A Study of Two Highly Active, Air-Stable Iron(III)-μ-Oxo Precatalysts: Synthetic Scope of Hydrophosphination using Phenyl- and Diphenylphosphine

Article abstract of DOI:10.1002/adsc.201501179

The importance of phosphines in synthetic chemistry cannot be underestimated. Catalytic hydrophosphination offers an ideal method to prepare P?C bonds without the need for harsh reaction conditions or stoichiometric amounts of waste by-product. We herein report our studies into two biocompatible iron(III) complexes in hydrophosphination chemistry using diphenylphosphine under mild and benign reaction conditions (room temperature, solvent-free) and our extended exploration of hydrophosphination with phenylphosphine, which can be tuned to operate in the absence of catalyst under thermal conditions for single hydrophosphination or solvent-free with an iron(III) precatalyst to generate the products of double hydrophosphination. (Figure presented.).

Full text of DOI:10.1002/adsc.201501179

FULL PAPERS
DOI: 10.1002/adsc.201501179
A Study of Two Highly Active, Air-Stable Iron(III)-m-Oxo
Precatalysts: Synthetic Scope of Hydrophosphination using
Phenyl- and Diphenylphosphine
Kimberley J. Gallagher,a Maialen Espinal-Viguri,a Mary F. Mahon,a,*
and Ruth L. Webstera,*
a
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, U.K.
E-mail: m.f.mahon@bath.ac.uk or r.l.webster@bath.ac.uk
Received: December 30, 2015; Revised: February 16, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201501179.
Abstract: The importance of phosphines in synthetic vent-free) and our extended exploration of hydro-
chemistry cannot be underestimated. Catalytic hy- phosphination with phenylphosphine, which can be
drophosphination offers an ideal method to prepare tuned to operate in the absence of catalyst under
À
P C bonds without the need for harsh reaction con- thermal conditions for single hydrophosphination or
ditions or stoichiometric amounts of waste by-prod- solvent-free with an iron(III) precatalyst to generate
uct. We herein report our studies into two biocom- the products of double hydrophosphination.
patible iron(III) complexes in hydrophosphination
chemistry using diphenylphosphine under mild and Keywords: homogeneous catalysis; iron; phosphines;
benign reaction conditions (room temperature, sol- porphyrins; Schiff bases
Introduction
iron(III) porphyrin complex 3.[4] We also wished to
explore the limits of the reactivity: catalysis with com-
Hydrophosphination (HP),[1] the addition of a P H plex 1 appears to be restricted to activated alkenes,
bond across an unsaturated bond, is a powerful tool but we have not explored the potential of using an ac-
in synthetic chemistry: it has the potential to be 100% tivated primary phosphine in catalysis. i.e., phenyl-
atom economic, has impressive functional group toler- phosphine. There are limited examples of HP with
À
À
ance in comparison to many traditional routes of P C primary phosphines in the literature. Examples in-
bond formation[2] and gives access to vital primary, clude Watermanꢀs elegant and mild Zr-catalyzed
secondary or tertiary phosphines depending upon che- route which can be tuned for single or double hydro-
moselectivity and/or the phosphorus source. HP with functionalization products (cf. 4 and 5 respectively,
an iron precatalyst is rare, with only a handful of ex- Scheme 1), depending on reagent stoichiometries, and
amples reported in the literature.[3] The attraction of is effective for unactivated alkenes such as 1-
iron lies in its abundance and resulting cost effective- hexene.[5] Waterman and Wright also report tin-medi-
ness: it is a sustainable, non-toxic base metal with ated HP which operates for styrene, 2,3-butadiene,
which to develop catalysis. Seminal work in the area phenylacetylene and diphenylacetylene[6] and finally
of iron-catalyzed HP of alkenes was presented by publications from Sarazin, Carpentier and Trifonov[7]
Gaumont and co-workers[3c] using only FeCl2 or FeCl3 on rare earth-catalyzed HP. These latter systems oper-
to furnish the anti-Markovnikov product (cf. 2, ate at 708C or below on styrene where a 1:1 ratio of
Scheme 1) or highly desirable Markovnikov products. styrene:H2PPh gives high levels of selectivity for the
Following this work, we reported the use of a highly secondary phosphine product (cf. 4, Scheme 1).
active iron(III) salen-m-oxo complex (1, Scheme 1)
The desire to harness and understand the catalytic
which catalyzes the HP of activated alkenes with a re- potential of iron, in particular the use of iron com-
markably low catalyst loading of 0.5 mol%.[3d] We plexes which do not need activation is an area of in-
questioned whether this reactivity is limited to 1, or terest. In the wider field of hydrofunctionalization,[8]
whether other N-ligands also facilitate HP when in iron has demonstrated its wide-reaching potential
a metal-m-oxo coordination environment, specifically across a range of transformations, not least in catalyt-
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Table 1. Optimization of HP reactivity in different sol-
AHCTUNGTRENNUNG
vents.[a]
Entry Solvent
Precat. 1
2a Spec. Yield
[%][b]
Precat. 3
2a Spec. Yield
[%][b]
1
2
3
4
5
6
7
toluene
dichloromethane 98
tetrahydrofuran 84
acetonitrile
pentane
ethanol
none
76
70
98
88
84
65
35
96
89
–
92[c]
98
[a]
General reaction conditions: styrene (120 mL, 1.04 mmol,
1.82 equiv.), HPPh2 (100 mL, 0.57 mmol), or
1
3
(0.0029 mmol, 0.5 mol%), 24 h, room temperature, inert
atmosphere.
[b]
[c]
Spec. Yield=spectroscopic yield, determined by
1H NMR spectroscopy using 1,2-DCE as a standard.
Methanol used as solvent.
neat (entries 6 and 7). We have already reported just
how active 1 is at low catalyst loading and indeed,
when the reaction is performed neat in the presence
of 0.5 mol% 3, the yield of 2a remains at 96%.
Scheme 1. Hydrophosphination of activated alkenes under
thermal or catalytic conditions.
We then proceeded to explore the substrate scope
ic hydrophosphination[3a,c] and hydrophosphonyla- with precatalyst 3 under the optimized reaction condi-
tion.[3b,9] In our continued efforts to develop transfor- tions. The reaction is performed solvent-free at room
mations of phosphines mediated by iron, we proceed- temperature for 24 h (Table 2). Unsurprisingly, the
ed to investigate the use of air-stable iron porphyrin- porphyrin complex performs competently in compari-
m-oxo complex, 3, for the HP of activated alkenes son to the simple Fe(III) salen-m-oxo complex under
with diphenylphosphine and compare it to the activity similar reaction conditions, albeit in MeCN. However,
observed with 1. We have also extended the reactivity interesting improvements in reactivity are seen with
to phenylphosphine in the hydrophosphination of ac- 4-chlorostyrene (Table 2, entry 4) and 2- and 4-vinyl-
tivated alkenes using 1 and 3.
pyridine (entries 10 and 11), where the reaction time
and temperatures are reduced compared to those
when 1 is employed. The improved reactivity, particu-
larly with 2-vinylpyridine, could be attributed to the
sterically congested reaction environment: the 4-coor-
dinate porphyrin ligand surrounds the iron center and
prevents competitive ligation and catalyst deactiva-
Results and Discussion
Reactions with HPPh2
To initiate our study we compared the catalytic com- tion by the product, 2j. Aguirre et al. have already
petency of complex 3 to 1 in the HP of styrene with demonstrated that 2j is a good ligand for palladium-
diphenylphosphine across a range of different solvents catalyzed olefin methoxycarbonylation,[10] so it is pos-
(Table 1). Unsurprisingly, at high catalyst loading sible that competitive ligation could occur at the iron
(5 mol%) both precatalysts are excellent at mediating center. The activity of 1 and 3 in MeCN was com-
this transformation. While it is difficult to argue pared: the turnover frequency for the formation of 2a
against the biocompatible, non-toxic and easy to over the initial 30 min is 80 hÀ1, slowing to 55 hÀ1 after
handle nature of both the iron porphyrin and salen one hour using 1 compared to 33 hÀ1 for the first
systems, the reactions remain mild: excellent spectro- 30 min and only slowing marginally to 30 hÀ1 after
scopic yield (Spec. Yield) is achieved in most solvents one hour for complex 3. It should be noted that for
at room temperature. Worth of note is the competen- simple styrenes reactions catalyzed by 1 tend to be
cy when the reaction is performed in alcohols and complete within 10 to 16 h, whereas reactions with 3
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A Study of Two Highly Active, Air-Stable Iron(III)-m-Oxo Precatalysts
Table 2. Substrate scope for hydrophosphination using
tend to need the full 24 h to go to completion. To
probe the reaction mechanism, the radical trap
TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) was
added to the HP reactions using both 1 and 3; there is
little variation in yield suggesting that catalysis is not
radical mediated.
HPPh2.[a]
To prove the synthetic utility of this transformation
and the benefits of using an air-stable precatalyst, the
reaction of HPPh2, styrene and 3 was performed in
a round-bottom flask fitted with a septum under
a steady stream of N2. The reaction was scaled to use
2.3 mmol (0.4 mL) HPPh2, 4.2 mmol (0.48 mL) sty-
rene and 0.5 mol% (13.6 mg) 3. Product 2a was ob-
tained in 85% spectroscopic yield, 63% (0.66 g) isolat-
ed yield.
Reactions with H2PPh
Overall, the ease and scale in which 1 and 3 can be
synthesized led us to research their ability to catalyze
the reaction of phenylphosphine and styrene. We
commenced this investigation by reacting phenylphos-
phine with styrene in the presence of iron precatalyst
at room temperature, using a range of reaction condi-
tions. We were somewhat surprised to find that very
little reaction takes place in the presence of 1. With
5 mol% 3 at room temperature, 37% of the single ad-
dition product (4a, SHP, where only one equivalent of
styrene reacts with phenylphosphine generating the
secondary phosphine) is obtained after 24 h in the ab-
sence of solvent. Extending the reaction time to 72 h
increases the yield to 62%. Although a good yield,
and a rare example of SHP at room temperature,[5–7]
the prolonged reaction time is somewhat limited: we
decided to probe the potential for catalyst-free ther-
mal reactivity. Undertaking the hydrophosphination
procedure in the absence of catalyst, under thermal
conditions, gives good conversion to the SHP product
(Scheme 2a). After a short optimization process we
found that a good yield of 4a could be obtained with
thermal treatment at 808C (61% 4a after 18 h at 808C
[a]
General reaction conditions: alkene (1.04 mmol,
1.82 equiv), HPPh2 (100 mL, 0.57 mmol),
1
or
3
(0.0029 mmol, 0.5 mol%), neat or MeCN (0.35 mL),
24 h, room temperature, under argon.
Reaction performed in MeCN (350 mL). Spec. Yield=
spectroscopic yield, determined using H NMR spectros-
copy with 1,2-DCE as a standard. Isolated yield [%]
given in square brackets.
[b]
[c]
1
Reaction performed neat, spectroscopic yield determined
1
using H NMR spectroscopy with 1,2-DCE as a standard.
Isolated yield [%] given in square brackets.
[d]
[e]
[f]
At 114 h.
At 608C.
For 72 h.
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Table 3. Substrate scope for thermal hydrophosphination
using H2PPh.[a]
Scheme 2. Reactivity of styrene and phenylphosphine under
a) thermal and b) catalytic conditions.
in MeCN). Addition of a further two equivalents of
styrene to this reaction mixture and thermal treat-
ment gives no further conversion, with only trace
amounts of 5a observed. Solvent is necessary for the
reaction to proceed cleanly; when performed neat im-
purities can be seen in the 31P{1H} NMR. It is interest-
ing to note that in our hands when a 1:1 ratio of phe-
nylphosphine:styrene is reacted in C6D6 at 608C in
a J-Young NMR tube 35% of 4a is obtained after
16 h.[11] When the reaction is repeated in a Schlenk
tube with stirring 60% 4a is obtained. This would sug-
gest that at temperatures of 608C or greater, no cata-
lyst is necessary and thermal conditions can be used,
analogous to work from Alonso and co-workers with
HPPh2.[12]
Surprisingly, the thermal reaction of phenylphos-
phine with activated alkenes has never been reported.
We are pleased to report that a range of activated
substrates undergo SHP with minimal conversion to
the tertiary phosphine product under these reaction
conditions (Table 3). Styrenes with functionality in
the para-position undergo thermal SHP with only
minor amounts of double addition (DHP, where two
equivalents of styrene functionalize phenylphosphine
furnishing a tertiary phosphine) being observed: elec-
tron-withdrawing and electron-donating groups are
tolerated, as well as styrenes with useful functionality,
for example, halogen-substituted styrenes (entries 4, 5
and 8). Vinylpyridines undergo hydrophosphination
with phenylphosphine, but unfortunately the reaction
appears to be less selective for the secondary phos-
phine product, with double hydrophosphination
taking place readily: 2-vinylpyridine undergoes HP
with a 3:2 ratio of 4i:5i being obtained (entry 9), 4-vi-
nylpyridine gives poor yield of 4j, with multiple prod-
ucts observed by 31P{1H} NMR (entry 10). Acrylates
are tolerated under these reaction conditions (en-
tries 11 and 12).
[a]
General reaction conditions: styrene (0.285 mmol,
1 equiv.), phenylphosphine (63 mL, 0.57 mmol, 2 equiv.),
MeCN (200 mL), 16 h, 808C, under argon.
[b]
Spec. Yield=spectroscopic yield, determined by
1H NMR spectroscopy using THF as a standard. Isolated
yield [%] given in square brackets.
[c]
Product of double hydrophosphination observed, spectro-
scopic yield shown in brackets.
Purification of the SHP products, even in the pres-
ence of DHP side-products, is trivial: the reaction
mixture is subjected to vacuum to remove any un- duced pressure with gentle heating to 608C allows dis-
reacted H2PPh and volatile styrenes, then use of tillation of products 4a to 4l away from any traces of
a short path distillation apparatus or cold finger at re- DHP product or unreacted, non-volatile, styrenes.
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Unfortunately no reaction is observed with unactivat- small amounts of SHP product it is immediately trans-
ed substrates; substrates primed for nucleophilic ferred to an iron-catalyzed HP cycle where it can un-
attack must be used, for example, allylbenzene and 1- dergo DHP, thus helping to drive forward the thermal
hexene give only trace amounts of product. Similarly, process. Alternatively, it is possible to undertake ther-
the transformation with cyclohexylphosphine fails to mal SHP at 808C to afford secondary phosphines of
deliver an appreciable amount of product.
the form 4, followed by addition of catalyst and fur-
We then proceeded to investigate whether we could ther reaction at room temperature to generate prod-
integrate thermal and catalytic HP. We anticipate that ucts of the form 5. Using the one-pot procedure,
the electronic nature of phosphine products 4a to 4l is 1.25 mol% 1 and heating to 408C, we observe clean
similar to that of diphenylphosphine and should thus formation of the DHP product, with only small quan-
be able to undergo iron-catalyzed HP in the presence tities of unreacted SHP product (<15%) and unreact-
1 or 3. By changing the reaction stoichiometries, the ed starting materials. In some Fe-catalyzed HP reac-
product of double hydrophosphination is observed tions small quantities of side product are observed in
(Scheme 2b). Using 1, no reaction is obtained using the 31P NMR.[13] These are believed to be products of
DHP conditions at room temperature and heating to Michael addition,[14] where styrene starting material
408C is needed (Table 4). We envisage that this reac- undergoes further attack by the HP product. This
tion proceeds via thermal SHP and on formation of may hint at a potential reaction mechanism which
proceeds via a zwitterionic intermediate. The reaction
proceeds best neat, presumably the increased concen-
tration results in more favorable DHP. However, in
an effort to use a lower reaction temperature, when
the catalyst loading is increased the reaction does not
proceed cleanly and mixtures of products start to
form. On the other hand 3 is an excellent precatalyst
for DHP at room temperature and, unlike 1, side-
products are not obtained at the higher catalyst load-
ing of 5 mol%.
Table 4. Substrate scope for catalytic double hydrophosphi-
nation.[a]
The phosphine products are oils at room tempera-
ture, however, the structure of phosphine 5a was con-
firmed by ligation to iron, which is achieved in good
yield (65% Fe-5a) by stirring two equivalents of the
ligand with FeCl2·THF1.5 at room temperature in dry
THF (Figure 1). Precipitation of the iron complex is
observed within minutes and it can be isolated by re-
Figure 1. X-ray crystal structure of complex Fe-5a (hydrogen
atoms omitted for clarity and ellipsoids represented at 30%
À
probability). Selected bond lengths (ꢂ) Fe1 Cl1 2.232(1);
Fe1 Cl2 2.238(1); Fe1 P1 2.433(1); Fe1 P2 2.415(1); P1
[a]
À
À
À
À
General reaction conditions: styrene (2.28 mmol,
À
À
À
4 equiv.), phenylphosphine (63 mL, 0.57 mmol, 1 equiv.),
1 (1.25 mol%) or 3 (5 mol%), neat, 24 h, 408C or room
temperature, under argon.
C1 1.827(4); P1 C9 1.830(4); P1 C17 1.815(4); P2 C23
1.822(4); P2 C31 1.835(4); P2 C39 1.818(4); C1 C2
À
À
À
À
À
À
1.533(6); C9 C10 1.540(5); C23 C24 1.536(5); C31 C32
[b]
À
À
Spec. Yield=spectroscopic yield, determined by
1.528(5). Selected bond angles (8): Cl2 Fe1 Cl1 127.30(4);
1H NMR spectroscopy using 1,2-DCE as a standard. Iso-
lated yield given in square brackets.
Cl2 Fe1 P1 102.55(4); Cl1 Fe1 P2 100.41(4); Cl2 Fe1 P2
À
À
À
À
À
À
À
À
À
À
111.64(4); Cl1 Fe1 P1 111.04(4); P2 Fe1 P1 101.25(4).
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moval of solvent by filtration followed by washing has not taken place. This could be due to rapid P-in-
with cold pentane. The iron complex is obtained as version at the Fe-center,[21] particularly at the raised
a distorted tetrahedral complex with bond lengths of reaction temperature, and/or due to lack of stereocon-
À
À
2.433(1) and 2.415(1) ꢂ, for Fe P1 and Fe P2 respec- trol induced by the metal complex. It is nonetheless
À
À
tively and 2.232(1) and 2.238(1) for Fe Cl1 and Fe
Cl2 respectively.
a useful method to make unsymmetrically substituted
tertiary phosphines.
With easy access to chiral salen complexes we then
questioned whether we could afford optically active
tertiary phosphines using our methodology. By first Conclusions
applying thermal conditions to generate the SHP
product, 4a, we should then be able to use a chiral In summary, we have demonstrated that an iron(III)
iron precatalyst to install a second alkyl substituent porphyrin complex can catalyze the hydrophosphina-
stereoselectively. P-stereogenic phosphines have tion of activated alkenes with diphenylphosphine. The
found extensive use in metal-mediated asymmetric transformation operates under environmentally
catalysis,[1a,15] notably in early leading research from benign conditions (solvent-free, room temperature)
Knowles into asymmetric hydrogenations.[16] Although with a low loading of a simple air-stable base-metal
excellent examples of transition metal-catalyzed enan- catalyst. In general, this porphyrin catalyst appears to
tioselective HP exist,[15a–d,17] this would be an unusual be as active over as wide a range of alkene substrates
example of iron mediating an enantioselective HP re- as our original iron(III) salen complex. We have also
action, with the other leading literature examples presented two new methods to functionalize activated
being stoichiometric studies[18] or of intermolecular alkenes with phenylphosphine; a thermal route which
hydrophosphonylation.[3b]
selectively forms the secondary phosphine products
We initiated our investigations by preparing the Ja- and an iron(III)-catalyzed route which can furnish
cobsenꢀs ligand motif and ligating it to Fe to form the symmetrical tertiary phosphines in one pot or a two-
corresponding m-oxo complex, 6.[19] When 4a is react- step method which can be used to synthesize unsym-
ed in the presence of two equivalents 4-chlorostyrene, metrically substituted tertiary phosphines. It is clear
0.5 mol% 6 at 608C for 60 h 90% 7 is obtained that iron precatalyst 6 is not able to induce enantiose-
(Scheme 3). Unfortunately no enantioinduction is ob- lective hydrophosphination and therefore further de-
tained with precatalyst 6 which was determined by ox- velopment is needed in this area in order to achieve
idation of the isolated phosphine, 7, with two equiva- this goal.
lents of H2O2 and extraction of the phosphine oxide
into CH2Cl2 to give a stable product that can be stud-
ied using chiral separation techniques. It is worth Experimental Section
noting that for the phosphine oxide of 7 Kaganꢀs
amide[20] and a selection of lanthanide shift reagents General Method for Hydrophosphination using
[Eu(FOD)3 and Eu(hfc)3] do not give peak separation HPPh2 and Precatalyst 3
by both 1H and 31P{1H} NMR. Instead, circular dichro-
ism was used to demonstrate that enantioinduction
Carried out under an argon atmosphere in an M-Braun
glove box, 3 (0.5 mol%) was weighed out into a Schlenk
tube. Styrene (1.04 mmol, 1.86 equiv.) was added followed
by diphenylphosphine (100 mL, 0.57 mmol, 1 equiv.). After
stirring at room temperature for 24 h, the Schlenk tube was
placed under vacuum and the excess starting styrene and
solvent were removed. For spectroscopic yields reaction sol-
utions were exposed to air and filtered through a silica gel
plug using CH2Cl2. Solvent was removed by blowing nitro-
gen over the oil before addition of 1,2-dichloroethane as an
integration standard. CDCl3 was used as the NMR solvent.
All products obtained have been previously reported and
characterized,[3d] NMR spectra for isolated products are pro-
vided.[13]
General Method for Thermal Single
Hydrophosphination
The reaction was performed under an argon atmosphere in
an M-Braun glove box. Styrene (0.285 mmol, 1 equiv.) was
placed in a Schlenk tube, acetonitrile (200 mL) and phenyl-
Scheme 3. Product of unsymmetrical HP.
phosphine (63 mL, 0.57 mmol, 2 equiv.) were added. After
6
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stirring at 808C for 16 h, the Schlenk tube was placed under 1434, 820, 741, 695 cmÀ1 ; HR-MS (EI): 243.0933 (calcd.),
vacuum and the excess starting styrene and solvent removed 243.0936 (obs.).
leaving a colorless oil. A spectroscopic yield was obtained
under an atmosphere of argon prior to the sample being pu-
rified by short-path distillation under reduced pressure (2ꢃ
10À2 mbar, 608C).
4d (Table 3, entry 4): Colorless oil; yield: 47 mg (66%);
1H NMR (500 MHz, 298 K, C6D6): d=7.34–7.32 (m, 2H),
7.10–7.08 (m, 3H), 7.06 (d, 2H, J=8.3 Hz), 6.58 (d, 2H, J=
8.3 Hz), 4.05 (ddd, 1H, J=206.4, 7.8, 5.9 Hz), 2.46–2.35 (m,
2H), 1.80–1.66 (m, 2H); 13C{1H} NMR (125 MHz, 298 K,
C6D6): d=139.8 (d, J=7.6 Hz), 134.7 (d, J=12.4 Hz), 132.9
(d, J=16.2 Hz) 131.1, 128.9, 127.7, 127.5, 127.3, 33.0 (d, J=
8.6 Hz), 24.2 (d, J=14.3 Hz); 31P{1H} NMR (202 MHz,
298 K, CDCl3): d=À53.0; IR (solid): n=2923, 2285, 1490,
General Method for Catalytic Double
Hydrophosphination
The reaction mixture was prepared under an argon atmos-
phere in an M-Braun glove box; 1 (4.7 mg, 1.25 mol%) was
weighed out into a Schlenk tube. Styrene (2.28 mmol,
4 equiv.) was added to this followed by phenylphosphine
(63 mL, 0.57 mmol, 1 equiv.). After stirring at 408C for 24 h,
the Schlenk tube was placed under vacuum and the excess
starting styrene removed. A spectroscopic yield was ob-
tained prior to purification by column chromatography (1%
EtOAc/petroleum ether).
1434, 734, 695 cmÀ1
265.0548 (obs.).
; HR-MS (EI): 265.0544 (calcd.),
4e (Table 3, entry 5: Colorless oil; yield: 65 mg (78%);
1H NMR (500 MHz, 298 K, C6D6): d=7.34–7.30 (m, 2H),
7.20 (d, 2H, J=8.3 Hz), 7.08–7.07 (m, 3H), 6.51 (d, 2H, J=
8.3 Hz), 4.03 (ddd, 1H, J=206.4, 7.3, 5.9 Hz), 2.41–2.32 (m,
2H), 1.81–1.64 (m, 2H); 13C{1H} NMR (125 MHz, 298 K,
C6D6): d=133.5 (d, J=15.6 Hz), 131.3, 129.8, 128.3 (d, J=
5.7 Hz), 128.2, 128.1, 128.0, 127.9, 33.6 (d, J=8.3 Hz), 24.8
(d, J=13.7 Hz); 31P{1H} NMR (202 MHz, 298 K, CDCl3):
d=À52.7; IR (solid): n=2924, 2283, 1586, 1487, 1434, 801,
741, 695 cmÀ1; HR-MS (EI): 291.1297 (calcd.), 291.1304
(obs.).
4f (Table 3, entry 6): Colorless oil; yield: 44 mg (55%);
1H NMR (400 MHz, 298 K, C6D6): d=7.43–7.39 (m, 1H),
7.31–7.25 (m, 4H), 7.08–7.05 (m, 2H), 6.74–6.72 (m, 1H),
6.65–6.63 (m, 1H), 4.00 (d, 1H, J=205.8 Hz), 2.43–2.37 (m,
2H), 1.74–1.62 (m, 2H);); 13C{1H} NMR (100 MHz, 298 K,
C6D6): d=135.8, 134.3 (d, J=15.6 Hz), 133.3 (d, J=
19.5 Hz), 130.0, 129.2, 129.1, 128.9, 125.9, 34.8 (d, J=
8.1 Hz), 25.3 (d, J=14.5 Hz); 31P{1H} NMR (162 MHz,
298 K, C6D6): d=À52.6; IR (solid): n=3073, 2310, 1550,
1479, 1366, 759, 655 cmÀ1.
4g (Table 3, entry 7): Colorless oil; yield: 61 mg (76%);
1H NMR (400 MHz, 298 K, C6D6): d=7.55–7.51 (m, 1H),
7.50–7.47 (m, 2H), 7.43–7.34 (m, 4H), 7.23–7.19 (m, 2H),
7.09–7.03 (m, 3H), 6.97–6.95 (m, 2H), 4.11 (ddd, 1H, J=
207.4, 7.6, 6.4 Hz), 2.72–2.57 (m, 2H), 1.97–1.85 (m, 2H);
13C{1H} NMR (100 MHz, 298 K, C6D6): d=141.8 (d, J=
11.3 Hz), 141.2, 139.1 (d, J=2.2 Hz), 133.6 (d, J=15.5 Hz),
128.7, 128.6, 127.2, 127.1, 127.0, 127.0, 126.9, 34.1 (d, J=
8.2 Hz), 25.1 (d, J=13.7 Hz); 1P{1H} NMR (162 MHz,
298 K, C6D6): d=À52.7; IR (solid): n=3065, 2284, 1602,
1432, 820, 747, 695 cmÀ1; HR-MS (EI): 291.1304 (calcd.),
291.1297 (obs.).
4h (Table 3, entry 8): Colorless oil; yield: 52 mg (61%);
1H NMR (400 MHz, 298 K, C6D6): d=7.28–7.26 (m, 2H),
7.15 (m, 2H, partially obscured by solvent), 7.08–7.04 (m,
3H), 6.69–6.65 (m, 1H), 6.60–6.59 (m, 1H), 3.98 (dm, 1H,
J=206.5 Hz), 2.38–2.29 (m, 2H), 1.74–1.57 (m, 2H); 13C{1H}
General Method for Catalytic Unsymmetrical Double
Hydrophosphination
The reaction mixture was prepared under an argon atmos-
phere in an M-Braun glove box; 6 (0.5 mol%) was weighed
out into a Schlenk tube. CH3CN (200 mL) was added to this
followed by 4a (0.5 mmol, 1 equiv.) and a substituted styrene
(1 mmol, 2 equiv.) was added. After stirring at 608C for
60 h, the Schlenk tube was placed under vacuum and the
excess starting styrene and solvent removed. A spectroscop-
ic yield was obtained prior to purification by column chro-
matography (1% EtOAc/petroleum ether).
Characterization Data
4a (Table 3, entry 1): Colorless oil; yield: 32 mg (53%);
1H NMR (500 MHz, 298 K, C6D6): d=7.34 (s, 2H), 7.13–
7.07 (m, 6H), 6.94–6.93 (m, 2H), 4.09 (dm, 1H, J=210 Hz),
2.61–2.56 (m, 2H), 1.93–1.84 (m, 2H); 13C{1H} NMR
(125 MHz, 298 K, CDCl3): d=142.1, 139.7, 135.7 (d, J=
4.8 Hz), 133.6 (d, J=1.9 Hz), 128.3 (d, J=4.8 Hz), 128.1,
127.9, 125.9, 34.5 (d, J=2.9 Hz), 25.2 (d, J=3.8 Hz); 31P{1H}
NMR (202 MHz, 298 K, CDCl3): d=À52.3; IR (solid): n=
2912, 2283, 1602, 1495, 1434, 740, 720, 692 cmÀ1; HR-MS
(EI): 213.0828 (calcd.), 213.0834 (obs.).
4b (Table 3, entry 2): Colorless oil; yield: 26 mg (40%);
1H NMR (500 MHz, 298 K, C6D6): d=7.36–7.33 (m, 2H),
7.07–7.04 (m, 3H), 6.95 (d, 2H, J=7.9 Hz), 6.88 (d, 2H, J=
7.9 Hz), 4.10 (dm, 1H, J=206.3 Hz), 2.67–2.53 (m, 2H), 2.12
(s, 3H), 1.90–1.80 (m, 2H); 13C{1H} NMR (125 MHz, 298 K,
CDCl3): d=139.1 (d, J=7.3 Hz), 135.8 (d, J=12.3 Hz),
133.5 (d, J=15.5 Hz), 129.1, 129.0, 128.3 (d, J=5.6 Hz),
128.1, 128.0, 34.0 (d, J=8.1 Hz), 25.3 (d, J=13.5 Hz), 20.7;
31P{1H} NMR (202 MHz, 298 K, CDCl3): d=À53.0; IR
(solid): n=2920, 2283, 1591, 1515, 1436, 807, 740 cmÀ1; HR-
MS (EI): 227.0984 (calcd.), 227.0987 (obs.).
À
NMR (101 MHz, 298 K, C6D6, C P not observed): d=133.5
(d, J=15.3 Hz), 131.2, 129.8, 129.7, 129.0, 128.4 (d, J=
5.6 Hz), 128.0, 126.6, 122.5, 33.9 (d, J=8.6 Hz), 24.6 (d, J=
14.0 Hz); 31P{1H} NMR (162 MHz, 298 K, CDCl3): d=
À52.6; IR (solid): n=2923, 2283, 1593, 1567, 1475, 1434,
882, 781, 741, 694 cmÀ1; HR-MS (EI): 293.0089 (calcd.),
293.0095 (obs.).
4c (Table 3, entry 3): Colorless oil; yield: 40 mg (70%);
1H NMR (500 MHz, 298 K, C6D6): d=7.40–7.32 (m, 2H),
7.09–7.00 (m, 3H), 6.88 (d, 2H, J=10 Hz), 6.76 (d, 2H, J=
10 Hz), 4.12 (dm, 1H, J=206.3 Hz), 3.33 (s, 3H), 2.65–2.56
4i (Table 3, entry 9): Colorless oil; 1H NMR (500 MHz,
298 K, C6D6): d=8.54–8.53 (m, 1H), 7.59–7.57 (m, 1H),
(m, 2H), 1.98–1.86 (m, 2H); 31P{1H} NMR (202 MHz, 298 K, 7.54–7.51 (m, 2H), 7.34–7.32 (m, 3H), 7.12–7.10 (m, 2H),
CDCl3): d=À52.8; IR (solid): n=2930, 2283, 1610, 1511, 4.18 (ddd, 1H, J=211.0, 7.9, 6.3 Hz), 2.98–2.91 (m, 2H),
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
7
ÞÞ
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FULL PAPERS
Kimberley J. Gallagher et al.
2.31–2.22 (m, 2H); 13C{1H} NMR (125 MHz, 298 K, CDCl3):
d=161.4 (d, J=7.8 Hz), 149.3, 136.3, 133.6 (d, J=15.4 Hz),
128.5, 128.4, 128.2, 122.7, 121.2, 36.8 (d, J=7.5 Hz), 23.2 (d,
J=12.5 Hz); 31P{1H} NMR (202 MHz, 298 K, CDCl3): d=
À51.7; IR (solid): n=2913, 2279, 1590, 1474, 1433, 811,
741 cmÀ1; HR-MS (EI): 216.0937 (calcd.), 216.0939 (obs.).
4j (Table 3, entry 10): Colorless oil; yield: 19 mg (31%);
1H NMR (500 MHz, 298 K, C6D6): d=8.51–8.50 (m, 2H),
7.32–7.29 (m, 2H), 7.09–7.07 (m, 3H), 6.51–6.50 (m, 2H),
4.00 (ddd, 1H, J=206.9, 7.8, 5.9 Hz), 2.36–2.25 (m, 2H),
1.73–1.62 (m, 2H); 13C{1H} NMR (125 MHz, 298 K, CDCl3):
d=150.0, 133.5 (d, J=15.6 Hz), 128.4 (d, J=5.7 Hz), 128.2,
128.1 (d, J=8.6 Hz), 127.9, 123.2, 33.4(d, J=7.6 Hz), 23.7 (d,
J=14.3 Hz); 31P{1H} NMR (202 MHz, 298 K, CDCl3): d=
À52.5; HR-MS (EI): 232.0886 (calcd.), 232.0889 (obs.).
4k (Table 3, entry 11): Colorless oil; yield: 36 mg (64%);
1H NMR (500 MHz, 298 K, C6D6): d=7.34–7.29 (m, 2H),
7.03 (m, 3H), 4.02 (d, 1H, J=207.4 Hz), 3.28 (s, 3H), 2.18–
2.17 (m, 2H), 1.88–1.86 (m, 2H); 31P{1H} NMR (202 MHz,
298 K, CDCl3): d=À51.2; IR (solid): n=2923, 2280, 1593,
1568, 1475, 1434 cmÀ1; HR-MS (EI): 181.0413 (calcd.),
181.0414 (obs.).
4l (Table 3, entry 12): Colorless oil; yield: 49 mg (72%);
1H NMR (500 MHz, 298 K, C6D6): d=7.32–7.29 (m, 2H),
7.03–7.02 (m, 3H), 4.06 (ddd, 1H, J=207.9, 8.3, 5.9 Hz),
3.95–3.92 (m, 2H), 2.28–2.19 (m, 2H), 2.00–1.89 (m, 2H),
1.38–1.32 (m, 2H), 1.18–1.12 (m, 2H), 0.76–0.73 (m, 3H);
13C{1H} NMR (125 MHz, 298 K, CDCl3, carbonyl carbon not
observed): d=134.4, 129.1 (d, J=5.7 Hz), 128.8 (d, J=
18.1 Hz), 128.7, 64.6, 33.5 (d, J=8.6 Hz), 31.3, 19.7, 19.3,
19.2, 14.1; 31P{1H} NMR (202 MHz, 298 K, CDCl3): d=
À51.2; IR (solid): n=2958, 2873, 2285, 1730, 1600, 1464,
1435, 1388, 803, 737 cmÀ1; HR-MS (EI): 291.1303 (calcd.),
291.1297 (obs.).
(202 MHz, 298 K, CDCl3): d=À24.6. Unknown side-prod-
ucts observed in reaction catalyzed by 1.
5d (Table 4, entry 4): Colorless oil; yield: 217 mg (80%);
1H NMR (500 MHz, 298 K, C6D6): d=7.49–7.47 (m, 2H),
7.34–7.30 (m, 7H), 6.95–6.93 (m, 4H), 2.60–2.48 (m, 4H),
1.99–1.86 (m, 4H); 13C{1H} NMR (125 MHz, 298 K, CDCl3):
d=141.4 (d, J=11.3 Hz), 137.3 (d, J=14.5 Hz), 132.5 (d, J=
19.2 Hz), 131.4, 129.8, 129.2, 128.5 (d, J=7.2 Hz), 119.7, 31.6
(d, J=15.7 Hz), 30.2 (d, J=13.2 Hz); 31P{1H} NMR
(202 MHz, 298 K, C6D6): d=À24.2.
5e (Table 4, entry 5): Colorless oil; yield: 224 mg (82%);
1H NMR (400 MHz, 298 K, C6D6): d=7.36 (mbr, 2H), 7.16–
7.15 (m, 3H, partially obscured by solvent), 7.13–7.12 (m,
4H, partially obscured by solvent), 6.73–6.64 (m, 4H), 2.39–
2.32 (m, 4H), 1.67–1.55 (m, 4H); 13C{1H} NMR (101 MHz,
298 K, CDCl3): d=144.9 (d, J=11.5 Hz), 132.7, 132.5, 131.2,
130.0, 129.3, 129.2, 128.7 (d, J=7.3 Hz), 126.9, 122.5, 32.0 (d,
J=16.0 Hz), 30.1 (d, J=13.3 Hz); 31P{1H} NMR (162 MHz,
298 K, CDCl3): d=À23.5. Unknown side-products observed
in reaction catalyzed by 1.
5f (Table 4, entry 6): Colorless oil; yield: 161 mg (88%);
1H NMR (400 MHz, 298 K, CDCl3): d=8.56–8.55 (m, 2H),
7.66–7.58 (m, 4H), 7.42–7.40 (m, 3H), 7.15–7.12 (m, 4H),
2.96–2.89 (m, 4H), 2.27–2.23 (m, 4H); 13C{1H} NMR
(125 MHz, 298 K, CDCl3): d=161.9, 149.2, 136.5, 132.6 (d,
J=19.1 Hz), 129.0, 128.5, 128.4, 122.6, 121.1, 34.5 (d, J=
16.2 Hz), 28.0 (d, J=12.4 Hz); 31P{1H} NMR (162 MHz,
298 K, CDCl3): d=À22.9; HR-MS (EI): 336.1392 (calcd.),
336.1395 (obs.).
Acknowledgements
We thank the University of Bath for a DTA studentship
(KJG), the EPSRC UK National Mass Spectrometry Facility
at Swansea University for MS analysis and the EPSRC for
additional funding (EP/M019810/1). We also appreciate Dr.
G. D. Pantos¸ꢀ help with CD and HPLC studies.
5a (Table 4, entry 1): Colorless oil; yield: 144 mg (79%);
1H NMR (500 MHz, 298 K, C6D6): d=7.50–7.48 (m, 2H),
7.20–7.18 (m, 6H), 7.14–7.04 (m, 3H), 7.00–6.99 (m, 4H),
2.67–2.54 (m, 4H), 1.93–1.81 (m, 4H); 13C{1H} NMR
(125 MHz, 298 K, CDCl3): d=142.8 (d, J=11.6 Hz), 138.0
(d, J=14.9 Hz), 132.6 (d, J=18.9 Hz), 129.1, 128.6, 128.5,
128.2, 126.0, 32.3 (d, J=15.3 Hz), 30.3 (d, J=12.9 Hz);
31P{1H} NMR (121.5 MHz, 298 K, CDCl3): d=À23.4; HR-
MS (EI): 319.1610 (calcd.), 319.1614 (obs.). Unknown side-
products observed in reaction catalyzed by 1.
5b (Table 4, entry 2): Colorless oil; yield: 134 mg (62%);
1H NMR (500 MHz, 298 K, C6D6): d=7.66–7.63 (m, 2H),
7.47–7.42 (m, 3H), 7.13 (d, 4H, J=8.6 Hz), 6.88 (d, 4H, J=
8.6 Hz), 3.82 (s, 6H), 2.75–2.64 (m, 4H), 2.13–2.01 (m, 4H);
13C{1H} NMR (125 MHz, 298 K, CDCl3): d=157.9, 134.9 (d,
J=11.7 Hz), 132.6 (d, J=18.8 Hz), 129.3 (d, J=6.3 Hz),
129.1, 129.0, 128.5 (d, J=7.0), 113.9, 55.3, 31.4 (d, J=
15.3 Hz), 30.6 (d, J=12.9 Hz); 31P{1H} NMR (202 MHz,
298 K, CDCl3): d=À24.4; IR (solid): n=2931, 1610, 1583,
1509, 1463, 1434, 817, 742, 696 cmÀ1; HR-MS (EI): 379.1821
(calcd.), 379.1826(obs.).
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[11] Crystal data for C44H46Cl2FeP2 (5a-Fe). M=763.50, l=
0.71073 ꢂ, monoclinic, space group P 1 21/c 1, a=
19.8018(9), b=10.4550(4), c=19.1365(7) ꢂ, a=90, b=
o
90.463(3), g=90
,
U=3961.7(3) ꢂ3, Z=4, 1cald
=
1.280 gcmÀ3, m=0.626 mmÀ1, F(000)=1600. Crystal
size=0.3020ꢃ0.2709ꢃ0.2043 mm, unique reflections=
21880, observed reflections [I>2s(I)]=12709, data/re-
straints/parameters=21880/0/443. Observed data; R1=
0.0600, wR2=0.1445. All data; R1=0.1036, wR2=
0.1550. Max peak/hole=0.929 and À0.550 eꢂÀ3, re-
spectively. CCDC 1437893 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
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Adv. Synth. Catal. 0000, 000, 0 – 0
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10 A Study of Two Highly Active, Air-Stable Iron(III)-m-Oxo
Precatalysts: Synthetic Scope of Hydrophosphination using
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Kimberley J. Gallagher, Maialen Espinal-Viguri,
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