Homo- and cross-olefin metathesis coupling of vinylphosphane oxides and electron-poor alkenes: Access to P-stereogenic dienophiles

Article abstract of DOI:10.1002/adsc.200505463

Vinylphosphane oxides 6 undergo catalytic olefin homo-metathesis leading to achiral and P-stereogenic diphosphane dioxides 7 with exclusive (E)-selectivity. Similarly, EWG-substituted vinylphosphane oxides 11, 12 could be prepared with complete (E)-olefin selectivity via olefin cross-metathesis with electron-deficient substrates, such as methyl acrylate and 2-fluorostyrene, using nitro-Hoveyda ruthenium pre-catalyst III. Cross- and homo-metathesis of chiral non-racemic vinylphosphane oxides proceeds without racemization of the phosphorus center of chirality.

Full text of DOI:10.1002/adsc.200505463

FULL PAPERS
DOI: 10.1002/adsc.200505463
Homo- and Cross-Olefin Metathesis Coupling of Vinylphosphane
Oxides and Electron-Poor Alkenes: Access to P-Stereogenic
Dienophiles
a
b
c
c
Nikolai Vinokurov, Anna Michrowska, Anna Szmigielska, Zbigniew Drzazga,
c
c
b,
Grzegorz W o´ jciuk, Oleg M.Demchuk, Karol Grela, *
b, c,
a,
K.Michał Pietrusiewicz, * Holger Butenschçn *
Institut für Organische Chemie, Universität Hannover, Schneiderberg 1B, 30167 Hannover, Germany
a
E-mail: holger.butenschoen@mbox.oci.uni-hannover.de
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
b
Fax: (þ48)-22-632-66-81, e-mail: grela@icho.edu.pl
c
Department of Organic Chemistry, Maria Curie-Skłodowska-University Lublin, ul.Gliniana 33, 20-614 Lublin, Poland
E-mail: michal@hermes.umcs.lublin.pl
Received: December 7, 2005; Accepted: March 16, 2006
Supporting Information for this article is available on the WWW under http://asc.wiley-vch.de/home/.
Abstract: Vinylphosphane oxides 6 undergo catalytic 2-fluorostyrene, using nitro-Hoveyda ruthenium pre-
olefin homo-metathesis leading to achiral and P-ster- catalyst III.Cross- and homo-metathesis of chiral
eogenic diphosphane dioxides 7 with exclusive (E)-se- non-racemic vinylphosphane oxides proceeds without
lectivity.Similarly, EWG-substituted vinylphosphane
racemization of the phosphorus center of chirality.
oxides 11, 12 could be prepared with complete (E)-
olefin selectivity via olefin cross-metathesis with elec- Keywords: catalysis; metathesis, P-stereogenic; ruthe-
tron-deficient substrates, such as methyl acrylate and nium, vinylphosphane oxide
Introduction
phane ligands, which have proved valuable in asymmet-
ric catalysis. Historically, the first homogeneous enan-
[
21]
Next to palladium-catalyzed coupling reactions, meta- tioselective hydrogenation reaction of prochiral sub-
thesis catalysis has proved to be the most valuable tool strates by using a chiral rhodium metal complex was re-
[
22]
for the construction of specific organic frameworks in ported by Knowles and Horner independently. Com-
[
1–6]
the last decade.
Nowadays there are many kinds of mon opticallyactive phosphane ligands developed in the
[
23]
alkene metathesis processes such as ring-opening meta- 1970s and 1980s in this context are DIOP 1, CHIRA-
[
1,7]
[24]
[25]
[26]
thesis polymerization (ROMP),
ring-closing meta- PHOS 2, NORPHOS 3, and BINAP 4, which
[11–14]
[
8–10]
thesis (RCM),
enyne metathesis,
cross meta-
[
15–17]
thesis,
all of which are subject of current research
and are frequently applied in the target-oriented syn-
thesis of complicated organic compounds important
for natural products synthesis, materials science and
other fields.The development of this methodology has
taken much advantage from the development of suitable
precatalysts now making available catalysts tolerating a
number of functional groups combined with high cata-
lytic activity and stability allowing one to routinely han-
[
18,19]
dle them in an organic chemistry laboratory.
The importance of phosphanes as well as chelating di-
phosphanes as ligands in homogeneous transition metal
[20]
catalysis has been known for decades and has gained Scheme 1. Selected chiral diphosphane ligands for asymmet-
particularimportance by the introduction of chiral phos- ric catalysis.
Adv. Synth. Catal. 2006, 348, 931 – 938
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FULL PAPERS
Nikolai Vinokurov et al.
have widely been used in asymmetric catalysis.These di- Results and Discussion
phosphanes and many other chiral diphosphanes have in
common that they share the 1,2-diphosphanylethane
Catalytic Homometathesis of Vinylphosphane Oxides
substructure and that the chiral information is located
in the carbon backbone connecting the two phosphane
fragments.This contrasts with P-stereogenic diphos-
According to a general classification published recently
[
49]
phanes, the first of which was DIPAMP 5, which had by Grubbs et al., a,b-unsaturated substrates, such as
been introduced by Knowles et al.as early as 1975 and acrylic acid derivatives, vinyl ketones or vinyl sulfones
[
28]
was applied in Monsantoꢁs DOPA process. In contrast that undergo homodimerization at a significantly lower
to most amines, phosphanes can show configurational rate than unsubstituted olefins, if at all, shall be de-
[29]
stability.
scribed as Type II or Type III substrates.One example
As in complexes of P-stereogenic phosphane ligands of Type III substrates (no homodimerization) are vinyl
[
46]
the chiral information is located much closer to the met- phosphonates. Recently, Gouverneur et al.reported
al atom than in complexes of phosphane ligands bearing an unsuccessful attempt at the preparation of 1,2-bis(di-
1
2
the chiral information in the molecular backbone, asym- phenylphosphanyl)ethene dioxide (7, R ¼R ¼Ph,
metric reactions taking place at the metal atom usually Scheme 2) via homometathesis of the corresponding vi-
[
30]
1
2
[50a]
proceed with a high degree of enantioselectivity. Ima- nylphosphane oxide (6, R ¼R ¼Ph).
moto et al.have investigated this field using P-stereo- During our research aiming for the preparation of
genic phosphane-boranes as ligand precursors and substituted P-stereogenic vinylphosphane oxides by ole-
[
51]
found exceptionally high enantiomeric excesses in rho- fin cross metathesis,
we found the unprecedented
[
31,32]
dium-catalyzed hydrogenation reactions.
merically pure vinylphosphane oxides are promising methyl(phenyl)vinylphosphane oxide 6a leading to ho-
[51]
Enantio- homo-cross metathesis of enantiomerically pure (S )-
P
[
33–35]
and versatile precursors to P-stereogenic ligands
modimer 7a as a single stereoisomer (Scheme 3).
and can be used as sources of chirality in the P to C chir- This serendipitous discovery prompted us to investigate
[
36,37]
ality transfer in conjugate addition reactions,
Diels– the homometathesis of vinylphosphane oxides 6 and
[39,40]
[
38]
Alder cycloadditions, [3þ2] cycloadditions,
and their cross-coupling with other electron-poor substrates
in more detail.
[
41]
substitution reactions.
The examples of homometathesis between two elec-
tron-deficient olefins of Type II are rare, and good yields
have only been reported for homodimerization of acryl-
[
52]
ates and enones, and for the cross metathesis of a,b-
unsaturated carbonyl and related substrates with styr-
[
53]
enes. In such challenging cases, the proper choice of
precatalysts and experimental conditions is of crucial
Scheme 2. Preparation of P-stereogenic 1,2-diphosphanyl- importance.To probe this aspect, a series of homometa-
ethene dioxides 7 via homometathesis.
thesis reactions of vinylphosphane oxide 6a, catalyzed
by a selection of modern ruthenium metathesis precata-
[
54–58]
lysts
I–VI (0.05 equivs.) was performed under ar-
The availability of enantiomerically pure P-stereo- gon at reflux temperature in dichloromethane
[
42]
genic vinylphosphane oxides 6 raises the question, (Scheme 3, Table 1).
in how far they may serve as substrates for catalytic ho-
As can be seen from Table 1, the homo-coupling reac-
mometathesis presumably leading to enantiometrically tions are visibly dependent on the chosen ruthenium
[
56]
[57,58]
pure P-stereogenic 1,2-diphosphanylethene oxides precatalyst, with electronically and sterically
acti-
Subsequently, these might undergo hydrogena- vated Hoveyda–Grubbs type complexes III–V being
44]
[
43]
[55]
7.
[
tion or cycloaddition reactions and stereoselective re- the most effective ones.Therefore, we decided that the
[45]
[60]
duction to give new P-stereogenic ligands for asym- stable, industrially tested
nitro-Hoveyda complex
metric catalysis (Scheme 2). trans-1,2-Bis(diphenyl- III, developed in our laboratories, is the most appropri-
1
2
[61]
phosphanyl)ethene dioxide (7, R ¼R ¼Ph) was suc- ate one from the practical point of view. In line with
[
51]
cessfully used for the preparation of NORPHOS the previous observation, the CM of 6a was in all cases
[25]
(
3), a highly active ligand possessing chirality centers highly stereoselective, as (E)-7a was the only isomer de-
1 31
in the rigid carbocyclic skeleton.Recently, intermolecu-
tected by H and P NMR.Careful spectroscopic in-
lar olefin cross metathesis and intramolecular ring-clos- spection of the reaction mixture reveals that no racemi-
ing metathesis were applied for preparation of function- zation takes place during the CM step as no trace of the
alized phosphorus compounds including allyl and vinyl respective meso CM product could be detected and the
[
46]
[47]
[62]
phosphonates,
allylphosphane oxides,
and allyl- ee of the obtained 7a (ee¼98ꢀ2%) is found to be
[
48]
[62]
phosphane-boranes.
identical with that of the substrate (ee¼98ꢀ2%).
932
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Metathesis Coupling of Vinylphosphane Oxides and Electron-Poor Alkenes
FULL PAPERS
Table 1. Optimization results of homometathesis of (S )-
P
[a]
6
a.
Entry
Precatalyst
Concentration
of 6a [M]
Yield of
[b]
7a [%]
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
I
I
I
II
0.020
0.125
0.200
0.125
0.200
0.005
0.020
0.125
0.200
0.020
0.125
0.200
0.020
0.125
0.200
0.200
(18)
(35)
(25)
(46)
(42)
(ca. 5)
(30)
76
80
(30)
75
78
44
II
III
III
III
III
IV
IV
IV
V
1
1
1
1
1
1
1
V
V
VI
71
67
(10)
Scheme 3. Screening of the catalytic activity of complexes I–
[
54–58]
VI
in the homometathesis of (S )-6a.Cy ¼cyclohexyl;
[a]
P
Reagents and conditions: 5.0 mol % of precatalysts I–VI,
DCM, 24 h, reflux.
b]
Mes¼2,4,6-trimethylphenyl.
[
Isolated yields of analytically pure products.In parenth-
3
1
eses conversions determined by P NMR are given.
cluding 1,2-dichloroethane and benzene, showing that
our initial choice of DCM was optimal.
In striking contrast to previously studied CM reac-
[
51]
tions of vinylphosphane oxides with olefins, the ho-
mometathesis of 6a has been found to be very dependent
not only on the substrate concentration but also on scale
and subtle experimental set-up.For example, dimeriza-
tion reactions conducted under optimized conditions
Scheme 4.
This clearly attests to the mildness of the method in gen- (0.100–0.125 M in DCM, under reflux) in the scale of
eral terms. 0.5 mmol gave the expected product in the 88–95%
[
51]
In some homodimerization reactions catalyzed by range of yield (two runs), while in 1.0–1.5 mmol scale
Hoveyda–Grubbs complexes III–V we have also isolat- reproducibly lower yields of 7a were obtained (63–80%,
ed phosphane oxides 8aIII, 8aIV and 8aV (Scheme 4), three runs).
products of CM between 6a and the corresponding pre-
catalyst.These by-products, formed in theoretical yields
Having identified ruthenium complex III as the effec-
tive precatalyst for this transformation, we decided to
(
ca. 5%), can be easily separated by flash chromatogra- extend this investigation to a more diverse set of achiral
phy because of their different polarity.The remainder of
and P-stereogenic substrates (Table 2).The behavior of
the mass balance was unreacted 6a, which can be easily differently substituted vinylphosphane oxides 6 as sub-
isolated by flash chromatography and recycled. strates for homometathesis was found to be more com-
It is evident from the data compiled in Table 1, that the plex.While attempted homometathesis reactions of vi-
yield of 7a is highly responsive to the concentration of nylphosphane oxides bearing either one aromatic (en-
[63]
[50a]
substrate 6a. For example, the reaction catalyzed by try 3)
or sterically demanding substituents (entry 4)
III at 0.020 M gave only 30% yield (entry 7), and a de- were in vain, the use of alkyl-aryl (entries 1, 2) or dialkyl
crease of the concentration further decreased the yield (entries 6, 7) vinylphosphane oxides 6 resulted in mod-
(
entry 6).However, an increase of the concentration in-
creased the yield, and highest yields were obtained at ucts 7.The rest of the mass balance consisted of unreact-
.125–0.200 M (entries 8, 9). Because of the limited sol- ed substrates 6, which could be easily recovered by chro-
erate to good yields of the desired homocoupling prod-
0
ubility of 6a in DCM, we repeated this homodimeriza- matography and reused, rendering this method useful
tion at 0.4 M in chlorobenzene, however, without im- from the practical point of view.
proving the conversion.The reaction of 6a catalyzed
It is well established that the cross metathesis of a,b-
by III was then further refined using other solvents, in- unsaturated substrates is very sensitive both to steric
Adv. Synth. Catal. 2006, 348, 931 – 938
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Nikolai Vinokurov et al.
Table 2. Homometathesis of representative vinylphosphane
oxides 6 catalyzed by III.
[a]
Scheme 5. Reagents and conditions: 10 mol % of precatalyst
III, DCM, 24 h, reflux.Isolated yields of analytically pure
products.
[
[
a]
b]
Reagents and conditions: 5.0 mol % of precatalysts III,
DCM, 24 h, reflux.Reaction in the scale of 01 .– 1
5
mmol.Isolated yields of analytically pure products.
1
Only E isomers observed by H NMR.
SP )-6a was used.When rac-6a was used, the correspond-
ing dl- and meso-isomers were formed in a 1: 1 ratio, as de-
(
31
termined by P NMR.
[
[
c]
Rac-6b was used; dl- and meso-isomers were formed in a
3
1
~
3: 1 ratio, as determined by P NMR.
d]
Reaction with 10 mol % of III.
hindrance and electron density of the reacting CꢁC dou-
[16]
ble bonds. One might therefore expect the ruthenium-
catalyzed homometathesis of more electron-rich diaryl-
vinylphosphane oxides, such as 6 h and 6i, to proceed
more readily than in the case of diphenylphosphane ox-
ide 6c.In order to learn about the influence of electronic
factors we have attempted a homodimerization of 6 h Scheme 6. Plausible mechanism for the formation of products
7
and 8.NHC ¼1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidi-
and 6i with 10 mol% of III (Scheme 5).
nylidene.
Disappointingly, no homometathesis was observed
with these substrates.Instead, in addition to unreacted
starting material (ca. 90% of mass balance) we isolated
minute amounts of cross metathesis products 8hIII and
Catalytic Cross Metathesis of Vinylphosphane Oxides
with Representative Olefins of Type II or III
[
64]
8
iIII formed during the initiation step (Scheme 6).
These results show that homodimerization of vinylphos-
phanes bearing two aromatic substituents (6c, 6 h, i) is To access other synthetically useful achiral and P-stereo-
[
65]
not possible even with highly active precatalyst III, genic phosphorus building blocks,
we attempted
and these substrates should therefore be classified as cross-coupling reactions of vinylphosphane oxides 6
[
50a]
pure Type III olefins.
with selected Type II or Type III olefins.Cross metathe-
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Metathesis Coupling of Vinylphosphane Oxides and Electron-Poor Alkenes
FULL PAPERS
sis dimerization between electron-deficient or bulky
substrates did not readily occur (Type II or Type III ole-
fins) and thus is another challenging reaction.For exam-
ple, it was observed that ortho-substituted styrenes bear-
ing electron-withdrawing or bulky functionalities (Type
III olefins) were poor CM substrates with acrylates
[
16]
(
Type II substrates). Therefore we have chosen meth-
yl acrylate 9 and 2-fluorostyrene 10 as challenging proto-
typical Type II and III substrates in our investigation.
Initial experiments of CM between 6a and 9 revealed
that under standard conditions (2 equivs.of 9, 5 mol %
Scheme 7. Cross metathesis of 6b with electron-rich Type I
styrene 13.
III, DCM, reflux) selectivity was low and homometathe- the formation of the desired cross metathesis product
sis product 7a was formed in large amounts (12%).To in 47% NMR yield.Utilizing 10 mol % of III increased
optimize this reaction, a set of CM conditions was inves- the yield of 11a to 64% (NMR; 62% isolated yield, Ta-
tigated.It was found that increasing the amount of meth-
yl acrylate to 30 equivs.almost completely suppressed
the undesired homometathesis of 6a and allowed for in the crude reaction mixture by H NMR.This by-prod-
ble 3, entry 1).
Varying amounts of dimethyl fumarate were detected
1
[
52a]
uct, formed in a homometathesis reaction of 9,
could
be easily separated by flash chromatography, while the
Table 3. Cross metathesis of vinylphosphane oxides 6 with excess of unreacted 9 could be removed under vacuum.
methyl acrylate 9 or 2-fluorostyrene 10 catalyzed by III.
In contrast to the above described homometathesis of
vinylphosphane oxides 6, changing the concentration
of 6a from 0.02 M to 0.200 M did not result in a further
improvement of the conversion.
Interestingly, in the cross metathesis reaction of 6a
with methyl acrylate, no coupling product 8aIII was iso-
3
1
lated after the reaction, or even detected by P-NMR.
This observation suggests that the acrylate 9 first reacts
with Ru-carbene complexes to form Ru¼CHꢁCO Me
2
species, and that the vinylphosphane oxides 6 then en-
[
52a]
ters the catalytic cycle.
As can be seen from the results compiled in Table 3,
under these optimized conditions, different vinylphos-
phane oxides, including diaryl ones (6c and 6j), can be
used as cross metathesis substrates for 9 and 10 to give
products in 29–62% yield and excellent stereoselectivi-
ty.
Use of a 30-fold excess of an electron pure CM partner
was unnecessary in the cases of hardly-dimerizing phos-
phanes 6c and 6j.The second generation Grubbsꢁ preca-
talyst I could be used in this transformation as well, how-
ever, a slightly lower yield was obtained in that case (Ta-
ble 3, entry 3).
It should be noted that CM of 6c with the more elec-
tron-rich 4-methoxystyrene 13 proceeds readily to give
[
50a]
the expected product 14
with practically equal yields
regardless if precatalyst I or III was used.
[
a]
Reagents and conditions: 6 (1 equiv.), 9 (30 equivs.) or 10
3 equivs.), precatalysts III (5.0–10.0 mol %), DCM, 24 h,
(
Conclusion
reflux.Isolated yields of analytically pure products.Homo-
dimerization products of 9 and 10 were not shown.
In conclusion, we have demonstrated that vinylphos-
phane oxides 6 could be successfully “dimerized” by cat-
alytic olefin homometathesis leading to a series of new
achiral and P-stereogenic diphosphane dioxides 7 with
exclusive E-selectivity.This unprecedented strategy al-
lows for direct access to these valuable compounds,
[
[
b]
c]
(
SP )-6a was used.
In the reaction with 5 mol % of III, the conversion calcu-
31
lated from P NMR was 47%.
rac-6b was used.
[
[
[
d]
e]
f]
With precatalyst I (5 mol %), the yield was 24%.
rac-6j was used.
Adv. Synth. Catal. 2006, 348, 931 – 938
ꢀ 2006 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
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FULL PAPERS
Nikolai Vinokurov et al.
sometimes hardly available by more traditional synthet- ringe was added degassed methyl acrylate (0.675 mL,
7
.5 mmol). The resulting mixture was stirred at 458C for 24 h.
ic strategies.Cross metathesis of 6 with electron-poor
substrates, such as methyl acrylate and 2-fluorostyrene
was a second challenging reaction tested in this study.
Further applications of this methodology are readily ex-
pected on the basis of the well-established synthetic util-
ity of products 7, 11 and 12.The use of 7a for the design
of new P-chiral diphosphane ligands is currently under
investigation.
The solvent was removed under reduced pressure.The crude
product 7 was purified by flash chromatography (ethyl ace-
tate-methanol, 20:1) to afford 11.
General Procedure for Cross Metathesis of
Vinylphosphane Oxides with 2-Fluorostyrene
[72]
To a mixture of vinylphosphane oxide 6 (0.36 mmol) and pre-
catalyst III (15.3 mg, 0.018 mmol) in CH Cl (18 mL) via sy-
2
2
ringe was added 2-fluorostyrene 10 (0.146 ml, 1.08 mmol).
The resulting mixture was stirred at 458C for 24 h.The solvent
was removed under reduced pressure.The crude product 12
was purified by flash chromatography (ethyl acetate then ethyl
acetate-methanol, 20:1).
Experimental Section
General
Unlessotherwise noted, all reactions were carried out under ar-
gon in pre-dried glassware using Schlenk techniques.The sol-
vents were dried by distillation over the following drying
agents and were transferred under argon: THF (K/benzophe- Acknowledgements
none), toluene (Na), n-pentane, n-hexane, CH Cl (CaH ),
2
2
2
Et O (LiAlH ).Flash column chromatography: Merck silica
gel 60 (230–400 mesh).NMR ( H, C, P) spectra were re-
corded on Bruker AVANCE 500, AVS 400 (400.1 MHz,
This work was supported by the Deutsche Forschungsgemein-
schaft (grant Bu814/12-1) and by the Institute of Organic Chem-
istry of the Polish Academy of Sciences (visiting grant for
G. W.). N. V. thanks the Gottlieb Daimler und Karl Benz-Stif-
tung for a graduate fellowship.
2
4
1
13
31
100.6; 162 MHz), Varian Gemini 200 and 400 spectrometers
in CDCl ; chemical shifts (d) are given in ppm relative to
3
TMS, coupling constants (J) in Hz.IR: Perkin-Elmer Spectrum
ꢁ
1
2
000 and 1170 FT-IR, wavenumbers in cm .MS (EI, LSI-MS):
AMD 604 Intectra GmbH, MAT 112 and MAT 312 Finnigan
0 eV.MS (ESI): Mariner Perseptive Biosystems, Inc.HR-
References and Notes
7
MS: Finnigan MAT 312, VG Autospec, peak matching with
PFK.Optical rotations: Perkin-Elmer 341 Polarimeter with so-
dium lamp (589 nm); Melting points: Electrothermal IA 9200
SERIES Digital Melting Point Apparatus (uncorrected).Mi-
cro-analyses were provided by Institute of Organic Chemistry,
[
1] General reviews on olefin metathesis reaction and cata-
lysts: Handbook of Metathesis, (Ed.: R. H. Grubbs), Wi-
ley-VCH, Weinheim, 2003, vols.1–3.
[
2] A.Fürstner, Angew. Chem. 2000, 112, 3140–3172; An-
gew. Chem. Int. Ed. 2000, 39, 3012–3043.
[56–58]
PAS, Warsaw.Precatalysts III–V
were prepared accord-
[36]
[3] D.L.Wright, Curr. Org. Chem. 1999, 3, 211–240.
[4] M.Schuster, S.Blechert, Angew. Chem. 1997, 109, 2124–
ing to the literature procedures.Vinylphosphane oxides 6a
[
67]
[67]
[68]
[69]
6
b, 6c, 6d and 6j were known compounds and were
2
144; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036–2056.
synthesized according to the literature procedures.Vinylphos-
[
5] O.R.Thiel, in: Transition Metals for Organic Synthesis,
(Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim,
2004, Vol.1, pp.321–334.
phane oxides 6e–i were prepared from the respective sec-
[
70]
phosphane oxides by the vinyl transfer methodology utiliz-
ing rac-phenyl vinyl sulfoxide as the vinyl donor and were
[71]
available from another study. All other substrates were com-
mercially available and were used as received.
[6] R.H. Grubbs, T.M. Trnka, in:
Synthesis (Ed.: S.-I. Murahashi), Wiley-VCH, Weinheim,
004, pp.153–178.
Ruthenium in Organic
2
[
7] A. Hafner, P.A.v.d. Schaaf, A. Mühlebach,
Chimia
General Procedure for Homometathesis of
Vinylphosphane Oxides 7
1996, 50, 131–134.
[72]
[8] S.K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998,
71–388.
9] R.H. Grubbs, S.J. Miller, G.C. Fu,
995, 28, 446–452.
3
To a mixture of vinylphosphane oxide 6 (1.0 mmol) in CH Cl
2
2
[
Acc. Chem. Res.
(
0
4–7 mL) was added a solution of precatalyst I–VI (0.05–
.10 mmol) in CH Cl (1 mL).The resulting mixture was stir-
1
2
2
[
[
10] U.Koert, Nachr. Chem. Tech. Lab. 1995, 43, 809–814.
11] A.Kinoshita, N.Sakakibara, M.Mori, J. Am. Chem. Soc.
red at 458C for 24 h.The solvent was removed under reduced
pressure.The crude product was purified by flash chromatog-
raphy.
1
997, 119, 12388–12389.
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Adv. Synth. Catal. 2006, 348, 931 – 938