Fast olefin metathesis: Synthesis of 2-aryloxy-substituted Hoveyda-type complexes and application in ring-closing metathesis

Article abstract of DOI:10.1002/adsc.201200956

Four 1-(4-R-phenoxy)-2-ethenylbenzenes (R=NMe₂, H, Cl, NO ₂) 4a, 4b, 4c and 4d were reacted with the ruthenium complexes [RuCl₂(NHC)(3-phenylindenylidene)(py)] in the presence of a protic resin to result in the formation of the respective Hoveyda-type complexes 5a-d {NHC=SIMes [1,3-bis(2,4,6-trimethylphenylimidazolin)-2-ylidene]} and 6a-d {NHC=SIPr [1,3-bis(2,6-diisopropylphenylimidazolin)-2-ylidene]} in 66-84% yield. The lower steric bulk and the decreased donation of the diaryl ether oxygen atoms in complexes 5 and 6 led to rapidly initiating precatalysts. The Ru(II/III) redox potentials of complexes 6 were determined (6a-d: ΔE=0.89-1.08 V). In the crystal structure of 5b two independent molecules were observed in the unit cell, displaying Ru-O distances of 226.6(4) and 230.5(3) pm. The catalytic performance of complexes 5 and 6 in various ring-closing metathesis (RCM) reactions was studied. Catalyst loadings of between 15-200 ppm are sufficient for the formation of >90% yield of the respective cyclic products. Complex 6b catalyzes the formation of N-protected 2,5-dihydropyrroles with up to TON 64,000 and TOF 256,000 h^-1, of the N-protected 1,2,3,6- tetrahydropyridines with up to TON 18,200 and TOF 73,000 h^-1 and of the N-protected 2,3,6,7-tetrahydroazepines with up to TON 8,100 and TOF 32,000 h^-1 with yields ranging between 77 and 96%.

Full text of DOI:10.1002/adsc.201200956

FULL PAPERS
DOI: 10.1002/adsc.201200956
Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted
Hoveyda-Type Complexes and Application in Ring-Closing
Metathesis
Pavlo Kos,a Roman Savka,a and Herbert Plenioa,*
a
Organometallic Chemistry, Petersenstr. 18, Technische Universitꢀt Darmstadt, 64287 Darmstadt, Germany
E-mail: plenio@tu-darmstadt.de
Received: October 31, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200956.
Abstract: Four 1-(4-R-phenoxy)-2-ethenylbenzenes 230.5(3) pm. The catalytic performance of complexes
(R=NMe2, H, Cl, NO2) 4a, 4b, 4c and 4d were react- 5 and 6 in various ring-closing metathesis (RCM) re-
ed with the ruthenium complexes [RuCl2ACTHNUTRGNEUNG(NHC)(3- actions was studied. Catalyst loadings of between
phenylindenylidene)(py)] in the presence of a protic 15–200 ppm are sufficient for the formation of
resin to result in the formation of the respective >90% yield of the respective cyclic products. Com-
Hoveyda-type complexes 5a–d {NHC=SIMes [1,3- plex 6b catalyzes the formation of N-protected 2,5-
bis(2,4,6-trimethylphenylimidazolin)-2-ylidene]} and dihydropyrroles with up to TON 64,000 and TOF
6a–d {NHC=SIPr [1,3-bis(2,6-diisopropylphenylimi- 256,000 hꢀ1, of the N-protected 1,2,3,6- tetrahydro-
dazolin)-2-ylidene]} in 66–84% yield. The lower pyridines with up to TON 18,200 and TOF 73,000 hꢀ1
steric bulk and the decreased donation of the diaryl and of the N-protected 2,3,6,7-tetrahydroazepines
ether oxygen atoms in complexes 5 and 6 led to rap- with up to TON 8,100 and TOF 32,000 hꢀ1 with
idly initiating precatalysts. The RuACHTNUTRGNEUNG(II/III) redox po- yields ranging between 77 and 96%.
tentials of complexes 6 were determined (6a–d:
DE=0.89–1.08 V). In the crystal structure of 5b two
independent molecules were observed in the unit Keywords: cyclic voltammetry; olefin metathesis;
ꢀ
cell, displaying Ru O distances of 226.6(4) and ring-closing metathesis; ruthenium
Introduction
the electron density of the oxygen donor leads to
a faster dissociation of the ruthenium-oxygen bond,
Progress in olefin metathesis depends on the continu- while electron-rich oxygen groups appear to be more
ous evolution of catalyst complexes.[1] As a conse- tightly bound to ruthenium.[4f,g,5] This is a useful
quence of the development of numerous efficient model in a dissociative scenario for catalyst activa-
ruthenium- and molybdenum-based complexes, olefin tion, but it was also shown later that electron-with-
metathesis has been firmly established as a powerful drawing substituents also led to enhanced precatalyst
synthetic tool in organic synthesis and polymer activation via an interchange activation pathway
chemistry.[2] Especially Hoveyda-type complexes com- which is aided by an electron-deficient ruthenium.[6]
bine excellent stability with high activity in various The initiation of such precatalysts occurs simultane-
olefin metathesis reactions and have been modified ously along two mechanistic pathways and finally
extensively to optimize their catalytic performance.[3] leads to faster precatalyst activation.[6b,7] Based on
Typically, such complexes are characterized by a 2-iso- a significant contribution of an interchange pathway,
propoxy group at the benzylidene ligand, whose this mechanistic model also explains why using the
oxygen atom also binds to ruthenium in a chelating small 2-methoxy group leads to significantly faster ini-
manner.[4] The behavior of such complexes in various tiation rates than with the 2-isopropoxy substituted
olefin metathesis transformations has been modified complexes.[6b,8]
extensively by introducing various electron-withdraw-
Despite the large number of modified Hoveyda-
ing or electron-donating groups at the 4- and 5-posi- type complexes,[4b] many of which were introduced by
tions of the six-membered ring. These modifications the Grela group,[9] 2-phenoxy-substituted complexes
are often based on the assumption that a decrease in have not been reported. Replacing an sp3-carbon by
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an sp2-carbon in a phenyl groups leads to a decrease metrical diaryl ethers 3 according to a literature pro-
in the oxygen donation. This should weaken the cedure.[11] For the synthesis of the nitro-substituted 3d
Ru···O interaction in such complexes and result in a slightly different approach was taken, by reacting 1-
faster initiation rates. Obviously such rapidly initiat- fluoro-4-nitrobenzene with 2-hydroxybenzaldehyde.
ing complexes offer the potential for fast and efficient Next, the aldehydes were converted into the respec-
olefin metathesis reactions. We want to present here tive vinyl-substituted ethers employing the Wittig re-
the synthesis and the characterization of new 2-phen- agent in yields of 77–84%. The synthesis of the new
oxy-substituted Hoveyda-type complexes as well as ruthenium complexes was achieved in 69–84% yield
studies probing the catalytic activity of these com- in the presence of Amberlyst resin at 408C using
plexes in various ring-closing metathesis (RCM) reac- [RuCl
(NHC)(3-phenylindenylidene)(py)]
(NHC=
tions.[10]
SIMes, SIPr)[12] and a slight excess (1.1 equiv.) of the
respective diaryl ethers 4. For the most electron-defi-
cient and least stable complex 5d the best yields are
obtained when the synthesis of this complex is carried
out in THF solvent at 08C. The removal of the pyri-
dine ligand from the reaction equilibrium by protona-
tion with the protic resin (Amberlyst) is essential for
Results and Discussion
Synthesis of 2-Aryloxy Hoveyda Complexes
The new ruthenium complexes 5 and 6 were synthe- the synthesis of the new complexes reported here –
sized according to Scheme 2. The nucleophilic substi- without the acidic resin the respective complexes 5
tution of 2-fluorobenzaldehyde with various 4-substi- and 6 are only formed in poor yields or not at all. The
tuted phenols (R=Cl, H, NMe2) furnishes the unsym- same strategy was recently used successfully for the
synthesis of related N-Hoveyda complexes.[13] Howev-
er, the idea of using the protic resin for the efficient
synthesis of Hoveyda-type complexes is based on a re-
lated approach introduced by Verpoort and Mon-
saert.[14] These authors reported on the facile synthesis
of 2-O-i-Pr-substituted Hoveyda complexes from
Grubbs I and II complexes in >90% yield via proto-
nation of PCy3 and removal as the respective phos-
phonium salt. An important advantage of the com-
plexes 5 and 6 reported here is their simple and high-
yielding synthesis, which will facilitate synthesis of
such complexes in multi-gram amounts.
Scheme 1. O-Hoveyda type complexes, complex 1(H) with
R=O-i-Pr, R4, R5 =H.
Scheme 2. Synthesis of diaryl ethers 4 (a: R=NMe2, b: H, c: Cl, d: NO2) and of the new complexes 5 and 6. Reagents and
conditions: (3a, b, c are known compounds, while 3d was synthesized from 1-fluoro-4-nitrobenzene and 2-hydroxybenzalde-
hyde in 70% yield; a) vinylation of aldehydes: [MePPh3]+Iꢀ, KO-t-Bu, THF, 08C!room temperature, overnight, yields: 77–
84%; b) synthesis of 5a–c and 6a–d: protic resin (Amberlyst), CH2Cl2, 408C, 30–60 min, yields: 71% (5a), 81% (5b), 69%
(5c) and 73% (6a), 84% (6b), 75% (6c), 66% (6d); synthesis of complex 5d: protic resin (Amberlyst), THF, 08C, 30 min,
yield: 75%.
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Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted Hoveyda-Type Complexes
Table 1. Redox potentials [V] and peak separations EaꢀEc
[mV] of complexes 5a–d and 6a–d.[a]
X-Ray Crystal Structure of Complex 5b
The crystal structure of a 2-phenoxy-substituted com-
plex was determined, in order to learn whether the
presence of the poorly donating diaryl ether oxygen
atom results in longer ruthenium-oxygen distances
than in the respective 2-isopropoxy complexes. In the
solid state two independent molecules of 5b are ob-
served, which differ with respect to the orientation of
the OPh group relative to the rest of the molecule. In
the rotamer displayed (Figure 1), the plane of the
C6H5 unit is nearly orthogonal (angle 828) to the
plane of the 1,2-substituted benzene ring, while in the
second molecule the corresponding angle amounts to
608. Other small changes of the geometric parameters
ꢀ
Redox potentials [V], (EaꢀEc) [mV]
R=
5
6
a NMe2
b H
c Cl
0.87
0.941(83)
0.99
1.07
G
0.886(97)
0.977(92)
1.013(92)
1.075(91)
d NO2
Solvent: CH2Cl2, scan rate: 100 mVsꢀ1, supporting elec-
[a]
trolyte 0.1M NBu4PF6, potentials vs Fc/Fc+
0.460 V.
E1/2 = +
[b]
Insufficient electrochemical reversibility.
are also seen, notably the Ru O bond differs by donor ability of the ligands coordinated to the
nearly 4 pm [226.4(4) or 230.5(3) pm] in the two iso- metal.[16] In the series of complexes 5 and 6 reported
ꢀ
mers. The shorter distance is close to the Ru O dis- here, the substituents in the 4-position are modulated
tance observed in the standard Hoveyda complex from strongly electron-donating (a: NMe2) to strongly
(226.1 ppm)[15] with an 2-isopropoxy instead of the 2- electron-withdrawing (d: NO2). The redox potentials
ꢀ
phenoxy group. The significant variability of the Ru
O distances in the two molecules of 5b is caused by mined in CH2Cl2 (Table 1). The SIPr 6 complexes are
of the eight complexes 5a–d and 6a–d were deter-
packing effects, and indicates that the energy poten- characterized by a quasi-reversible electrochemistry.
ꢀ
tial curve for Ru O bond is shallow and thus sensitive The redox potentials of the rapidly initiating SIMes
to small perturbations.
complexes could not be determined with good preci-
sion, due to the lack of sufficient reversibility in the
cyclic voltammograms. A comparison of the redox po-
tentials of the different complexes 5 and 6 with those
of the 2-isopropoxy-substituted complexes 1 and 2 re-
veals that the substituents R4 and R5 (Scheme 1) in
the latter complexes have a much stronger influence
on the redox potential than the R group in the com-
plexes reported here. Especially the 4-substituent R4
(trans to the benzylidene carbon in complexes 1) has
a pronounced effect on the redox potential, which
ranges from 0.46 V for 1 (R4 =NEt2) to 1.04 V for
1 (R4 =NO2).[6b] This corresponds to a redox potential
spread of 580 mV. In contrast, within the series of
complexes 6 only a modest 190 mV shift is found be-
tween R=NEt2 and NO2. This underlines our previ-
ous hypothesis that the electronic communication be-
Figure 1. ORTEP (50% probability) of complex 5b, only tween ruthenium and the substituents mainly occurs
one of the two independent molecules in the crystal is dis-
played. Important bond lengths (pm) and angles (o) (first
number(s) given correspond to rotamer 1 followed by the
via the Ru=CHR unit and only to a lesser degree via
the Ru O interaction.
[6b]
ꢀ
ꢀ
respective data for rotamer 2): Ru O 226.6(4), 230.5(3);
ꢀ
Ru C
G
Precatalyst Activation of Complexes 5 and 6
180.9(5), Ru Cl 230.7(2), 232.3(2), 232.1(2), 234.0(2); Cl
ꢀ
Ru Cl 153.71(6), 158.31(6) (data deposited as CCDC
Due to the electron-deficient nature of the diphenyl
oxygen, both complexes 5 and 6 are characterized by
weak ruthenium-oxygen interactions. Consequently, in
the presence of excess olefin this bond is broken rap-
idly, as evidenced by a correspondingly rapid decrease
in the absorbance of the LMCT band (Figure 2),[17]
which is normally observed between 360–400 nm for
908389. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif).
Redox Potentials
The cyclic voltammetry-derived Ru
ACHTUNGERTN(NUNG II/III) redox po- such complexes. This dissociation reaction requires
tentials provide useful information concerning the less than 20 sec in 5d, even at a very low concentra-
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Figure 2. Left: UV/Vis traces of complex 5d (1.0·10ꢀ4 mol·Lꢀ1) during reaction with BuVE (0.01M) in toluene at T=308C.
Right: corresponding absorbance-time trace at 370 nm. The data are fitted using [y=A1·exp
N
tion of butyl vinyl ether (0.01 mol·Lꢀ1) and at a tem-
perature slightly above ambient (308C). The new
complexes appear to be the fastest initiating Hovey-
da-type complexes, which should be also useful in
ROMP reactions. However, the SiMes complexes 5
initiate circa 10 times faster than the SiPr complexes
6. Following RCM transformation, this absorbance
fails to recover intensity and consequently the UV/
Vis spectra provide no evidence for a significant
return of the 2-phenoxystyrene following the olefin
metathesis transformation.[18] Other than that, the ki-
netics of the new complexes 5 and 6 reveal more de-
tails than those of the 2-isopropoxy-substituted com-
plex 1. Due to the very fast loss of the benzylidene
ligand additional steps are observed in the UV/Vis
spectra. A pronounced feature is the absorbance at
510 nm, which builds up with the same rate as the loss
Figure 3. RCM
reaction
of
N,N-diallyltosylamide
(0.1 mol·Lꢀ1) at 08C in toluene with complexes 1(H), 5b
and 6b (0.025 mol%; 250 ppm).
of intensity of the 370 nm band, but decays with a dif-
ferent rate. We are currently working on a detailed ki-
netic and mechanistic analysis of such complexes.
at only 250 ppm (0.025 mol%) of 6b. After 120 min
the reactions almost reach the final conversion for
complexes 5b and 6b, while it takes longer for the less
rapidly initiating complex 1(H). It was, however, un-
Evaluation of the Catalytic Activity of Complexes 5
and 6 in RCM
The new complexes 5 and 6 are characterized by expected to see no performance difference between
rapid precatalyst initiation, which enables efficient 5b and 6b in the initial stage of the RCM reaction,
RCM reactions at low reaction temperatures. To dem- since it is known that SIMes-based complexes initiate
onstrate this, the conversion-time curves for the RCM faster than those with SIPr.[13] To test this, another
reaction of diallyl-N-tosylamide catalyzed by com- conversion-time curve with shorter sampling intervals
plexes 5b and 6b were determined at 08C and plotted (Figure 4) was recorded. With this more detailed
together with the respective curves for complex 1(H) view, at least during the first 6 min, the faster initiat-
(Figure 3). The faster precatalyst activation of com- ing complex 5b produces more product. Obviously,
plexes 5b and 6b compared to 1(H) is evidenced by the lower initiation efficiency is rapidly offset by the
the faster initial transformation of substrate diallyl-N- higher catalytic performance of complex 6b.
tosylamide into the respective RCM product. Notably,
In order to demonstrate the efficiency of the newly
within 60 min at 08C a conversion of 80% is observed synthesized ruthenium complexes an extensive screen-
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Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted Hoveyda-Type Complexes
malonate (DEDAM) has become something like
a benchmark substrate for RCM reactions.[19] The
comparison of the yields reported for complexes 5
and 6 with previous data observed for this substrate
underline the excellent performance of the complexes
reported here. Four out of the eight new complexes
(5c, 6a, 6b, 6c) give more than 80% conversion for
DEDAM at 100 ppm (0.01 mol%) of catalyst loading,
which is a considerably lower catalyst loading than
described recently in the Grela galaxy benchmark
paper.[19a] Recently other examples of olefin metathe-
sis reactions employing low catalyst loading were re-
ported. Nolan, Slugovc et al.[20] described the high ac-
tivity of complexes based on the SIPr ligand, whose
performance is comparable to that of the complexes 6
reported here. Grubbs et al. demonstrated excellent
activities in RCM reactions of DEDAM using robotic
equipment in a glove box.[21] On the other hand, the
synthesis of various five-, six- and seven-membered
Figure 4. RCM
reaction
of
N,N-diallyl-tosylamide
(0.1 mol·Lꢀ1) at 08C in toluene with complexes 5b and 6b
(0.025 mol%; 250 ppm)
ing was done for eight different RCM substrates and N-heterocycles was reported by Pederson, Grubbs
the eight newly synthesized complexes 5 and 6 et al.; however, in their work 500 ppm of Ru complex
(Table 2). In general, the complexes reported here were used for the full conversion of nitrogen-contain-
provide excellent substrate conversions within less ing substrates leading to the respective heterocycles
than 15 min of reaction time at low catalyst loadings during 8 h reaction time.[22] For BocN
ACTHNUTRGNEG(NU diallyl)2
of between 15–100 ppm (0.0015–0.01 mol%) at 508C (Table 2, entry 5) this leads to TON 2,000 and TOF
in toluene as solvent. Over the years diethyl diallyl- 310 hꢀ1, while the same reaction employing complex
Table 2. Screening of catalysts in ring-closing metathesis reactions.
cat
ACHTUNGTRENNUNG
[ppm][a]
1
5a
5b
5c
5d
6a
6b
6c
6d
Substrate
Conversion[b] [%]
200
100
50
200
100
50
29
90
52
92
75
83
49
99
80
37
86
64
33
89
77
80
88
89
82
66
73
54
51
42
98
78
94
51
73
54
40
36
100
50
95
80
75
70
79
25
15
83
64
90
74
73
64
83
99
91
81
78
99
92
96
50
25
91
86
80
41
98
92
77
60
70
86
76
100
50
93
60
71
92
54
77
89
99
91
83
98
200
100
92
99
81
50
39
61
90
72
84
[a]
100 ppm correspond to 0.01 mol%.
[substrate]=0.5M, conversions determined by GC, average of two runs.
[b]
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6b takes place with TON 64,000 and TOF 256,000 hꢀ1.
The efficiency of the complexes 5 and 6 reported here
is close to the excellent activities recently demonstrat-
ed for N-Hoveyda complexes with diarylamino li-
gands.[13] As observed before, for RCM reactions
leading to disubstituted olefins, the SIPr-based com-
plexes are more powerful catalysts, while for the syn-
thesis of trisubstituted olefins the SIMes complexes
tend to perform better. We note that the use of puri-
fied reaction solvent (toluene) and especially of the
purified substrates is an essential requirement for the
observation of excellent catalytic activities and for
avoiding premature catalyst decomposition.
In conclusion, the formation of N-protected 2,5-di-
hydropyrroles with complex 6b proceeds with TON of
64,000 (yield 87%) and TOF 256,000 hꢀ1, of the N-
protected 1,2,3,6-tetrahydropyridines with TON
18,200 (92% yield) and TOF 73.000 hꢀ1 and of the re-
spective N-protected 2,3,6,7-tetrahydroazepines in
TON 8,100 (95% yield) and TOF 32,000 hꢀ1 with
yields ranging between 77–96% for the various sub-
strates.
and pressurized with argon (0.1–1 bar), followed by succes-
sive passages through a column filled with activated alumina
and a second column, either filled with a supported copper
catalyst (pentane) or again activated alumina (toluene,
CH2Cl2). Dimethylformamide was refluxed over calcium hy-
dride and distilled under an argon atmosphere. Tetrahydro-
furan was dried with sodium and distilled under an argon at-
mosphere. Toluene was additionally dried over CaH2 and
distilled onto molecular sieves (4 ꢃ). All solvents were
1
stored over molecular sieves (4 ꢃ). H and 13C NMR spectra
were recorded on a Bruker DRX300 spectrometer. The
chemical shifts are given in parts per million (ppm) on the
delta scale (d) and are referenced to tetramethylsilane (1H,
13C NMR=0.0 ppm) or the residual peak of CHCl3
(1H NMR=7.26 ppm, 13C NMR=77.16 ppm). Abbreviations
for NMR data: s=singlet; d=doublet; t=triplet; q=quar-
tet; sep=septet; m=multiplet; bs=broad signal. Prepara-
tive chromatography was performed using Merck silica 60
(0.063–0.02 mesh). GC experiments were run on a Clarus
500 GC with autosampler and FID detector; column: Varian
CP-Sil 8 CB (l=15 m, di=0.25 mm), N2 (flow: 17 cmsꢀ1
;
split 1:50); injector temperature: 2708C, detector tempera-
ture: 3508C. Cyclic voltammograms were recorded in dry
CH2Cl2 under an argon atmosphere at ambient temperature.
A three-electrode configuration was employed. The working
electrode was a Pt disk (diameter 1 mm) sealed in soft glass
with a Pt wire as counter electrode. The pseudo reference
electrode was an Ag wire. Potentials were calibrated inter-
nally against the formal potential of ferrocene [E1/2 = +
0.46 V (CH2Cl2)]. NBu4PF6 (0.1 mol/L) was used as support-
ing electrolyte.
Conclusions
The reactions of [RuCl2ACTHNUTRGNE(NUG NHC)(3-phenylindeneylide-
ne)(py)] (NHC=SIMes, SIPr) with 1-ethenyl-2-phe-
noxybenzenes (with EWG/EDG groups R para to
ethenyl) gave eight new Hoveyda-type complexes in
yields between 66–84%. This synthesis critically relies
on the efficient removal of pyridine as the respective
pyridinium salt using the acidic Amberlyst resin. The
new complexes feature the excellent stability of Hov-
eyda-type complexes, but undergo full precatalyst ac-
tivation within a few seconds. The fast precatalyst ini-
General Procedure for the Synthesis of 2-
(Aryloxy)benzaldehydes (3a–d)
2-(Aryloxy)benzaldehydes ACHTNUTRGNE(NUG 3a-c) were synthesized following
a literature procedure[11] with modifications. Into a dry
Schlenk flask under argon atmosphere were added the cor-
responding phenol (17.7 mmol), 2-fluorobenzaldehyde
tiation translates into rapid olefin metathesis reac- (2.0 g, 16.1 mmol), potassium carbonate (5.6 g, 40.3 mmol)
and anhydrous DMF (40 mL) at room temperature. The
mixture was warmed in a sealed flask to 1708C and stirred
at this temperature for 2 h ACTHNUTRGENUGN(3b, 3c) or at 1508C for 1.5 h
(3a). Then the mixture was allowed to cool to room temper-
ature and was treated with water (200 mL) and the product
was extracted with diethyl ether (3ꢄ50 mL). The combined
organic layers were washed with NaOH (1M, 50 mL), brine
(150 mL), dried over anhydrous MgSO4 and evaporated
under vacuum. The residue was purified by column chroma-
tions – even at low reaction temperatures. The cata-
lytic activity in various RCM reactions was probed
and the new complexes found to be highly efficient;
only 15–100 ppm (0.0015–0.01 mol%) are needed to
reach >90% conversion within less than 15 min of re-
action time for a variety of RCM reactions.
tography [cyclohexane/ethyl acetate 10:1, v/v for ACTHNUTRGNEUG(N 3b, 3c)] or
Experimental Section
used in the next reaction without purification (3a).
2-[4-(Dimethylamino)phenoxy]benzaldehyde (3a) was
obtained as a white solid; yield: 3.07 g (79%). 1H NMR
(300 MHz, CDCl3): d=10.59 (d, J=0.8 Hz, 1H), 7.90 (dd,
J=7.8, 1.8 Hz, 1H), 7.44 (ddd, J=8.5, 7.3, 1.8 Hz, 1H),
7.12–7.05 (m, 1H), 7.03–6.97 (m, 2H), 6.84–6.74 (m, 3H),
2.96 (s, 6H); 13C NMR (75 MHz, CDCl3): d=189.85, 161.75,
148.14, 145.47, 135.76, 128.33, 126.05, 122.23, 121.25, 116.90,
114.18, 41.34.
General Experimental Details
All chemicals were purchased as reagent grade from com-
mercial suppliers and used without further purification,
unless otherwise noted. All reactions involving ruthenium
complexes were performed under an atmosphere of argon.
CH2Cl2 (99.5%) and pentane (99%) were obtained from
Grꢂssing GmbH, Toluene from Sigma–Aldrich (Lab. Re-
agent grade, 99.3%). These solvents were dried and de-
gassed by using a column purification system as described
by Grubbs et al.[23] In this system, the solvents are sparged
2-Phenoxybenzaldehyde (3b) was obtained as a yellow
oil; yield: 2.52 g (79%). 1H NMR (300 MHz, CDCl3): d=
10.52 (d, J=0.8 Hz, 1H), 7.94 (dd, J=7.8, 1.8 Hz, 1H), 7.51
6
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Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted Hoveyda-Type Complexes
(ddd, J=8.4, 7.3, 1.8 Hz, 1H), 7.43–7.35 (m, 2H), 7.22–7.15
(m, 2H), 7.10–7.04 (m, 2H), 6.90 (dd, J=8.4, 0.8 Hz, 1H);
13C NMR (75 MHz, CDCl3) d 189.45, 160.10, 156.53, 135.85,
130.22, 128.55, 127.03, 124.44, 123.44, 119.51, 118.60.
calcd. for C16H17NO (239.13): C 80.30, H 7.16, N 5.85; found
C 79.88, H 7.11, N 5.83.
1-Phenoxy-2-vinylbenzene (4b) was obtained as a colorless
1
solid; yield: 0.99 g (82%). H NMR (500 MHz, CDCl3): d=
2-(4-Chlorophenoxy)benzaldehyde (3c) was obtained as
a yellow solid; yield: 3.07 g (82%). 1H NMR (500 MHz,
CDCl3): d=10.48 (d, J=0.7 Hz, 1H), 7.94 (dd, J=7.8,
1.8 Hz, 1H), 7.53 (ddd, J=8.4, 7.3, 1.8 Hz, 1H), 7.37–7.33
(m, 2H), 7.24–7.19 (m, 1H), 7.03–6.99 (m, 2H), 6.89 (dd, J=
8.4, 0.7 Hz, 1H); 13C NMR (126 MHz, CDCl3): d=189.14,
159.62, 155.20, 135.95, 130.26, 129.65, 128.85, 127.13, 123.91,
120.72, 118.60.
7.62 (dd, J=7.8, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 7.24 (dd,
1H), 7.16–7.13 (m, 1H), 7.07 (tt, J=7.6, 1.1 Hz, 1H), 7.01
(dd, J=17.7, 11.1 Hz, 1H), 6.97–6.94 (m, 2H), 6.92 (dd, J=
8.1, 1.1 Hz, 1H), 5.81 (dd, J=17.7, 1.3 Hz, 1H), 5.29 (dd, J=
11.1, 1.3 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=158.05,
153.75, 131.12, 129.97, 129.83, 129.14, 126.77, 124.21, 122.81,
120.23, 117.91, 115.51; analysis calcd. for C14H12O (196.09):
C 85.68, H 6.16; found C 85.49, H 6.11.
2-(4-Nitrophenoxy)benzaldehyde (3d): Into a dry Schlenk
flask under an argon atmosphere were added 1-fluoro-4-ni-
trobenzene (2.0 g, 14.2 mmol), salicylic aldehyde (2.1 g,
17.0 mmol), potassium carbonate (4.9 g, 35.5 mmol) and an-
hydrous DMF (40 mL). The mixture was warmed in
a sealed flask to 1008C and stirred at this temperature over-
night. Then the mixture was allowed to cool to room tem-
perature, treated with water (200 mL) and the product was
extracted with diethyl ether (3ꢄ50 mL). Combined organic
layers were washed with NaOH (1M in water, 50 mL) and
brine (150 mL), dried over anhydrous MgSO4 and evaporat-
ed under vacuo. Residue was purified by column chromatog-
raphy (cyclohexane/ethyl acetate 4:1, v/v) to afford 3d as
a yellow solid; yield: 2.40 g (69%). 1H NMR (300 MHz,
CDCl3): d=10.34 (d, J=0.7 Hz, 1H), 8.28–8.23 (m, 2H),
8.00 (dd, J=7.8, 1.8 Hz, 1H), 7.66 (dd, J=8.3, 7.4, 1.8 Hz,
1H), 7.41–7.35 (m, 1H), 7.13–7.06 (m, 3H); 13C NMR
(75 MHz, CDCl3): d=188.36, 162.64, 157.14, 143.61, 136.26,
129.71, 128.14, 126.31, 125.85, 120.93, 117.87; HR-MS: m/z=
243.0531, calcd. for C13H9NO4: 243.0542; analysis calcd. for
C13H9NO4 (243.05): C 64.18, H 3.73, N 5.76; found: C 64.23,
H 3.72, N 5.88.
1-(4-Chlorophenoxy)-2-vinylbenzene (4c) was obtained
as
a
colorless liquid; yield: 1.20 g (84%). 1H NMR
(300 MHz, CDCl3): d=7.60 (dd, J=7.7, 1.8 Hz, 1H), 7.28–
7.20 (m, 3H), 7.18–7.12 (m, 1H), 6.99–6.87 (m, 2H), 6.87–
6.82 (m, 2H), 5.78 (dd, J=17.7, 1.3 Hz, 1H), 5.27 (dd, J=
11.1, 1.2 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=156.76,
153.32, 130.85, 130.07, 129.79, 129.26, 127.77, 126.93, 124.66,
120.33, 118.97, 115.86; HR-MS: m/z=230.04815, calcd. for
C14H11ClO: 230.0494; analysis calcd. for C14H11ClO (230.69):
C 72.89, H 4.81; found C 72.82, H 4.92.
1-(4-Nitrophenoxy)-2-vinylbenzene (4d) was obtained as
a yellow solid; yield: 1.15 g (77%). 1H NMR (300 MHz,
CDCl3): d=8.22–8.16 (m, 2H), 7.68–7.64 (m, 2H), 7.38–7.24
(m, 2H), 7.04–7.00 (m, 1H), 6.97–6.91 (m, 1H), 6.79 (dd, J=
17.7, 11.1 Hz, 1H), 5.79 (dd, J=17.7, 1.1 Hz, 1H), 5.29 (dd,
J=11.1, 1.1 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=
163.61, 151.47, 142.67, 130.74, 130.20, 129.65, 127.31, 126.21,
126.14, 121.73, 116.81, 116.51; HR-MS: m/z=241.0714,
calcd. for C14H11NO3: 241.0739; analysis calcd. for
C14H11NO3 (241.25): C 69.70, H 4.60, N 5.81; found C 69.93,
H 4.68, N 5.69.
General Procedure for the Synthesis of Complexes
(5a–d, 6a–d)
General Procedure for the Synthesis of 1-Phenoxy-2-
vinylbenzenes (4a–d)
Complexes (5a–c, 6a–d): A flame-dried Schlenk tube con-
A Schlenk flask containing methyltriphenylphosphonium
iodide (3.0 g, 7.42 mmol) was evacuated and back-filled with
argon three times. Anhydrous tetrahydrofuran (50 mL) was
added by syringe and the formed suspension was cooled to
ꢀ108C. KO-t-Bu (902 mg, 8.04 mmol) was added in portions
to the stirred mixture under a stream of argon, and stirring
continued at ꢀ108C for 20 min. Next, the 2-(aryloxy)benzal-
dehyde (3a–d) (6.18 mmol) was added. The mixture was al-
lowed to warm to room temperature, stirred overnight and
poured into water (500 mL). The product was extracted with
diethyl ether (3ꢄ100 mL). The organic phases were com-
bined, washed with brine and dried over magnesium sulfate.
The solvent was removed under vacuum and the residue
was purified by column chromatography (cyclohexane/ethyl
acetate 20:1, v/v).
N,N-Dimethyl-4-(2-vinylphenoxy)aniline (4a) was ob-
tained as a colorless solid; yield: 1.18 g (80%). 1H NMR
(300 MHz, CDCl3): d=7.58 (dd, J=7.7, 1.8 Hz, 1H), 7.20–
7.01 (m, 3H), 6.96–6.89 (m, 2H), 6.80 (dd, J=8.2, 1.2 Hz,
1H), 6.76 (d, J=9.0 Hz, 2H), 5.82 (dd, J=17.7, 1.4 Hz, 1H),
5.30 (dd, J=11.1, 1.4 Hz, 1H), 2.93 (s, 6H); 13C NMR
(75 MHz, CDCl3): d=155.69, 147.37, 131.49, 128.89, 128.66,
126.61, 122.78, 120.11, 117.92, 115.02, 114.34, 41.51; HR-MS:
m/z=239.1310, calcd. for C16H17NO: 239.1304; analysis
taining
[RuCl2ACHNUTGTRENNUNG
(SIMes)(3-phenylindeneylidene)(py)]
(200 mg, 0.27 mmol) or [RuCl CTHGNUTRENNUNG
2A(SIPr)(3-phenylindeneylide-
ne)(py)] (200 mg, 0.24 mmol) was evacuated and back-filled
with argon three times. Methylene chloride (4 mL), the re-
spective 1-alkoxy-2-vinylbenzene [0.30 mmol for complexes
G
ACHTUNGTREN(NUNG 6a-d)] and Amberlyst
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
or at room temperature for 1 h for complex (6a) and then
filtered, to separate the resin. The filtrate was evaporated
under vacuum and the remaining solid was treated with pen-
tane (10 mL) and the resulting suspension was kept in an ul-
trasonic bath for 1 min. The solid residue was filtered,
washed with methanol (5 mL) and pentane (10 mL) and
dried under vacuum.
Complex (5a) was obtained as a green solid; yield:
135 mg (71%). 1H NMR (500 MHz, CDCl3): d=16.71 (s,
1H), 7.37 (t, J=7.5 Hz, 1H), 7.13 (d, J=8.3 Hz, 2H), 7.03
(s, 4H), 6.98 (d, J=7.3 Hz, 1H), 6.90 (t, J=7.3 Hz, 1H),
6.61 (d, J=8.0 Hz, 3H), 4.15 (s, 4H), 2.93 (s, 6H), 2.47 (s,
12H), 2.37 (s, 6H); 13C NMR (126 MHz, CDCl3): d=292.65,
210.50, 154.24, 143.89, 138.79, 136.22, 129.54, 129.46, 128.74,
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Pavlo Kos et al.
FULL PAPERS
127.69, 123.66, 122.90, 122.53, 113.86, 113.13, 51.81, 41.20,
21.24, 19.43; HR-MS: m/z=703.1661, calcd. for
C36H41N3O4Cl2Ru: 703.16809.
Complex (6c) was obtained as a green solid; yield: 141 mg
(75%). H NMR (500 MHz, CDCl3): d=16.57 (s, 1H), 7.50
1
(t, J=7.7 Hz, 2H), 7.39–7.35 (m, 1H), 7.34–7.29 (m, 6H),
7.26–7.23 (m, 2H), 7.00–6.88 (m, 2H), 6.55 (d, J=8.3 Hz,
1H), 4.15 (s, 4H), 3.61 (sep, J=6.8 Hz, 4H), 1.27 (d, J=
6.9 Hz, 12H), 1.18 (d, J=6.6 Hz, 12H); 13C NMR (126 MHz,
CDCl3): d=286.85, 212.24, 153.61, 151.49, 148.85, 142.93,
137.00, 131.91, 129.82, 129.62, 129.37, 124.69, 124.51, 124.32,
122.34, 113.69, 54.76, 28.73, 26.49, 23.97; HR-MS: m/z=
778.1784, calcd. for C40H47N2OCl3Ru: 778.17584; analysis
calcd. for C40H47N2OCl3Ru (778.80): C 61.63, H 6.08, N 3.60;
found: C 61.19, H 6.16, N 3.68.
Complex (5b) was obtained as a green solid; yield:
142 mg (80%). 1H NMR (300 MHz, CDCl3): d=16.71 (d,
J=0.9 Hz, 1H), 7.44–7.36 (m, 1H), 7.25–7.14 (m, 5H), 7.03
(s, 4H), 7.00 (d, J=1.8 Hz, 1H), 6.94 (td, J=7.5, 0.8 Hz,
1H), 6.66 (d, J=8.3 Hz, 1H), 4.16 (s, 4H), 2.46 (s, 12H),
2.37 (s, 6H); 13C NMR (75 MHz, CDCl3): d=292.53, 210.04,
153.24, 153.04, 144.21, 138.85, 136.03, 129.52, 129.44, 126.03,
124.21, 122.82, 122.08, 51.79, 21.22, 19.44; HR-MS: m/z=
660.1239, calcd. for C34H36N2OCl2Ru: 660.1253.
Complex (6d) was obtained as a green solid; yield:
125 mg (66%). 1H NMR (500 MHz, CDCl3): d=16.55 (s,
1H), 8.18–8.14 (m, 2H), 7.53–7.47 (m, 4H), 7.45–7.40 (m,
1H), 7.33 (d, J=7.7 Hz, 4H), 7.00–6.98 (m, 2H), 6.63 (d, J=
8.3 Hz, 1H), 4.16 (s, 4H), 3.57 (sep, J=6.7 Hz, 4H), 1.27 (d,
J=6.9 Hz, 12H), 1.17 (d, J=6.6 Hz, 12H); 13C NMR
(126 MHz, CDCl3): d=285.70, 211.08, 157.97, 152.17, 148.89,
145.60, 143.22, 136.77, 129.97, 129.39, 126.16, 125.35, 124.71,
123.29, 122.80, 116.78, 114.27, 54.77, 28.79, 26.51, 23.89; HR-
MS: m/z=789.2029, calcd. for C40H74N3O3Cl2Ru: 789.2032.
Complex (5c) was obtained as a green solid; yield: 129 mg
(69%). H NMR (500 MHz, CDCl3): d=16.70 (s, 1H), 7.42
1
(t, J=7.1 Hz, 1H), 7.24–7.18 (m, 4H), 7.06–6.94 (m, 6H),
6.65 (d, J=8.1 Hz, 1H), 4.16 (s, 4H), 2.45 (s, 12H), 2.38 (s,
6H); 13C NMR (75 MHz, CDCl3): d=292.09, 209.55, 152.61,
151.71, 144.10, 138.98, 138.83, 135.94, 131.40, 129.55, 124.60,
123.43, 122.96, 114.00, 51.80, 21.23, 19.41; HR-MS: m/z=
694.0845, calcd. for C34H35N2OCl3Ru: 694.0820.
Complex (5d): A flame-dried Schlenk tube containing
[RuCl
G
(200 mg,
0.27 mmol) was evacuated and back-filled with argon three
times. Tetrahydrofuran (5 mL) was added and resulting sus-
pension was cooled to 08C. Then 1-(4-nitrophenoxy)-2-vinyl-
benzene (65.7 mg, 0.27 mmol) and Amberlyst resin (275 mg,
dry form, 4.70 mmol H+/g) were added and the mixture was
stirred at 08C for 30 min, filtered and evaporated under
vacuum. The solid residue was washed with methanol
(5 mL), pentane (10 mL) and dried under vacuum to afford
Preparation of Catalyst Stock Solution
The ruthenium complex (c=0.75 mmolLꢀ1: 4.0·10ꢀ6 mol)
was weighed into a 10 mL Schlenk tube. The tube was evac-
uated, backfilled with argon and 5.34 mL of dried toluene
were added under a stream of argon. The Schlenk tube was
kept in an ultrasonic bath for 1 min for complete dissolution
of the precatalyst.
5d as
a
green solid; yield: 141 mg (75%). 1H NMR
(500 MHz, CDCl3): d=16.69 (s, 1H), 8.12 (d, J=7.2 Hz,
2H), 7.49 (s, 1H), 7.35 (d, J=7.4 Hz, 2H), 7.04 (s, 6H), 6.79
(d, J=7.3 Hz, 1H), 4.18 (s, 4H), 2.43 (s, 12H), 2.40 (s, 6H);
13C NMR (126 MHz, CDCl3): d=291.42, 208.52, 158.38,
150.86, 145.17, 144.58, 139.16, 138.94, 129.59, 129.46, 125.78,
125.30, 123.47, 121.80, 114.94, 51.79, 21.28, 19.43; MS (EI):
m/z=705 [M+] (HR-MS could not be obtained).
Complex (6a) was obtained as a green solid; yield:
139 mg (73%). 1H NMR (500 MHz, CDCl3): d=16.59 (s,
1H), 7.49 (t, J=7.6 Hz, 2H), 7.32 (d, J=7.6 Hz, 5H), 7.22
(d, J=8.1 Hz, 2H), 6.95–6.83 (m, 2H), 6.64–6.52 (m, 3H),
4.13 (s, 4H), 3.64 (sep., J=6.2 Hz, 4H), 2.92 (s, 6H), 1.27
(d, J=6.7 Hz, 12H), 1.19 (d, J=6.4 Hz, 12H); 13C NMR
(126 MHz, CDCl3): d=287.86, 213.42, 148.85, 142.88, 137.25,
129.67, 129.33, 124.67, 123.74, 123.46, 121.94, 113.73, 113.04,
54.77, 41.10, 28.70, 26.49, 24.07; HR-MS: m/z=787.2600,
calcd. for C42H53N3OCl2Ru: 787.2567; analysis calcd. for
C42H53N3OCl2Ru (787.88): C 64.03, H 6.78, N 5.33; found C
64.56, H 6.96, N 5.12.
Catalyst Screening
All reactions were carried out in sealed 10-mL Schlenk
tubes under an atmosphere of argon at 508C. In a 10-mL
Schlenk tube, substrate (0.2–0.6 mmol) was dissolved in dry
toluene under an atmosphere of argon. This solution was
either ice-cooled to 08C or heated to 508C and catalyst
(0.0015–0.025 mol%) (15–250 ppm) from a stock solution
(0.75 mmolLꢀ1) in toluene was added (for screenings carried
out at 08C, the stock solution was precooled to 08C). The
substrate concentration was defined as c(S)=n(S)/[V(S)+
VACTHNUTRGNE(NUG toluene)+V(stock solution)]. For the determination of
substrate conversion, samples (10 mL, substrate conc. 0.5M)
were taken after the specified times under a stream of argon
and injected into GC vials containing 250 mL of a 25% (v/v)
ethyl vinyl ether solution in toluene. The conversions were
determined by GC.
Supporting Information
Full experimental details including NMR spectra, cyclic vol-
tammograms, mass spectra and crystal structure data are
contained in the Supporting Information.
Complex (6b) was obtained as a green solid; yield:
151 mg (84%). 1H NMR (500 MHz, CDCl3): d=16.59 (d,
J=0.5 Hz, 1H), 7.49 (t, J=7.7 Hz, 2H), 7.39–7.24 (m, 9H),
7.23–7.18 (m, 1H), 6.95 (dd, J=7.6, 1.6 Hz, 1H), 6.89 (t, J=
7.4 Hz, 1H), 6.56 (d, J=8.3 Hz, 1H), 4.14 (s, 4H), 3.63 (sep,
J=6.7 Hz, 4H), 1.27 (d, J=6.9 Hz, 12H), 1.17 (d, J=6.6 Hz,
12H); 13C NMR (126 MHz, CDCl3): d=287.38, 212.79,
154.03, 153.04, 148.87, 143.08, 137.11, 129.74, 129.50, 129.33,
126.46, 124.66, 123.93, 123.16, 122.19, 113.85, 54.76, 28.71,
26.51, 23.97; HR-MS: m/z=744.2178, calcd. for
C40H48N2OCl2Ru: 744.2185.
Acknowledgements
This work was supported by the DFG via grant Pl 178/13-1.
Sabine Foro is thanked for data collection, crystal structure
solution and refinement of complex 5b. The Umicore AG &
8
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Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted Hoveyda-Type Complexes
Co KG is thanked for the generous donation of ruthenium
complexes.
A. M. Dunne, M. Rivard, N. Buschmann, J. Jiricek, S.
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10 Fast Olefin Metathesis: Synthesis of 2-Aryloxy-Substituted
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