometallics, 2011, 30, 5304‐5313.
10.
W. E. Piers, A. J. V. Marwitz and L. G. Mercier, Inorg.
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Conclusions
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L. A. Berben, Chem. Eur. J., 2015, 21, 2734‐2742.
J.‐J. Cao, F. Zhou and J. Zhou, Angew. Chem. Int. Ed., 2010,
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The catalytic hydrophosphination of alkenes with Ph2PH using
tin catalysts has been explored. The previously reported
catalyst for this reaction,
competitive phosphine dehydrocoupling, but this undesired
reactivity can be suppressed by running reactions under a
hydrogen atmosphere. Compound
hydrophosphination catalyst. While
broad of a substrate scope as , indications are that
require a hydrogen atmosphere because dehydrocoupling
reactivity under these conditions by is non‐existent. Tin(IV)
appears to be essential for this reactivity because did not
afford hydrophosphination products under the conditions
tested. A large kinetic isotope effect value measured in an
internal competition experiment suggests that the P–H bond
1, suffers from substantial
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View Article Online
DOI: 10.1039/C5DT04272K
Tin-Catalyzed Hydrophosphination of Alkenes
John P W. Stelmach, Christine A. Bange, and Rory Waterman†
Department of Chemistry, University of Vermont, Cook Physical Sciences, Burlington, Vermont, 05405,
United States
rory.waterman@uvm.edu