Unprecedented control of selectivity in Nickel-catalyzed hydrophosphorylation of alkynes: Efficient route to mono- and bisphosphonates

Article abstract of DOI:10.1002/adsc.201400123

A unique nickel-based catalytic system was developed where the direction of the hydrophosphorylation reaction can be controlled by varying the catalyst loading. A flexible one-pot access to vinylmonophosphonates and alkylbisphosphonates was demonstrated using simple starting materials in an atom-economic reaction without any specific solvents or ligands. Monitoring of the reaction mechanism with joint NMR and MS studies revealed key information about the reaction intermediates. The synthetic scope of the developed catalytic system was explored and the utility of the synthesized products for the fire protection of cotton materials was demonstrated.

Full text of DOI:10.1002/adsc.201400123

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DOI: 10.1002/adsc.201400123
Unprecedented Control of Selectivity in Nickel-Catalyzed
Hydrophosphorylation of Alkynes: Efficient Route to Mono-
and Bisphosphonates
Levon L. Khemchyan,a Julia V. Ivanova,a Sergey S. Zalesskiy,a
Valentine P. Ananikov,a,* Irina P. Beletskaya,b and Zoya A. Starikovac
a
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, 119991, Russia
Fax : (+7)-499-135-5328; e-mail: val@ioc.ac.ru
Chemistry Department, Lomonosov Moscow State University, Vorob’evy gory, Moscow, 119899, Russia
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, Moscow, 119991,
b
c
Russia
Received: February 3, 2014; Published online: March 3, 2014
Dedicated to the memory of Z. A. Starikova.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400123.
Abstract: A unique nickel-based catalytic system was mation about the reaction intermediates. The syn-
developed where the direction of the hydrophos- thetic scope of the developed catalytic system was
phorylation reaction can be controlled by varying explored and the utility of the synthesized products
the catalyst loading. A flexible one-pot access to vi- for the fire protection of cotton materials was dem-
nylmonophosphonates and alkylbisphosphonates was onstrated.
demonstrated using simple starting materials in an
atom-economic reaction without any specific solvents
or ligands. Monitoring of the reaction mechanism Keywords: alkynes; homogeneous catalysis; nickel;
with joint NMR and MS studies revealed key infor- phosphorylation; selectivity
Introduction
Bisphosphonates are valuable phosphoro-organic
compounds with a number of derivatives being uti-
Mono- and bisphosphonates are proven as well-suited lized as drugs against bone, dental, and other diseases
building blocks for plenty of applications in various (including osteoporosis and Pagetꢀs disease).[8] Due to
fields. Monophosphonates serve as monomers,[1] envi- the capability for metal chelation, the bisphospho-
ronmentally-friendly halogen-free flame retardants,[2] nates play a significant role as complexing agents.[9]
versatile building blocks in organic synthesis,[3] and The initial non-medical applications of bisphosphon-
demanding materials for a large number of medical
ates pertain to the oil industry[10] with potential inter-
ACHTUNGTRENNUNG
applications.[4] For instance, a-arylvinylphosphonates est for the future development.[11]
were successfully used for the synthesis of drug ana-
New fire safety standards have enforced a re-think-
logues such as Naproxen, Ibuprofen, and Fosmidomy- ing the concept of flame retardants and demanded
cin.[5] Vinylphosphonates can be used as simple and novel organophosphonate derivatives.[12] Efficient syn-
convenient precursors of 3,4-substituted derivatives of thetic strategies are required to access a variety of
(2S)-2-amino-4-phosphonobutanoic acid (L-AP4).[6] compounds with different substituents to fulfill re-
L-AP4 is a well-known drug with recognized and quirements in the area of fire protection.
promising potential to treat central nervous system
A number of vinylphosphonates is available via cat-
diseases (including Parkinsonꢀs and Alzheimerꢀs dis- alytic hydrophosphorylation of alkynes (addition of
eases).[7] Variations in the nature of the substituents H-phosphonates to the carbon-carbon triple bond).
in the starting vinylphosphonate allow the preparation Numerous findings in this area were reported and the
of L-AP4 derivatives with desirable structural and subject was discussed in numerous reviews.[13] The
medical properties.
vast majority of the reactions utilized palladium com-
Adv. Synth. Catal. 2014, 356, 771 – 780
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Levon L. Khemchyan et al.
plexes as catalysts,[5a,b,14] however several examples of complete conversion of 2a into 3aa in only 40 min. To
Rh- and Ni-catalyzed reactions were also reported.[15] prove the catalytic effect we conducted the same reac-
Unfortunately the existing methods of alkyne hy- tion in the absence of NiACHTNUTRGNEUNG(acac)2. Without the catalyst
drophosphorylation have some drawbacks that are only traces (2–3%) of 4aa were detected by
often crucial for practical applications, particularly 31P{1H} NMR.
the use of expensive (Rh, Pd) or unstable [Ni
G
An unusual finding was the dependence of the
metal catalysts, predominant use of phosphine ligands product yield and composition on the catalyst loading
and organic solvents which results in the formation of (Table 1, entries 1–3). Utilization of 4.5 and 2 mol%
toxic wastes. Moreover, to the best of our knowledge, of Ni decreased the yield of 3aa to 86 and 47%, re-
there is only one example describing the synthesis of spectively, while the conversion of H-phosphonate 2a
bisphosphonates via the double hydrophosphorylation was kept at 100%. An analysis of the 31P{1H} NMR
of terminal alkynes [5 mol% of PdACHTNURTGNE(UNG PPh3)4 as a catalyst, spectra of the reaction mixtures revealed the forma-
suitable only for a limited range of alkynes].[16,17] Be- tion of bisphosphonate 4aa as reaction product to-
sides the limited scope of substrates, another common gether with 3aa (Table 1, entries 2 and 3). The yield
drawback of known synthetic procedures is low reac- of 4aa was higher at decreased loadings of NiACHTUNGTRENNUNG(acac)2.
tion selectivity leading to the formation of mixtures Indeed, as little as 1 mol% of Ni catalyst led to a 63%
of mono- and bisphosphonates. Finally, examples of yield of 4aa after 3.5 h (Table 1, entry 4). Eventually,
catalytic double hydrophosphorylation of internal al- application of 1 mol% of Ni
ACHTUNGTNER(NNUG acac)2 and optimization
kynes have not been reported up to date. of the reaction conditions (reaction time and 1a:2a
Herein we report a new and efficient catalytic ratio) allowed us to reach a quantitative yield of bi-
system which is not affected by the shortcomings sphosphonate 4aa without traces of 3aa or other side-
listed above. We employed inexpensive commercially products (Table 1, entry 5). Thereby, the selective syn-
available Ni
G
thesis of either 3aa or 4aa was found to be possible by
a simple change of the nickel catalyst loading and the
1a:2a ratio.
Results and Discussion
The unprecedented catalytic switch discovered in
the present study is superior to tune the direction of
The hydrophosphorylation of diphenylacetylene 1a the addition reaction. Due to the absence of ligands,
with (i-PrO)2P(O)H 2a was chosen as the model reac- solvent or additives the synthesized monophospho-
tion (Table 1). The reaction does not proceed upon nate 3aa and bisphosphonate 4aa could be easily iso-
heating of the mixture of 1a, 2a and NiACTHNUGTRENUNG(acac)2. How- lated from the crude reaction mixture. As expected,
ever, we have found that addition of a catalytic 4aa represented a composition of racemate and meso-
amount of diisobutylaluminum hydride (DIBAL) form which were successfully separated by means of
allows us to reach 100% conversion of starting mate- dry column chromatography. The structure of meso-
rials 1a and 2a. Indeed, the use of the NiACHTUNTRGNEUNG(acac)2 4aa was confirmed with the combination of 1D,
(9 mol%)/DIBAL system led to the desired syn-addi- 2D NMR
experiments
and
X-ray
analysis.
1
1
tion product 3aa with 99% yield and complete stereo- 1H-31P HMBC, H-13C HSQC and H-13C HMBC ex-
selectivity (Table 1, entry 1). Remarkably, no solvent, periments were used to establish the structure of rac-
ligand or any other additive was required to reach the 4aa, the measured chemical shifts and coupling con-
Table 1. The model hydrophosphorylation of 1a with 2a: dependence of selectivity on NiACHTUNGTRNEUNG
(acac)2 loadings.[a]
Entry
Ni
9
4.5
2
1
1
(acac)2 [mol%]
Conditions (time and 1a:2a molar ratio)
Yield of 3aa[b] [%]
Yield of 4aa[b,c] [%]
1
2
3
4
5
40 min (1:1)
1 h (1:1)
1 h (1:1)
3.5 h (1:1)
28 h (1:2.5)
99
86
47
36
0
0
13
52
63
99
[a]
2 equiv. of DIBAL relative to NiACTHNURGTNEUNG(acac)2 were used, see the Experimental Section for details.
[b]
Determined by 31P{1H} NMR. In the cases of entries 1–4 the yields are given based on the initial amount of H-phospho-
nate 2a; in the case of entry 5 the yield is given based on the initial amount of alkyne 1a.
4aa represents a mixture of rac- and meso-forms.
[c]
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Unprecedented Control of Selectivity in Nickel-Catalyzed Hydrophosphorylation
Table 2. The model hydrophosphorylation of 1a with 2a:
evaluation of performance of different Ni catalyst precur-
AHCTUNGTRENNUNG
sors.[a]
Entry Catalyst precursor
Yield 3aa/4aa[b] [%]
With DIBAL Without DIBAL
1
2
3
4
Ni
NiBr2
NiCl2
G
86/13
93/3
87/3
0/0
0/0
0/0
Ni
53/46
9/0[c]
[a]
1a (1 mmol), 2a (1 mmol), [Ni] (4.5 mol%), DIBAL
(9 mol%), 1208C, 3 h; see the Experimental Section for
additional details.
[b]
[c]
Determined by 31P{1H} NMR.
9 mol% of NiACHTNUTRGNE(NUG COD)2, 1208C, 19 h.
Scheme 1. Hydrophosphorylation of 3aa with 2a [4.5 mol%
The case of Ni
is well-known that NiAHCTUNGTRENNUNG
ACHTUNGTRENNUNG
of Ni
ACHTUNGTRENNUNG(acac)2 and 9 mol% of DIBAL; see the Experimental
Section for details].
pound due to the presence of the Ni(0) center and
labile cyclooctadiene ligands. However, in our case
stants were in agreement with literature data for simi- only a trace amount of product 3aa was formed in the
lar phosphorus-containing molecules.[18]
absence of DIBAL (Table 2, entry 4). It is evident
Formation of bisphosphonate 4aa is a one-pot pro- that Ni(0) itself does not govern the catalytic cycle.
cess which proceeds via subsequent hydrophosphory- This means that in the Ni(acac)2/DIBAL system the
AHCTUNGTRENNUNG
lation of vinylphosphonate 3aa with a second mole- latter component serves not only to reduce Ni(II) to
cule of 2a. To explore this step, four independent ex- Ni(0), but also to promote the formation of Ni-con-
periments were conducted (Scheme 1). Freshly syn- taining catalytically active species. It is known that re-
thesized and purified 3aa was used as the starting ma- duction of Ni(II) upon interaction of Ni
terial for the reaction with 2a. Good yields of 4aa DIBAL proceeds via formation of acacNi-i-Bu species
were reached in the presence of the Ni
(acac)2/DIBAL (A) (Scheme 2).[19] Further b-hydride elimination
ACHTUNGTERNN(UNG acac)2 with
AHCTUNGTRENNUNG
or DIBAL alone. Thus, it can be proposed that the leads to formation of active nickel hydride acacNiH
transformation of monophosphonate to bisphospho- (A’) and isobutylene (detected in our study by in situ
nate was mediated by a catalytic amount of DIBAL. 1H and 13C NMR). On the next step interaction with
The observed dependence of reaction selectivity on H-phosphonate molecule yields complex B which
Ni
ACHTUNGTRENNUNG
following factors. At higher NiAHCNUTGTRENNUNG
phosphonate 2a is rapidly converted into 3aa. Indeed,
It should be noted that the initial presence of H-
31P{1H} NMR monitoring of the reaction with 1a:2a= phosphonate 2a in the catalytic system was essential
1:1 molar ratio revealed that the use of 9 mol% of for the activation of catalyst precursor and to avoid
NiACHTUNGTRENNUNG(acac)2 (Table 1, entry 1) leads to approximately degradation of in situ formed active hydride species.
80% of 2a being consumed in 5 min with 3aa being This fact was proven by the additional experiment
the only product. Lowering the catalyst loading with the reversed order of reagent addition: 1a and
(while retaining the 1:1 phosphonate to alkyne molar 2a were placed in the reaction vessel after mixing of
ratio) leads to decrease in 3aa formation rate making Ni
it possible for the H-phosphonate 2a to react with in to the mixture of 1a, 2a and Ni
situ formed 3aa leading to bisphosphorylation adduct 48% conversion of 2a was observed [9 mol% of
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
4aa. To achieve quantitative yield of 4aa the excess of NiACTHNUTRGNEUNG
(acac)2, 1 h].[20] It is known that 2a exists in equilib-
H-phosphonate to alkyne was used (Table 1, entry 5). rium with its tautomeric form (i-PrO)2P-OH[21] which
Furthermore, we examined the performance of dif- has a lone electron pair on the phosphorus atom.
ferent nickel catalyst precursors in the model reaction Thus, the H-phosphonate can also act as a ligand to
(Table 2). The use of NiBr2 and NiCl2 showed good stabilize the species B and D.[22]
results comparable to those for Ni
G
To get insight into the mechanistic picture we per-
lectivity was slightly better (Table 2, cf. entries 1, 2 formed combined NMR and ESI-MS monitoring of
and 3). However, among the studied Ni(II) catalyst the hydrophosphorylation reaction.[20] The use of both
precursors, NiACHTUNGTRENNUNG(acac)2 is preferable to design a halo- NMR and MS allowed a number of Ni-containing
gen-free catalytic system.
complexes to be independently detected (see the Sup-
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Levon L. Khemchyan et al.
Scheme 2. Plausible catalytic cycle for the hydrophosphorylation reaction based on ESI-MS and NMR monitoring.[20]
porting Information, Figures S1, S2, and S3). The in- unsymmetrical internal alkyne 1b (Table 3, entries 3
teraction of A’ with 2a leads to the formation of inter- and 4).
mediate
B
which was intercepted by ESI-MS
The developed catalytic procedure demonstrated
(Scheme 2, Figure S1). The next step involves the for- high yields of bisphosphonates formed from alkynes
mation of complex C via coordination of alkyne 1a to 1c–1e at high and low Ni loadings (Table 3, entries 5–
the Ni atom of complex B. Subsequent insertion of 10). In case of internal alkyne 1f the monophospho-
À
the alkyne into the Ni H bond in C results in forma- nate 3fa was selectively formed with 90% yield with
tion of vinyl complex D, which was successfully inter- 9 mol% of Ni
A
cepted by ESI-MS (Scheme 2, Figure S1) and inde- formed when 1 mol% of NiACHTGNUTRENNUNG
pendently detected by NMR (31P{1H} chemical shift: (Table 3, entries 11 and 12). Various other bis- and
106.2 ppm; Figures S2 and S3).[20] The observed for- monophosphonates were prepared in good to high
mation of complex D is in agreement with theoretical yields using our catalytic system (Table 3, entries 13–
calculations, where it was shown that alkyne insertion 17).
into the metal-hydrogen bond is much more favorable
Although nickel complexes are known to promote
compared to alkyne insertion into the metal-phospho- alkyne polymerization,[24] in the present case this side
rus bond.[23] Further reductive elimination of product reaction did not make a significant contribution, thus
3aa from complex D leads to regeneration of B after having no impact on the performance of the synthetic
reaction with 2a.
Subsequently we tested the application of the de- system was tolerant to the steric bulkiness of R3 sub-
veloped Ni(acac)2/DIBAL catalytic system towards stituents (i-C3H7, C6H5, C12H25) in compound 2, allow-
procedure. Furthermore, the developed catalytic
ACHTUNGTRENNUNG
the synthesis of different mono- and bisphosphonates ing a number of corresponding products to be success-
(Table 3). The corresponding products 3 and 4 were fully synthesized (Table 3).
obtained with excellent yields both for symmetrical
Finally, we studied the efficiency of the synthesized
internal alkyne 1a (Table 3, entries 1 and 2) and for compounds as potential flame protection materials.
The specimens of cotton textile (control sample and
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Unprecedented Control of Selectivity in Nickel-Catalyzed Hydrophosphorylation
Table 3. The scope of the Ni-catalyzed hydrophosphorylation of alkynes.[a]
Entry
Alkyne
H-phosphonate
Ni (mol%)
Yield[b] [%]
Product
1
2
3
4
5
6
7
8
1a
1a
1b
1b
1c
1c
1d
1d
1e
1e
1f
1f
1a
1b
1a
1b
1d
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2c
2c
2b
9
1
9
1
9
1
9
1
9
1
9
1
9
9
4.5
4.5
9
99
99
90
75
97
80
99
72
85
80
90
19
95
60
95
77
95
3aa
4aa
3ba
4ba
4ca
4ca
4da
4da
4ea
4ea
3fa
3fa
3ab
3bb
3ac
3bc
4db
9
10
11
12
13
14
15
16
17
[a]
See the Experimental Section and Supporting Information for details.
[b]
Determined by 31P{1H} NMR. In the cases of entries 1, 3, 5–17 the yields are given based on the initial amount of H-phos-
phonate 2; in the case of entries 2 and 4the yields are given based on the initial amount of alkyne 1a.
two samples impregnated with solutions of 3aa and ure 1A and C, D). The product of double phosphory-
meso-4aa) were investigated by field-emission scan- lation reaction showed slightly better protection prop-
ning electron microscopy (FE-SEM) after combus- erties (the larger thickness of individual fibers was
tion. The study demonstrated a high impact of the preserved after burning; Figure 1D). However, this is
pretreatment of cotton textile on their flame resistivi- a preliminary observation only that needs to be fur-
ty (Figure 1).
ther studied in more detail.
FE-SEM showed that the native textile consisted of
the regular structure with the mean fiber diameter of
about 14 mm (Figure 1A). After combustion of the Conclusions
textile the structure had dramatically changed. The
average fiber diameter was lowered down to 4 mm re- In summary, the superior performance of the
sulting in formation of a deformed structure (Fig- NiACTHNUGRTENUNG(acac)2/DIBAL system in catalytic hydrophosphory-
ure 1B). For the samples pretreated with 3aa and lation of alkynes was revealed. Remarkably, no specif-
meso-4aa FE-SEM revealed negligible changes in the ic solvents or ligands were required to reach complete
general morphology after combustion (Figure 1C and conversion of the starting materials into the desired
D). The fine structure of the fibers had no cracks, products. The unique selectivity switch discovered in
spikes and the fibers possessed a smooth surface. Ap- the present study made it possible to direct the reac-
parently, compounds 3aa and meso-4aa protected tion in the desired way by a simple change of the cat-
cotton fibers from structural distortions. In the case of alyst loading and reagent ratio. The formation of
3aa the mean fiber diameter was about 13 mm and in either mono- or bisphosphonates can be achieved
the case of meso-4aa about 14 mm. Thus, both com- with the developed system.
pounds showed good efficiency as potential fire pro-
tection materials. In fact, no critical deformations catalyst precursor NiAHCNUTGTRENNUNG
The inexpensive, halogen-free and easy to handle
(acac)2 makes the synthetic pro-
were observed on comparing native non-burned tex- cedure convenient for practical usage. The catalytic
tile and pretreated samples after burning (cf. Fig- system developed provides a cost-efficient and green
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Levon L. Khemchyan et al.
Figure 1. FE-SEM images of the cotton textile: native material before burning (A), after burning without pretreatment (B),
after pretreatment with 3aa and meso-4aa followed by burning (C and D, respectively).
(entry 3); 1.0ꢂ10À2 mmol (2.6 mg) (entry 4). The used quan-
tities of DIBAL (1M solution in THF) were 18ꢂ10À2 mmol
(0.18 mL) (entry 1); 9ꢂ10À2 mmol (0.09 mL) (entry 2); 4ꢂ
10À2 mmol (0.04 mL) (entry 3); 2ꢂ10À2 mmol (0.02 mL)
(entry 4).
À
chemical method to create C P bonds. Demanding
fire-protective phosphonate derivatives were prepared
in one-pot procedures from readily available starting
compounds.
Conditions ii (for entry 5): 1a (1.0 mmol, 178.2 mg), 2a
(1.0 mmol, 0.167 mL), and NiACHTNUGRTNEUNG
(acac)2 (1.0ꢂ10À2 mmol,
Experimental Section
2.6 mg) were placed into a reaction vessel and stirred at
room temperature for 5 min. DIBAL (1M solution in THF,
2ꢂ10À2 mmol, 0.02 mL) was added to the obtained green
mixture under stirring and a continuous flow of argon. The
color of the mixture immediately turned from green to
black. The reaction was carried out at 1208C under stirring.
After 4 h the heating was stopped and 2a (1.5 mmol,
0.250 mL), DIBAL (1M solution in THF, 2ꢂ10À2 mmol,
0.02 mL) were added to the reaction mixture under a contin-
uous flow of argon. The heating was continued at the same
temperature for 24 h under stirring.
General Synthetic Procedure (Table 1)
Conditions i (for entries 1–4): 1a (1.0 mmol, 178.2 mg), 2a
(1.0 mmol, 0.167 mL), and NiACHTNUTRGENNG(U acac)2 were placed into a reac-
tion vessel and stirred at room temperature for 5 min.
DIBAL (1M solution in THF) was added to the obtained
green mixture under stirring and a continuous flow of argon.
The color of the mixture immediately turned from green to
black. The reaction was carried out at 1208C under stirring.
See Table 1 for reaction times. Molar ratio Ni
DIBAL was 1/2 for all reactions. The used quantities of Ni-
(acac)2 were 9ꢂ10À2 mmol (23.1 mg) (entry 1); 4.5ꢂ
10À2 mmol (11.6 mg) (entry 2); 2.0ꢂ10À2 mmol (5.1 mg)
ACHTUNGTNER(NUNG acac)2/
ACHTUNGTRENNUNG
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Unprecedented Control of Selectivity in Nickel-Catalyzed Hydrophosphorylation
(0.4 bar) and dry gas (4.0 LminÀ1); interface temperature
was set at 1808C. Recorded spectra were processed using
the Bruker DataAnalysis 4.0 software package.
Hydrophosphorylation of 3aa with 2a (Scheme 1)
The conditions i of the general synthetic procedure as de-
scribed above were used. 3aa (1.0 mmol, 344.2 mg) was
taken as starting material. Molar ratio 3aa/2a was 1/1 (the
used quantities: 344.2 mg of 3aa, 0.167 mL of 2a) for all re-
FE-SEM Experiments
For the FE-SEM measurements samples were mounted on
a 25 mm aluminum specimen stub and fixed by conductive
silver paint. The observations were carried out using a Hita-
chi SU8000 field-emission scanning electron microscope
(FE-SEM). Images were acquired in secondary electron
mode at 10 kV accelerating voltage and at the working dis-
tance of 8–10 mm. For the sample of native cotton textile,
metal coating with a thin film (10 nm) of Pt/Pd alloy (80/20)
was performed using the magnetron sputtering method as
described earlier.[25] The morphology of the coated samples
was studied as adjusted for the metal coating surface effects.
For burning experiments (Figure 1C, D) cotton material
was treated with a solution of vinylphosphonate 3aa (50 mg)
or 1,2-bisphosphonate meso-4aa (50 mg) in dichloromethane
(1 mL) at room temperature for two minutes. Then the ma-
terial was dried at 508C for 10 min. All samples were kept
under standard atmospheric pressure for at least 24 h prior
to experiments.
actions except the reaction where the NiACTHNUTRGENUG(N acac)2/DIBAL cat-
alytic system was utilized. In the latter case a 1/1.5 molar
ratio of 3aa/2a was used (the used quantities: 344.2 mg of
3aa, 0.250 mL of 2a). See Scheme 1 for more details.
Evaluation of Performance of Different Ni Catalyst
Precursors (Table 2)
1a (1.0 mmol, 178.2 mg), 2a (1.0 mmol, 0.167 mL), and Ni
catalyst precursor (4.5ꢂ10À2 mmol) were placed into a reac-
tion vessel and stirred at room temperature for 5 min.
DIBAL (1M solution in THF, 9ꢂ10À2 mmol, 0.09 mL) was
added to the obtained mixture under stirring and a continu-
ous flow of argon. The reaction was carried out at 1208C for
3 h under stirring.
NMR Experiments
All NMR measurements were performed with Bruker DRX
500 and Avance 600 spectrometers operating at 500.1 and Purification and Characterization of Products
1
600.1 MHz for H, 202.5 and 242.9 MHz for 31P and 125.8
After completion of the reaction the products were purified
and 150.9 MHz for 13C nuclei. Unless otherwise noted, the
by dry column vacuum chromatography on silica.[26] Hex-
anes/ethyl acetate/ethanol gradient elution was applied.
After evaporation of solvents under vacuum the pure prod-
samples for NMR experiments were prepared directly after
1
the end of heating. The H NMR chemical shifts are report-
ed relative to TMS as internal standard. The 13C NMR
ucts were obtained. Dry column flash chromatography has
chemical shifts are reported relative to the corresponding
several practical advantages: 1) only a small amount of
deuterated solvent signals used as internal reference. The
silica required, 2) quick elution, and 3) economy of solvents.
31P NMR chemical shifts are reported relative to external
However, slightly better isolated yields (by 5–10%) may be
standard H3PO4/H2O. The spectra were processed with the
achieved using conventional column chromatography.
Bruker Topspin 2.1 software package.
Diisopropyl
[(E)-1-methyl-2-phenylvinyl]phosphonate
(3ba): Yellow oil; yield; 200 mg (71%). 1H NMR
ESI-MS Experiments
The samples for ESI-MS analysis of the isolated pure prod-
ucts 3 and 4 were prepared in 1.5 mL Eppendorf tubes
(MeCN solutions). All plastic disposables (Eppendorf tubes
and tips) used in sample preparation were washed with
MeCN before use.
The samples for mechanistic ESI-MS investigation of the
hydrophosphorylation reaction (see also the Supporting In-
formation) were prepared by taking an aliquot of the reac-
tion mixture under an argon atmosphere using a glass sy-
ringe. The aliquot was then immediately diluted with MeCN
directly in the syringe and injected into the ion source of the
mass spectrometer.
ESI-mass spectra were recorded on a high resolution
Bruker maXis instrument equipped with an electrospray
ionization (ESI) ion source. The measurements were per-
formed in a positive (+MS) ion mode (interface capillary
voltage: 4500 V) with scan range m/z: 50–3000. External cal-
ibration of the mass spectrometer was performed with Elec-
trospray Calibrant Solution (Fluka). A direct syringe injec-
tion was used for all the analyzed solutions in MeCN (flow
rate: 3 mLminÀ1). Nitrogen was used as nebulizer gas
(500.1 MHz, CDCl3, 258C, TMS): d=7.48 [d, 3J
24.9 Hz, 1H], 7.42–7.34 (m, 4H), 7.34–7.26 (m, 1H), 4.77–
4.66 (m, 2H), 2.07 [d, 3J
(P,H)=15.2 Hz, 3H], 1.38 [d,
(H,H)=6.2 Hz, 6H], 1.32 [d, (H,H)=6.2 Hz, 6H];
13C NMR (125 MHz, CDCl3): d=141.96 [2J
(P,C)=11.9 Hz],
136.11 [3J
(P,C)=23.8 Hz], 129.53, 128.47, 128.30, 127.60
[1J(P,C)=178.8 Hz], 70.40 [2J(P,C)=5.6 Hz], 24.23 [3J
(P,C)=
3.9 Hz], 24.01 [3J(P,C)=4.6 Hz], 14.52 [2J
(P,C)=9.0 Hz];
ACHTUGNTREN(NUNG P,H)cis =
AHCTUNGTRENNUNG
J
G
JACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
G
G
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
31P NMR (202 MHz, CDCl3): d=20.33; HR-MS (ESI):
m/z=305.1282, calcd. for C15H23O3P: 305.1277 [M+Na]+
(D=1.6 ppm); elemental analysis calcd. (%) for C15H23O3P:
C 63.82, H 8.21, P 10.97; found: C 63.52; H 8.16; P 10.94.
Diphenyl [(E)-1-methyl-2-phenylvinyl]phosphonate (3bb):
Yellow oil; yield: 175 mg (50%). 1H NMR (500.1 MHz,
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CDCl3, 258C, TMS): d=7.67 [d, 3J
7.41–7.35 (m, 4H), 7.35–7.28 (m, 5H), 7.28–7.21 (m, 4H),
G
7.65–7.50 (m, 4H), 7.38–7.21 (m, 6H), 4.17–4.07 (m, 2H),
4.04–3.94 (m, 2H), 3.83 [dd, 3J(P,H)=3.0 Hz, 2J
(P,H)=
7.7 Hz, 2H], 1.06 [d, (H,H)=6.1 Hz, 6H], 0.99 [d,
(H,H)=6.1 Hz, 6H], 0.63 [d, J(H,H)=6.1 Hz, 6H], 0.43 [d,
(H,H)=6.1 Hz, 6H]; 13C NMR (125 MHz, CDCl3): d=
135.97, 131.03, 128.18, 127.39, 72.06, 69.41, 49.06, 48.70,
48.15, 47.59, 47.23, 24.65, 23.77, 23.32, 22.44; 31P NMR
(202 MHz, CDCl3): d=25.23; HR-MS (ESI): m/z=511.2379,
calcd. for C26H40O6P2: 511.2373 [M+H]+ (D=1.2 ppm); ele-
mental analysis calcd. (%) for C26H40O6P2: C 61.17, H 7.90,
P 12.13; found: C 61.00; H 8.13; P 12.07. The determined
molecular structure of meso-4aa is presented in Figure 2.
E
ACHTUNGTRENNUNG
3
JACHTUNGTRENNUNG
7.18–7.10 (m, 2H), 2.25 [d, J
(150.9 MHz, CDCl3): d=150.60 [2J
[2J(P,C)=12.5 Hz], 135.27 [3J
(P,C)=25.4 Hz], 129.81, 129.64,
128.92, 128.56, 125.11, 124.7 [1J
(P,C)=181.1 Hz], 120.58
[3J [2J 31P NMR
(P,C)=4.5 Hz], 14.60 (P,C)=9.0 Hz];
J
J
N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(202 MHz, CDCl3): d=15.96; HR-MS (ESI): m/z=351.1144,
calcd. for C21H19O3P: 351.1145 [M+H]+ (D=0.3 ppm); ele-
mental analysis calcd. (%) for C21H19O3P: C 71.99, H 5.47, P
8.84; found: C 71.69; H 5.37; P 8.70.
Didodecyl
[(E)-1-methyl-2-phenylvinyl]phosphonate
(3bc): Yellow oil; yield: 358 mg (67%).
1H NMR
(500.1 MHz, CDCl3, 258C, TMS): d=7.46 [d, 3J
24.8 Hz, 1H], 7.41–7.35 (m, 4H), 7.35–7.26 (m, 1H), 4.15–
ACHTUGNTREN(NUNG P,H)cis =
3
3.90 (m, 4H), 2.06 [d, J
4H), 1.48–1.14 (m, 36H), 0.95–0.83 (m, 6H); 13C NMR
(150.9 MHz, CDCl3): d=142.68 [2J
(P,C)=11.6 Hz], 135.82
[3J(P,C)=23.8 Hz], 129.55, 128.47, 128.42, 126.05 [1J
(P,C)=
178.5 Hz], 65.95 [2J
(P,C)=5.7 Hz], 32.03, 30.65, 30.61, 29.76,
29.74, 29.69, 29.66, 29.46, 29.30, 25.72, 22.80, 14.44 [2J
(P,C)=
ACHTUNGTRNE(NUNG P,H)=15.3 Hz, 3H], 1.77–1.61 (m,
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
9.0 Hz], 14.21; 31P NMR (202 MHz, CDCl3): d=22.67; HR-
MS (ESI): m/z=557.4087, calcd. for C33H59O3P: 557.4094
[M+Na]+ (D=1.3 ppm); elemental analysis calcd. (%) for
C33H59O3P: C 74.11, H 11.12, P 5.79; found: C 74.03; H
11.02; P 5.69.
The compounds 3aa, 3fa, 3ab, 3ac were identified by com-
parison with the published spectral data.[15f]
rac-Tetraisopropyl
(1,2-diphenylethane-1,2-diyl)bis-
(phosphonate) (rac-4aa): Yellow oil; yield: 179 mg (35%).
Figure 2. The molecular structure of meso-4aa determined
by X-ray analysis.
CCDC 975404 contains the supplementary crystallograph-
ic data for meso-4aa. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
1H NMR (500.1 MHz, CDCl3, 258C, TMS): d=7.25–7.07 (m,
10H), 4.83–4.66 (m, 2H), 4.41–4.25 (m, 2H), 3.89 [d,
Tetraisopropyl (1-phenylethane-1,2-diyl)bis(phosphonate)
2J
N
ACHTUNGTRNE(NUNG H,H)=
(4ca): Yellow oil; yield: 163 mg (75%).
1H NMR
JACHTUNGTRENNUG
(125 MHz, CDCl3): d=132.94, 132.54, 127.37, 127.29, 71.72,
70.38, 45.71, 45.45, 44.89, 44.33, 44.07, 24.41, 24.15, 22.99;
31P NMR (202 MHz, CDCl3): d=25.68; HR-MS (ESI):
m/z=511.2366, calcd. for C26H40O6P2: 511.2373 [M+H]+
(D=1.4 ppm); elemental analysis calcd. (%) for C26H40O6P2:
C 61.17, H 7.90, P 12.13; found: C 60.79; H 8.02, P 12.32.
(500.1 MHz, CDCl3, 258C, TMS): d=7.41–7.34 (m, 2H),
7.31–7.19 (m, 3H), 4.72–4.60 (m, 1H), 4.56–4.46 (m, 1H),
4.46–4.29 (m, 2H), 3.44–3.29 (m, 1H), 2.51–2.32 (m, 2H),
meso-Tetraisopropyl
(1,2-diphenylethane-1,2-diyl)bis-
(phosphonate) (meso-4aa): White crystals; yield: 92 mg
(18%). 1H NMR (500.1 MHz, CDCl3, 258C, TMS): d=
1.32–1.27 (m, 6H), 1.21 [d, JACHTGNUTRENNUNG
J
J
J
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
U
778
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FULL PAPERS
Unprecedented Control of Selectivity in Nickel-Catalyzed Hydrophosphorylation
[2J
5.6 Hz], 70.08 [2J
28.04 [1J
(P,C)=140.0 Hz], 24.22, 23.91, 23.83, 23.56, 23.03;
31P NMR (202 MHz, CDCl3): d=27.20 [d, J
N
E
(P,C)=
Milnes, J. R. Ebdon, B. J. Hunt, P. Joseph, Polym.
Degrad. Stab. 2002, 77, 227–233; c) S.-Y. Lu, I. Hamer-
ton, Prog. Polym. Sci. 2002, 27, 1661–1712.
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
3
G
[3] a) T. Minami, J. Motoyoshiya, Synthesis 1992, 333–349;
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calcd. for C20H36O6P2: 435.2060 [M+H]+ (D=0.7 ppm); ele-
mental analysis calcd. (%) for C20H36O6P2: C 55.29, H 8.35,
P 14.26; found: C 55.24; H 8.20; P 14.11.
Tetraisopropyl heptane-1,2-diylbis(phosphonate) (4da):
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CDCl3, 258C, TMS): d=4.75–4.62 (m, 4H), 2.22–1.87 (m,
3H), 1.82–1.55 (m, 4H), 1.55–1.45 (m, 1H), 1.45–1.33 (m,
1H), 1.33–1.06 (m, 26H), 0.92–0.71 (m, 3H); 13C NMR
(125 MHz, CDCl3): d=70.22 [2J
[1J
24.08, 22.49, 14.06; 31P NMR (202 MHz, CDCl3): d=31.18
[d, 3J(P,P)=78.3 Hz], 28.92 [d, 3J
(P,P)=78.3 Hz]; HR-MS
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(ESI): m/z=429.2524, calcd. for C19H42O6P2: 429.2529 [M+
H]+ (D=1.2 ppm).
Tetraisopropyl ethane-1,2-diylbis(phosphonate) (4ea):
Yellow oil; yield: 116 mg (65%). 1H NMR (500.1 MHz,
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CDCl3, 258C, TMS): d=4.76–4.62 (m, 4H), 1.95–1.88 (m,
4H), 1.32 [d, JACHTUNGTRENNUNG
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C 46.92, H 9.00, P 17.29; found: C 46.64; H 9.15; P 17.13.
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Department of Structural Studies of Zelinsky Institute of Or-
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for recording SEM images. This research was supported by
Russian Foundation for Basic Research (grants 12-03-31518
and 13-03-01210).
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Adv. Synth. Catal. 2014, 356, 771 – 780