Metathesis Catalysts with Fluorinated Unsymmetrical NHC Ligands

Article abstract of DOI:10.1021/om501077w

The synthesis of new fluorinated ruthenium(II) carbene second-generation precatalysts with unsymmetrical N-heterocyclic carbene ligands has been developed. The reaction profiles of these complexes have been studied in RCM with model substrates such as diethyl diallyl- and allylmethallyl-malonate, and CM model reaction of allylbenzene with 1,4-diacetoxybut-2-ene. In olefin metathesis reactions, the new fluorinated second-generation Grubbs complexes exhibit comparable activity with respect to commercially available Grubbs catalysts. On the other hand, in RCM reactions, the Hoveyda-type catalysts present a latent character, which is not present in the classical second-generation Hoveyda catalyst. (Chemical Presented).

Full text of DOI:10.1021/om501077w

Article
pubs.acs.org/Organometallics
Metathesis Catalysts with Fluorinated Unsymmetrical NHC Ligands
Salekh M. Masoud,†,∥ Artur K. Mailyan,†,‡ Vincent Dorcet,§ Thierry Roisnel,§ Pierre H. Dixneuf,∥
Christian Bruneau,*,∥ and Sergey N. Osipov*,†
†A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28, 119991, Moscow, Russia
‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, United States
§UMR 6226 CNRS-Universite
Beaulieu, 35042 Rennes, France
∥UMR 6226 CNRS-Universite
de Rennes 1, Institut des Sciences Chimiques de Rennes, Organomet
́
de Rennes 1, Institut des Sciences Chimiques de Rennes, Centre de Diffractomet
́
rie X, Campus de
́
́
alliques: Materiaux et Catalyse,
́
Centre for Catalysis and Green Chemistry, Campus de Beaulieu, 35042 Rennes, France
S
* Supporting Information
ABSTRACT: The synthesis of new fluorinated ruthenium(II) carbene
second-generation precatalysts with unsymmetrical N-heterocyclic carbene
ligands has been developed. The reaction profiles of these complexes have
been studied in RCM with model substrates such as diethyl diallyl- and
allylmethallyl-malonate, and CM model reaction of allylbenzene with 1,4-
diacetoxybut-2-ene. In olefin metathesis reactions, the new fluorinated
second-generation Grubbs complexes exhibit comparable activity with
respect to commercially available Grubbs catalysts. On the other hand, in
RCM reactions, the Hoveyda-type catalysts present a latent character, which is not present in the classical second-generation
Hoveyda catalyst.
the catalyst stability, reactivity, and selectivity, thus stimulating
the search for new tailor-made systems including mono- and
multidentate uNHC ligands.8
INTRODUCTION
■
Transition-metal-catalyzed olefin metathesis is a powerful tool
for the synthesis of carbon−carbon double bonds in a wide
variety of applications.1 In particular, the development of well-
defined ruthenium alkylidene complexes has broadened the
scope and utility of the olefin metathesis reaction in the
synthesis of small molecules, preparation of complex bioactive
compounds, natural products2 as well as construction of various
functionalized materials and polymers.3
On the other hand, fluorinated compounds have found
widespread applications in key industrial fields such as the
pharmaceutical9 and medicinal chemistry10 or crops11 and
material sciences,12 due to the unique physicochemical features
of fluorine atoms introduced in organic molecules. This
modification can dramatically alter the key chemical character-
istics such as acidity/basicity of neighboring groups, H-bonding
ability, electron density distribution, or conformations to result
in more desired properties, e.g., such as increased lipophilicity
or chemical stability.13
In the field of ruthenium−alkylidene complexes, the steric
and electronic impact of fluorine and fluoroalkyl groups on
their catalytic properties has been mainly studied by usage of
properly modified phosphine,14 styrene15 ligands, as well as by
the replacement of one or two chlorine atoms at ruthenium, for
example, with perfluoroalkoxylates and fluorocatecholates.16
Therefore, it is somewhat surprising that the number of
publications on metathesis catalysts decorated with fluorinated
NHC ligands is extremely limited,17 with the first report
Despite remarkable progress in the area, the design of new
more effective catalysts that are readily available, easy to handle,
and highly selective continues to be crucial. Indeed, still many
metathesis applications such as asymmetric,4 sterically demand-
ing,5 or aqueous6 transformations can be essentially improved
by discovering more active catalytic systems. Recent progress in
developing new Ru-based olefin metathesis catalysts is evidently
related to the modification of the N-heterocyclic carbene
(NHC) ligand architecture of the commercially available
second-generation Grubbs and Hoveyda complexes, which
has directly influenced the catalysts performance. For instance,
the fine-tuning of the electronic and steric properties of the
substituents on the nitrogen atoms located in the vicinity of the
carbenic center has had a significant impact on catalyst activity,
stability, and selectivity in many metathesis applications.7
In this context, the importance of unsymmetrical N-
heterocyclic carbenes (uNHCs) as ligands in metathesis
initiators is incontestable. While uNHCs show similar proper-
ties as compared with symmetrical NHCs, desymmetrization
allows for further fine-tuning. The introduction of chelation,
bifunctionality, shielding effects, and chirality transfer influences
appearing in early 2000. For example, Furstner et al. described
̈
an unsymmetrical complex with a C6F13(CH2)2 group at one of
the imidazolyl nitrogen to increase the solubility of the catalyst
Special Issue: Mike Lappert Memorial Issue
Received: November 2, 2014
© XXXX American Chemical Society
A
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
in supercritical CO2.18 In 2006, Grubbs reported rate
acceleration in RCM of diethyl diallylmalonate arising from a
Ru···F interaction between one ring of a N,N′-bis(2,6-
difluorophenyl)imidazol-2-ylidene and the metal center in the
Grubbs II catalyst analogue.19 This work has been further
extended with studies of synthesis and catalytic activities of
closely related nonsymmetrical analogues20 (1 and 2, Chart 1).
Scheme 1. Synthesis of p-Fluoroalkylaryl-Substituted
uNHC
a
Chart 1. Fluorinated Metathesis Catalysts with
Unsymmetrical Imidazolinylidene Ligands
a
(a) HFA·1.5 H2O, p-TSA (1 mol %), 100 °C, 95%; (b) PhCHO,
toluene, 110 °C; (c) MeI, K2CO3, MeCN; 70 °C then HCl/H2O, rt;
72% for 3 steps; (d) ClCH2C(O)Cl, DMAP, CH2Cl2, rt; (e) NaI,
acetone, rt; 74% for 2 steps; (f) MesNH2 (15-fold excess), rt; 94%; (g)
BH3·SMe2, THF, 85%; (h) MeOH/HCl, rt then HC(OEt)3, 100 °C,
60%. HFA = hexafluoroacetone; p-TSA = p-tolylsulfonic acid, DMAP
= dimethylaminopyridine.
formate ester led to the formation of the desired imidazolinium
salt 9.
For the preparation of the analogous ortho-substituted salt 17
(Scheme 2), the amine 10 formed upon alkylation of 2,4-
Very recently, Grela and co-workers have published the first
indenylidene-type precatalyst with a C6F5CH2-containing
uNHC ligand21 (3, Chart 1). Therefore, the development of
new metathesis catalysts bearing fluorinated unsymmetrical
NHC ligands is of current interest.
Scheme 2. Synthesis of o-Fluoroalkylaryl-Substituted
uNHC
a
We have previously described several metathetic trans-
formations of various unsaturated fluorine-containing molecules
using commercially available Grubbs and Hoveyda complexes
and ruthenium−allenylidene catalysts developed by us22 to
afford a new family of CF3-containing heterocyclic com-
pounds.23 Now, we wish to disclose an efficient route to a novel
type of metathesis catalysts comprising an unsymmetrical
imidazolinylidene ligand with a hexafluoroisopropylalkoxy
[(CF3)2(OR)C−] group in one of the N-aryl substituents (4
and 5, Chart 1) as well as our initial results of their catalytic
activity.
RESULTS AND DISCUSSION
■
First, we directed our efforts toward the synthesis of the
unsymmetrical 1,3-bis(aryl)-4,5-dihydroimidazolium salt 9
(Scheme 1) as a precursor of the corresponding NHC ligand
bearing the hexafluoroisopropylmethoxy group in the para-
position of the N-aryl moiety. For this purpose, the fluorinated
aniline 6 was synthesized via a simple procedure including (a)
the alkylation of 2,6-dimethylaniline with commercially
available hexafluoroacetone hydrate,24 (b) protection of the
amino function with benzaldehyde to form the corresponding
Schiff base, and (c) selective O-methylation/N-deprotection to
afford 6 in good yield. To construct the imidazoline ring, the
fluorinated amine 6 was further acetylated by chloroacetyl
chloride with subsequent halogen exchange with NaI to give
the iodide 7. Then, a slightly modified literature route involved
condensation of 7 with mesitylamine, reduction of the amide
function, and conventional treatment with HCl and an ortho-
a
(a) HFA·1.5 H2O, p-TSA (1 mol %), 100 °C, 92%; (b)
ClCH2C(O)Cl, DMAP, CH2Cl2, rt; (c) HCl/MeOH, rt; (d) NaI,
acetone, rt; 79% for 3 steps; (e) MesNH2 (15-fold excess), rt; 94%; (f)
BH3·SMe2, THF, 75% for 2 steps; (g) TFAA/Py, CH2Cl2, rt; (h) MeI,
K2CO3, DMF; 14 93% for 2 steps; (i) KOH, 18-crown-6, DMSO/
H2O, 130 °C, 15 75%; (j) CH3CO2CHO, CH2Cl2, rt, 16 71%, (k)
TfOH, rt, 1 h then Tf2O, 60 °C, 1 h, then DIPEA, 80 °C, 2 h; 17 95%.
DIPEA = diisopropylethylamine.
B
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
dimethylaniline with HFA hydrate was directly treated with
chloroacetyl chloride to give the corresponding benzoxazine 11
quantitatively. After ring opening of 11 under mild acidic
conditions, the same procedure as for compound 8 (Scheme 1)
was used to afford the hydroxylated diamine 13. In order to
introduce an alkyl substituent selectively on the OH function,
we successively protected the diamino moiety of 13 with two
trifluoroacetyl groups, performed O-alkylation, and then
removed the protecting groups treating 14 with KOH, yielding
the diaminoether 15. Since all our attempts to get the
imidazoline ring from 15 using conventional methods failed,
we slightly modified the protocol recently developed by Organ
and co-workers25 for sterically demanding imidazolinium salts.
Thus, we found that 15 can be selectively formylated at the
more sterically accessible amino group using acetic−formic
mixed anhydride to give 16 (Scheme 3) in good yield.
Scheme 4. Synthesis of Fluorinated Metathesis Catalysts 4
and 5
a
Scheme 3. Plausible Mechanism for the Formation of 17
a
(a) KHMDS, G-I catalyst, toluene, room temperature, 2 h; (b)
KHMDS, H-I catalyst, toluene, 80 °C, 40 min.
case of phosphine-containing complex 4a, a mixture of two
rotational isomers (∼2:1) is formed. It can be rationalized by
the different location of mesityl and fluorinated aryl rings above
the benzylidene group due to possible π−π stacking
interaction.28 In contrast, the sole carbene proton signal of
4b (20.2 ppm) is observed as the result of hindered rotation of
the NHC ligand due to the anchoring effect of the bulky ortho-
substituent. 2D NMR (HMBC) experiment unambiguously
evidences the location of the fluorinated aryl moiety above the
benzylidene ring (cross-peak between styrene ortho-H (7.33
ppm) and quaternary carbon (84.35 ppm) of (CF3)2C-OMe
group; see the Supporting Information).
Single crystals of good quality for X-ray analysis from
complexes 5a,b were obtained (Figures 1 and 2).29
Successive addition of stoichiometric amounts of triflic acid
(TfOH) and triflic anhydride (Tf2O) to the formylated
compound 16 provided conditions for Vilsmeyer−Haack
reaction. The use of Hunig’s base (DIPEA) has proved to be
̈
optimal for the final cyclization step to produce the desired
imidazolinium triflate salt 17 (Scheme 3). Fortunately, in
contrast to Organ’s salts,25 the final fluorinated imidazolinium
triflates 17 can be easily purified by single recrystallization from
hexanes.
Figure 1. X-ray structure of 5a.
With these new fluorinated uNHC salts in hand, we prepared
the ruthenium complexes 4 and 5. Following the conventional
route by the reaction of in situ generated carbene with
commercially available RuCl2(PCy3)2(CHPh) G-I26 and
RuCl2(PCy3)(CH(o-iPrO-C6H4)) H-I,27 these complexes
were obtained in moderate yields. Purification by silica gel
chromatography and further recrystallization from a DCM/n-
pentane mixture afforded dark-brown (4) and dark-green (5),
air stable solids (Scheme 4).
Complexes 4a,b and 5a,b were completely characterized by
NMR spectroscopy and elemental analysis (see the Supporting
Information). The NHC ligands of complexes 5a,b rotate fast
on the NMR timescale, and therefore, only one absorption is
1
observed in the benzylidene region of the H NMR spectra
(around 16.5 ppm) for these phosphine-free complexes. In the
Figure 2. X-ray structure of 5b.
C
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
The structures of complexes 5a and 5b were compared to
that of the olefin metathesis catalyst RuCl2(bis(mesityl)imida-
zolinylidene)(ortho-isopropoxybenzylidene) H-II.30 These
three complexes crystallize in a monoclinic system. All bond
lengths and angles are quite similar, which shows that the
substitution does not have a strong effect on the structures of
the different complexes, especially around the metal center
(Table 1). The chelate (Ru-C(1)-C(3)-O) is almost planar and
Table 1. Selected Structural Data for 5a and 5b
H-II30
5a
5b
bond length (Å)
Figure 3. RCM of DEDAM with catalysts 4a, 4b, 5a, and 5b as
compared to G-II and H-II.
Ru−C(1)
1.828(5)
1.832(4)
1.825(5)
(benzylidene)
Ru−C(2) (NHC)
Ru−O
1.981(5)
1.987(4)
1.975(5)
2.261(3)
2.257(3)
2.272(3)
the NHC in a Grubbs-type second-generation catalyst is not
observed when a hexafluoroisopropyl group is located at the
same position (4a).33
The ring-closing metathesis of the more sterically hindered
diethyl allylmethallylmalonate was also achieved with the new
catalysts 4a,b and 5a,b (Figure 4). A similar reactivity profile as
starting from diallyl malonate was observed, but the reaction
rates were lower in all cases, as previously reported for G-II and
H-II.31
Ru−Cl1
2.3279(12)
2.3393(12)
2.3492(11)
2.3505(11)
2.3116(14)
2.3393(13)
Ru−Cl2
angle (deg)
C(1)−Ru−C(2)
C(1)−Ru−O
C(2)−Ru−O
Cl1−Ru−Cl2
101.59(19)
79.28(17)
176.22(14)
156.47(5)
100.18(15)
100.12(15)
96.59(12)
90.89(12)
102.64(17)
79.59(15)
177.69(14)
159.88(5)
98.37 (14)
98.54(14)
93.46(11)
93.40(11)
101.2(2)
78.91(17)
177.96(16)
156.80(6)
98.92(15)
100.30(15)
97.02(13)
91.86(14)
C(1)−Ru−Cl1
C(1)−Ru−Cl2
C(2)−Ru−Cl1
C(2)−Ru−Cl2
torsion angle (deg)
C(2)−Ru−C(1)−C(3) 171.0(3)
176.2(3)
80.8(3)
88.3(3)
3.2(3)
176.6(4)
84.1(4)
82.9(4)
1.4(3)
Cl1−Ru−C(1)−C(3)
Cl2−Ru−C(1)−C(3)
O−Ru−C(1)−C(3)
78.0(3)
90.1(3)
5.3(3)
parallel to the plane of the five-membered NHC ring. The two
chloride atoms are in a trans-position with a Cl1−Ru−Cl2 angle
of 156−159°, in a plane which is perpendicular to the bidentate
isopropoxybenzylidene and NHC ligands.
It can be noted that, in the solid state, the fluorinated group
in the Hoveyda-type complex 5a is located at the opposite side
of the benzylidene ligand, whereas, for complex 5b, this group
sits above the benzylidene ligand, bringing more steric
hindrance on the carbene side.
Catalytic activities of the prepared precatalysts 4a,b and 5a,b
were investigated in RCM reactions with diethyl diallylmalo-
nate (DEDAM), diethyl allylmethallylmalonate as well as in
CM reaction of allylbenzene with 1,4-diacetoxybut-2-ene
following standard protocols for evaluation of olefin metathesis
catalysts.31 The commercially available RuCl2(PCy3)(H2IMes)-
(CHPh) (G-II)32 and RuCl2(PCy3)(H2IMes)(CH-
(o-iPrO-C6H4)) (H-II)30 catalysts were used as reference
catalysts (H2IMes = bis(mesityl)imidazolinylidene).
The G-II and H-II catalysts are efficient for the RCM of
diethyl diallylmalonate at 30 °C, and full conversion is obtained
within 30 min.31 The Grubbs-type catalysts 4a and 4b behaved
similarly with very close kinetic profiles (Figure 3). On the
other hand, the Hoveyda-type catalysts 5a and 5b presented a
very different reactivity from the H-II catalyst. A pronounced
initiation period (about 30 min) was necessary before they
could achieve full conversion with lower reaction rates and thus
in longer reaction times (2−4 h). The significant negative effect
of an electron-withdrawing substituent such as a chloride
directly connected to the ortho-position of an aryl substituent of
Figure 4. RCM of diethyl allylmethallylmalonate with catalysts 4a, 4b,
5a, and 5b as compared to G-II and H-II.
In these RCM reactions, the reactivity of the Grubbs-type
catalysts 4a and 4b was not strongly affected by the presence of
the fluorinated substituents of the NHC ligands as compared to
G-II. On the contrary, a strong influence was observed in the
Hoveyda-type catalysts 5a and 5b. The presence of the
hexafluoroisopropoxy group induced a long induction period
and a latent behavior before the catalytic systems operate
efficiently.34 The reaction rates were lower, but the robustness
of these catalysts allowed reaching high conversion of the
substrates after long reaction times. It is noteworthy that this
initiation period is more pronounced with complex 5b featuring
the fluorinated ortho-substituted NHC ligand.
In the cross-metathesis of allylbenzene with an excess of 1,3-
diacetoxybut-2-ene, these differences in reactivity did not exist
and all complexes allowed reaching an equilibrium at 70−80%
conversion within 30 min with closely related kinetic profiles
(Figure 5).
CONCLUSION
Two new fluorinated imidazolidinium salts, precursors of N-
heterocyclic carbene ligands, have been prepared. They contain
■
D
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
hexafluoroisopropoxyl aniline. This compound was further treated
with benzaldehyde (12.5 g, 118 mmol) in toluene (160 mL) in the
presence of PTSA (0.7 g, 4 mmol) under refluxing in a Dean−Stark
apparatus for 3 h. After cooling to r.t. and toluene removal, the residue
was redissolved in acetonitrile (150 mL). Iodomethane (2.8 g, 102
mmol) and potassium carbonate (21.7 g, 157 mmol) were added to
the solution, and the mixture was stirred at 70 °C for 5 h. Then, the
cooled (r.t.) reaction mixture was treated with H2O (100 mL) and
extracted with EtOAc (3 × 100 mL). Organic layers were concentrated
to the dryness under reduced pressure. 6 N HCl (300 mL) was added
to the residue, and the mixture was stirred at r.t. for 3 h. The formed
precipitate was separated by filtration, washed with petroleum ether,
and treated with saturated solution of NaHCO3 (200 mL) under
stirring at r.t. for 1 h. The resulting solid was filtered off and dried to
the constant weight to yield 17.0 g (68%) of 6 as a white solid. mp
84−85 °C. 1H NMR (400 MHz, CDCl3): δ 7.12 (s, 2H, ArH), 3.79 (s,
2H, NH2), 3.47 (s, 3H, OCH3), 2.22 (s, 6H, CH3); 13C{1H} NMR
Figure 5. CM of allylbenzene with 1,3-diacetoxybut-2-ene with
catalysts 4a, 4b, 5a, and 5b as compared to G-II and H-II.
1
(101 MHz, CDCl3): δ 144.6, 128.2, 122.9 (q, JC,F = 288 Hz), 121.5,
2
115.8, 83.1 (quint, JC,F = 28 Hz), 54.0, 18.0; 19F{1H} NMR (376
MHz, CDCl3): δ 6.58 (s). Anal. Calcd for C12H13F6NO (%): C, 47.85;
H, 4.35; N, 4.65. Found: C, 47.79; H, 4.43; N, 4.58.
a hexafluoroisopropylmethoxy group connected in the ortho- or
para-position of one N-aryl-substituted imidazolidine deriva-
tive, whereas the other nitrogen atom is connected to a mesityl
group, leading to unsymmetrical NHC ligands. Ruthenium
complexes featuring such an unsymmetrical NHC ligand and a
benzylidene ligand, in the families of second-generation Grubbs
and Hoveyda olefin metathesis catalysts, have been prepared.
These ligands do not bring significant structural modifications
with respect to the symmetrical RuCl2(H2IMes) Hoveyda
catalyst. The performance of the Grubbs catalysts in olefin
metathesis is similar to the classical Grubbs second-generation
catalyst. On the other hand, the new Hoveyda-type catalysts
behave differently from the symmetrical Hoveyda-II catalyst
equipped with the H2IMes carbene ligand in ring-closing
metathesis of malonate derivatives and show a latent character
characterized by an induction period, followed by a lower
reaction rate. Profit could be taken of this property for
applications in ROMP of strained olefins including fluorinated
ones. The latency might be increased by introduction of
additional electron-withdrawing trifluoromethylated groups on
the NHC ligand.
Synthesis of N-(4-(1,1,1,3,3,3-Hexafluoro-2-methoxypropan-
2-yl)-2,6-dimethylphenyl)-2-iodoacetamide (7). Chloroacetyl
chloride (3.5 g, 31.0 mmol) was added dropwise to the solution of
6 (8.5 g, 28.2 mmol) and DMAP (4.48 g, 36.7 mmol) in 120 mL of
anhydrous CH2Cl2 at 0 °C. The reaction mixture was stirred overnight
at r.t. Then, the mixture was concentrated to 30 mL under reduced
pressure, treated with 5% HCl (100 mL), and extracted with CH2Cl2
(3 × 50 mL). Combined organic layers were washed with saturated
solution of NaHCO3 (50 mL) and of water (50 mL) and dried over
MgSO4. After solvent removal under vacuum, the crude acetylated
intermediate was purified by column chromatography in a gradient
manner using EtOAc/petroleum ether (1:4−1:2−1:1−1:0) as the
eluent to yield 8.2 g (77%) of the corresponding chloromethylamide as
a white solid. This compound was further dissolved in acetone (190
mL), and then sodium iodide (8.2 g, 54.5 mmol) was added. The
reaction mixture was stirred at r.t. for 24 h. After filtration, the mother
liquor was concentrated, and the residue was dissolved in EtOAc (50
mL) and washed with a 5% solution of Na2S2O3 (50 mL). The organic
layer was separated, and the aqueous layer was extracted with EtOAc
(3 × 30 mL). Combined organic layers were dried using CaCl2,
filtered, and concentrated. The crude product was recrystallized from
petroleum ether to give 9.8 g (20.9 mmol, 74% for 2 steps) of 7 as a
1
white solid. H NMR (400 MHz, Acetone-d6): δ 9.08 (s, 1H, NH),
EXPERIMENTAL SECTION
7.33 (s, 2H, ArH), 3.98 (s, 2H, CH2), 3.51 (s, 3H, OCH3), 2.34 (s, 6H,
■
CH3); 13C{1H} NMR (101 MHz, Acetone-d6): δ 167.1, 137.6, 128.4,
General Remarks. All solvents were freshly distilled from
appropriate drying agents before use. All other reagents were
recrystallized or distilled as necessary. Syntheses of ruthenium
complexes were performed under an argon atmosphere using a
standard Schlenk technique. Analytical TLC was performed with
Merck silica gel 60 F254 plates. Visualization was accomplished by UV
light (254 and 366 nm), spraying by Ce(SO4)2 solution in 5% H2SO4
or KMnO4 solution in water. Column chromatography was carried out
using Merck silica gel 60 (230−400 mesh ASTM) and ethyl acetate/
petroleum ether or ethyl acetate/CH2Cl2 as eluent. NMR spectra were
recorded at room temperature on Bruker AV-300, AV-400, AV-600
1
2
126.4, 123.5 (q, JC,F = 290 Hz), 83.6 (q, JC,F = 28 Hz), 54.9, 18.7,
−0.8; 19F{1H} NMR (376 MHz, Acetone-d6): δ 6.26 (s). Anal. Calcd
for C14H14F6INO2 (%): C, 35.84; H, 3.01; N, 2.99. Found: C, 35.76;
H, 3.13; N, 2.89.
Synthesis of N1-(4-(1,1,1,3,3,3-Hexafluoro-2-methoxy-
propan-2-yl)-2,6-dimethylphenyl)-N2-mesitylethane-1,2-dia-
mine (8). A mixture of 7 (9.8 g, 20.9 mmol) and mesitylamine (42.3 g,
313.3 mmol) was stirred at r.t. for 4 days. After reaction completion,
the mixture was treated with a 10% solution of NaHCO3 (100 mL)
and extracted with EtOAc (3 × 60 mL). Combined organic layers were
washed with brine and water and then dried over MgSO4 and
concentrated under reduced pressure. The excess of MesNH2 was
removed at 70 °C/0.05 mm Hg. The residual solid was recrystallized
from petroleum ether to give 9.4 g (19.6 mmol, 94%) of the
corresponding adduct as a white solid. This compound was further
dissolved in anhydrous toluene (100 mL), and BH3·SMe2 (44.1 mL of
2 M solution in THF, 88.2 mmol) was added dropwise under an argon
atmosphere at r.t. The resulting mixture was stirred at 90 °C for 3 h.
After cooling to r.t., MeOH was slowly added until ceasing of gas
evolution. Then, a 5% solution (300 mL) of HCl was added and
resulting mixture was extracted with EtOAc (2 × 120 mL). The
aqueous layer was separated, treated with NaHCO3, and extracted with
EtOAc (2 × 120 mL). Combined organic layers were washed with a
saturated solution of NaHCO3, dried over MgSO4, and concentrated
1
spectrometers operating at 300, 400, and 600 MHz for H; 101 and
151 MHz for 13C; 282 and 376 MHz for 19F (CF3CO2H as reference),
and 121 MHz for 31P (85% H3PO4 as reference). The chemical shifts
are frequency referenced relative to the residual undeuterated solvent
peaks.
Synthesis of 4-(1,1,1,3,3,3-Hexafluoro-2-methoxypropan-2-
yl)-2,6-dimethylaniline (6). A mixture of 2,6-dimethylaniline (10.0
g, 82.6 mmol), hexafluoroacetone sesquihydrate (30 g, 153.8 mmol),
and PTSA (200 mg, 1.1 mmol) was heated at 100 °C for 20 h. After
cooling to r.t., water (50 mL) was added and a resulting mixture was
extracted with EtOAc (3 × 30 mL). The combined organic layers were
washed with H2O and brine and then dried over MgSO4. The solvent
was removed under reduced pressure, and the resulting solid was
recrystallized from petroleum ether to give 23.7 g of the corresponding
E
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
under reduced pressure. The crude product was purified by column
mL of water and dried over MgSO4. Then, solvents were evaporated
under reduced pressure, the residue was dissolved in MeOH (300
mL), and concentrated HCl (15 mL) was added to the solution. The
mixture was stirred overnight. Then, solvents were removed under
reduced pressure and the residue was treated with a saturated solution
of NaHCO3 (500 mL) and extracted with EtOAc (2 × 200 mL).
Combined organic layers were washed with 200 mL of water, dried
using MgSO4, filtered, and concentrated under low pressure. The
residual dark brown solid was recrystallized from petroleum ether to
afford 17.7 g (93%) of the corresponding chloromethylamide as a light
brown solid. This compound was further dissolved in acetone (300
mL), and then sodium iodide (12.1 g, 80.7 mmol) was added. The
reaction mixture was stirred at r.t. for 24 h. After filtration, the mother
liquor was concentrated, and the residue was dissolved in EtOAc (50
mL) and washed with a 5% solution of Na2S2O3 (50 mL). The organic
layer was separated, and the aqueous layer was extracted with EtOAc
(3 × 30 mL). Combined organic layers were dried over MgSO4,
filtered, and concentrated. The crude product was recrystallized from
petroleum ether to give 12.5 g, 79% (for 3 steps) of 12 as a brown
chromatography using EtOAc/petroleum (1:6) ether as eluent to yield
1
7.7 g (16.7 mmol, 80% for 2 steps) of 8 as a colorless oil. H NMR
(400 MHz, Acetone-d6): δ 7.18 (s, 2H, ArH), 6.77 (s, 2H, ArH), 4.30
(bs, 1H, NH), 3.52 (bs, 1H, NH), 3.47 (s, 3H, OCH3), 3.37 (t, 3JH,H
=
3
5.9 Hz, 2H, CH2), 3.12 (t, JH,H = 6.0 Hz, 2H, CH2), 2.36 (s, 6H, o-
CH3), 2.21 (s, 6H, o-CH3), 2.17 (s, 3H, p-CH3); 13C{1H} NMR (101
MHz, Acetone-d6): δ 149.6, 144.47, 131.8, 131.0, 130.1, 129.3, 129.2,
1
2
123.8 (q, JC,F = 290 Hz), 119.0, 83.7 (q, JC,F = 28 Hz), 54.5, 49.4,
48.8, 20.7, 19.5, 18.5; 19F{1H} NMR (376 MHz, Acetone-d6): δ 6.11
(s). Anal. Calcd for C23H28F6N2O (%): C, 59.73; H, 6.10; N, 6.06.
Found: C, 59.71; H, 6.12; N, 5.99.
Synthesis of 1-(4-(1,1,1,3,3,3-Hexafluoro-2-methoxypropan-
2-yl)-2,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazolium
Chloride (9). Concentrated HCl (10 mL, 120 mmol) was added to
the solution of 8 (6 g, 13.0 mmol) in MeOH (100 mL) and stirred for
10 min. The solution was evaporated under reduced pressure. To the
residual solid CH(OEt)3 (26.7 g, 180 mmol) was added, and the
mixture was heated at 100 °C for 4 h. Then, the excess of CH(OEt)3
was removed under vacuum and the resulting solid was washed with
100 mL of Et2O. The recrystallization from EtOAc gave pure 9 (3.98
1
solid, mp 143−145 °C. H NMR (300 MHz, CDCl3): δ 8.13 (s, 1H,
NH), 7.26 (s, 1H, ArH), 7.20 (s, 1H, ArH), 5.04 (s, 1H, OH), 3.74 (s,
2H, CH2), 2.35 (s, 3H, CH3), 2.23 (s, 3H, CH3); 13C{1H} NMR (101
MHz, CDCl3): δ 166.5, 138.7, 137.3, 134.6, 134.2, 131.9, 127.0−126.8
(m), 124.6, 121.5, 80.7−79.2 (m), 21.3, 18.8, −1.5; 19F{1H} NMR
(282 MHz, CDCl3): δ 3.86 (s). Anal. Calcd for C13H12F6INO2 (%): C,
34.31; H, 2.66; N, 3.08. Found: C, 34.26; H, 2.73; N, 2.98.
1
g, 60%) as a white solid. mp 190−194 °C. H NMR (400 MHz,
Acetone-d6): δ 10.41 (s, 1H, H2I CH), 7.48 (s, 2H, ArH), 7.00 (s, 2H,
ArH), 4.86−4.69 (m, 4H, H2I CH2CH2), 3.53 (s, 3H, OCH3), 2.64 (s,
6H, o-CH3), 2.47 (s, 6H, o-CH3), 2.28 (s, 3H, Mes p-CH3); 13C{1H}
NMR (101 MHz, Acetone-d6): δ 162.0, 140.6, 138.6, 137.0, 136.7,
132.2, 130.4, 129.6, 129.4, 123.3 (q, 1JC,F = 290 Hz), 83.6 (t, 2JC,F = 28
Hz), 55.2, 52.6, 52.3, 21.0, 18.8, 18.2; 19F{1H} NMR (376 MHz,
Acetone-d6): δ 6.44 (s). Anal. Calcd for C24H27ClF6N2O (%): C,
56.64; H, 5.35; N, 5.50. Found: C, 56.54; H, 5.42; N, 5.48.
Synthesis of 1,1,1,3,3,3-Hexafluoro-2-(2-((2-(mesitylamino)-
ethyl)amino)-3,5-dimethylphenyl)propan-2-ol (13). A mixture of
12 (12.5 g, 27.5 mmol) and mesitylamine (55.7 g, 412.0 mmol) was
stirred at r.t. for 4 days. After reaction completion, the mixture was
treated with a 10% solution of NaHCO3 (100 mL) and extracted with
EtOAc (3 × 60 mL). Combined organic layers were washed with brine
and water and then dried over MgSO4 and concentrated under
reduced pressure. The excess of MesNH2 was removed at 70 °C/0.05
mmHg. The residual solid was recrystallized from petroleum ether to
give 12.0 g (25.9 mmol, 94%) of the corresponding adduct as a white
solid. This compound was further dissolved in anhydrous toluene (150
mL), and BH3·SMe2 (58.3 mL of 2 M solution in THF, 116.6 mmol)
was added dropwise under an argon atmosphere at r.t. The resulting
mixture was stirred at 90 °C for 3 h. After cooling to r.t., MeOH was
slowly added until ceasing of gas evolution. Then, a 10% solution (300
mL) of HCl was added and resulting mixture was extracted with
EtOAc (2 × 120 mL). The aqueous layer was separated, treated with
NaHCO3, and extracted with EtOAc (2 × 120 mL). Combined
organic layers were washed with a saturated solution of NaHCO3,
dried over MgSO4, and concentrated under reduced pressure. The
crude product was recrystallized from petroleum ether to give 9.3 g
(20.7 mmol, 75% for 2 steps) of 13 as a beige solid. mp 148−150 °C.
1H NMR (600 MHz, CDCl3): δ 13.78 (s, 1H, NH), 7.34 (s, 1H, ArH),
7.16 (s, 1H, ArH), 6.87 (s, 2H, Mes ArH), 4.01 (s, 1H, NH), 3.26−
3.22 (m, 2H, CH2), 3.08−3.03 (m, 2H, CH2), 2.35 (s, 3H, CH3), 2.35
(s, 3H, CH3), 2.31 (s, 6H, Mes o-CH3), 2.25 (s, 3H, CH3); 13C{1H}
NMR (151 MHz, CDCl3): δ 142.3, 141.6, 136.4, 135.6, 133.7, 132.7,
130.6, 129.8, 127.5, 124.2, 123.5 (q, 1JC,F = 288 Hz), 80.5 (quint, 2JC,F
= 29 Hz), 51.0, 47.8, 21.3, 20.7, 18.5, 17.2; 19F{1H} NMR (282 MHz,
CDCl3): δ 2.11 (s). Anal. Calcd for C22H26F6N2O (%): C, 58.92; H,
5.84; N, 6.25. Found: C, 58.85; H, 5.93; N, 6.20.
Synthesis of 2,2,2-Trifluoro-N-(2-(1,1,1,3,3,3-hexafluoro-2-
methoxypropan-2-yl)-4,6-dimethylphenyl)-N-(2-(2,2,2-tri-
fluoro-N-mesitylacetamido)ethyl)acetamide (14). TFAA (1.5 g,
13.4 mmol) and pyridine (1.1 g, 13.4 mmol) were added sequentially
to the solution of 13 (3 g, 6.7 mmol) in CH2Cl2 (30 mL) at 0 °C. The
reaction mixture was stirred at r.t. for 1 h, and then water (30 mL) was
added to the mixture. The organic layer was separated; the aqueous
layer was extracted with CH2Cl2 (2 × 20 mL). Combined organic
layers were dried over MgSO4, filtered, and concentrated under
reduced pressure. The crude product was recrystallized from
petroleum ether to yield 4.0 g (6.3 mmol, 94%) of the corresponding
protected diamine as a white solid. This compound (2.0 g, 3.2 mmol)
was solved in dry DMF (25 mL). MeI (1.3 g, 9.5 mmol) and
Synthesis of 2-(2-Amino-3,5-dimethylphenyl)-1,1,1,3,3,3-
hexafluoropropan-2-ol (10). A mixture of 2,4-dimethylaniline
(10.0 g, 82.6 mmol), hexafluoroacetone sesquihydrate (30 g, 153.8
mmol), and PTSA (200 mg, 1.1 mmol) was heated at 100 °C for 20 h.
After cooling to r.t., water (50 mL) was added and the resulting
mixture was extracted with EtOAc (3 × 30 mL). The combined
organic layers were washed with H2O and brine and then dried over
MgSO4. The solvent was removed under reduced pressure, and the
crude product was recrystallized from petroleum ether to give 21.9 g
(92%) of 10 as a brown solid. mp 110−112 °C. 1H NMR (400 MHz,
CDCl3): δ 7.26 (s, 1H, ArH), 7.12 (s, 1H, ArH), 5.58 (bs, 3H, NH2,
OH), 2.32 (s, 3H, CH3), 2.29 (s, 3H, CH3); 13C{1H} NMR (101
MHz, CDCl3): δ 137.2, 135.0, 134.3, 132.8, 127.1−127.0 (m), 123.6,
1
2
123.6 (q, JC,F = 289 Hz), 80.3 (quint, JC,F = 30 Hz), 21.2, 18.2;
19F{1H} NMR (376 MHz, CDCl3): δ 2.59 (s). Anal. Calcd for
C11H11F6NO (%): C, 46.00; H, 3.86; N, 4.88. Found: C, 46.05; H,
3.91; N, 4.76.
Synthesis of 2-(Chloromethyl)-6,8-dimethyl-4,4-bis-
(trifluoromethyl)-4H-benzo[d][1,3]oxazine (11). (isolated as
intermediate in synthesis of 12). Chloroacetyl chloride (0.21 g, 1.9
mmol) was added dropwise to the solution of 10 (0.5 g, 1.7 mmol)
and DMAP (0.21 g, 1.7 mmol) in 20 mL of anhydrous CH2Cl2 at 0 °C
and stirred overnight at r.t. The reaction mixture was treated with 5%
HCl (30 mL) and extracted with CH2Cl2 (2 × 20 mL). Combined
organic layers were washed with a solution of NaHCO3 and water and
dried over MgSO4. The solvent was removed under reduced pressure,
and the crude product was purified by column chromatography using
EtOAc/petroleum ether (1:6) as the eluent to yield 250 mg (0.7
1
mmol, 43%) of 11 as a colorless oil. H NMR (300 MHz, CDCl3): δ
7.18 (s, 1H, ArH), 7.10 (s, 1H, ArH), 4.23 (s, 2H, CH2), 2.39 (s, 3H,
CH3), 2.35 (s, 3H, CH3); 19F{1H} NMR (282 MHz, CDCl3): δ 1.80
(s). Anal. Calcd for C13H10ClF6NO (%): C, 45.17; H, 2.92; N, 4.05.
Found: C, 45.09; H, 2.99; N, 4.01.
Synthesis of N-(2-(1,1,1,3,3,3-Hexafluoro-2-hydroxypropan-
2-yl)-4,6-dimethylphenyl)-2-iodoacetamide (12). Chloroacetyl
chloride (7.0 g, 62.6 mmol) was added dropwise to the solution of
10 (15 g, 52.2 mmol) and DMAP (6.4 g, 52.2 mmol) in 20 mL of
anhydrous CH2Cl2 at 0 °C and stirred overnight at r.t. The reaction
mixture was treated with 5% HCl (150 mL) and extracted with
CH2Cl2 (3 × 60 mL). Combined organic layers were washed with 60
F
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
anhydrous K2CO3 (1.74 g, 12.6 mmol) were added, and the resulting
solution was heated overnight at 80 °C. Then, after cooling to r.t., 20
mL of water was added to the mixture. The crude product was
extracted with EtOAc (3 × 15 mL). Combined organic layers were
dried over MgSO4, filtered, and concentrated under reduced pressure
to afford 2.1 g (99%) of 14 as a white solid. mp 118−120 °C. 1H NMR
(400 MHz, CDCl3): δ 7.30 (s, 1H, ArH), 7.27 (s, 1H, ArH), 6.93 (s,
2H, Mes ArH), 4.23 (td, JH,H = 11.6, 3.7 Hz, 1H, CH2CH2), 4.13 (td,
JH,H = 11.8, 4.8 Hz, 1H, CH2CH2), 3.91 (td, JH,H = 11.6, 4.8 Hz, 1H,
CH2CH2), 3.75 (s, 3H, OCH3), 3.32 (td, JH,H = 11.9, 3.5 Hz, 1H,
CH2CH2), 2.42 (s, 3H, CH3), 2.36 (s, 3H, CH3), 2.30 (s, 3H, CH3),
2.17 (s, 6H, Mes o-CH3); 13C{1H} NMR (101 MHz, CDCl3): δ 158.7
4.54−4.24 (m, 4H, H2I CH2CH2), 3.57 (s, 3H, OCH3), 2.43 (s, 3H,
CH3), 2.40 (s, 3H, CH3), 2.34 (s, 3H, CH3), 2.28 (s, 3H, CH3), 2.26
(s, 3H, CH3); 13C{1H} NMR (101 MHz, CDCl3): δ 161.3, 141.4,
140.9, 139.0, 135.8, 135.2, 134.7, 130.5, 130.4−130.0 (m), 129.9,
2
124.2, 123.5, 122.1, 121.3, 120.6, 119.0, 83.5 (t, JC,F = 30 Hz), 55.7,
53.0, 51.7, 21.5, 21.1, 18.7, 17.9, 17.4; 19F{1H} NMR (376 MHz,
CDCl3): δ 10.44 (s), 6.69 (br.s), −1.21 (s). Anal. Calcd for
C25H27F9N2O4S (%): C, 46.00; H, 3.86; N, 4.88. Found: C, 45.97;
H, 3.88; N, 4.86.
General Procedure for the Synthesis of Grubbs-Type
Catalysts 4a and 4b. In a flame-dried Schlenk flask, imidazolinium
salt (1.00 mmol) was mixed with 20 mL of anhydrous toluene. The
resulting mixture was cooled to 0 °C and degassed three times, and
then KHMDS (1.04 mL of 1 M solution in THF, 1.04 mmol) was
added to the mixture under an argon atmosphere. The reaction
mixture was stirred for 30 min at r.t.; then Grubbs’ catalyst G-I (0.63 g,
0.82 mmol) was added and mixture was stirred for 2 h. During this
time, the reaction mixture changed color from violet to red-brown.
Once complete (TLC-control), solvents were removed from the
reaction mixture under reduced pressure, and the resulting substance
was purified by column chromatography in a gradient manner using
EtOAc/petroleum ether (1:8−1:3) as eluent under an argon
atmosphere. The resulting solid was recrystallized from MeOH to
yield 4 as a brown solid.
(q, 2JC,F = 36 Hz), 158.3 (q, 2JC,F = 36 Hz), 139.3, 139.0, 138.7, 136.6,
1
136.2, 135.8, 134.8, 134.5, 130.0, 129.7, 128.6, 126.4, 123.3 (q, JC,F
=
1
293 Hz), 116.1 (q, JC,F = 288 Hz), 84.6−83.0 (m), 57.7, 51.1, 49.0,
21.4, 21.1, 19.6, 18.3, 18.1; 19F{1H} NMR (376 MHz, CDCl3): δ
10.24−10.09 (m), 9.62 (br.s), 7.94−7.78 (m), 6.91 (s). Anal. Calcd for
C27H26F12N2O3 (%): C, 49.55; H, 4.00; N, 4.28. Found: C, 49.49; H,
4.13; N, 4.19.
Synthesis of N1-(2-(1,1,1,3,3,3-Hexafluoro-2-methoxy-
propan-2-yl)-4,6-dimethylphenyl)-N2-mesitylethane-1,2-dia-
mine (15). A mixture of 14 (2.1 g, 3.2 mmol), 18-crown-6 (5 mg, 0.02
mmol), and a solution of KOH (15.1 g, 0.270 mmol) in water (8 mL)
was heated in DMSO (15 mL) at 130 °C for 1.5 h; then the reaction
mixture was allowed to stir overnight at r.t. Water (30 mL) was added,
and the crude product was extracted with EtOAc (3 × 20 mL).
Combined organic layers were washed with 20 mL of water, dried over
MgSO4, and concentrated. The product was purified by column
chromatography using EtOAc/petroleum ether (1:20) as eluent to
Catalyst RuCl2{1-(4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-
yl)-2,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazol-2-ylidene}-
(CH-Ph)(PCy3) (4a). 1H NMR (400 MHz, C6D6): δ 19.79, 19.53 (s,
1H, CHPh), 8.35 (s, 1H, ArH), 7.61 (s, 1H, ArH), 7.05−6.71 (m, 6H,
ArH), 6.23 (s, 1H), 3.33−1.04 (m, 54H); 13C{1H} NMR (101 MHz,
C6D6): δ 296.7 (d, 2JC,P = 122 Hz), 295.8 (d, 2JC,P = 134 Hz) 221.5 (d,
1
yield 1.05 g (71%) of 15 as a yellowish oil. H NMR (300 MHz,
2
2JC,P = 76 Hz), 220.3 (d, JC,P = 79 Hz), 153.2, 152.0, 142.5, 141.2,
CDCl3): δ 7.07 (s, 1H, ArH), 7.00 (s, 1H, ArH), 6.84 (s, 2H, Mes
ArH), 5.21 (br.s, 1H, NH), 3.51 (s, 3H, OCH3), 3.17 (s, 4H,
CH2CH2), 2.32 (s, 3H, CH3), 2.31 (s, 6H, Mes o-CH3), 2.26 (s, 3H,
CH3), 2.24 (s, 3H, CH3); 19F{1H} NMR (282 MHz, CDCl3): δ 8.31
(s). Anal. Calcd for C23H28F6N2O (%): C, 59.73; H, 6.10; N, 6.06.
Found: C, 59.71; H, 6.19; N, 6.01.
140.2, 139.2, 138.9, 138.5, 137.7, 137.5, 137.1, 135.6, 130.4, 129.5,
1
128.8, 128.7, 128.6, 128.4, 127.5, 123.4 (q, JC,F = 290 Hz), 123.0 (q,
1JC,F = 290 Hz), 84.0−82.8 (m), 54.5, 54.3, 52.1, 51.6, 51.3, 33.0, 32.9,
32.1, 31.9, 29.6, 29.3, 28.3, 28.2, 27.9, 27.8, 26.7, 26.5, 21.2, 21.0, 20.8,
20.5, 19.4, 19.0; 19F{1H} NMR (376 MHz, C6D6): δ 7.42 (s); 31P{1H}
NMR (162 MHz, C6D6): δ 28.00 (s), 23.07 (s). Anal. Calcd for
C49H65Cl2F6N2OPRu (%): C, 57.98; H, 6.45; N, 2.76. Found: C,
57.93; H, 6.49; N, 2.74.
Synthesis of N-(2-((2-(1,1,1,3,3,3-Hexafluoro-2-methoxy-
propan-2-yl)-4,6-dimethylphenyl)amino)ethyl)-N-mesityl-
formamide (16). Acetic formic anhydride (0.4 g, 4.54 mmol) was
added dropwise to the solution of 15 (1.05 g, 2.27 mmol) in CH2Cl2
(20 mL). After homogenization, the reaction mixture was allowed to
stir for 30 min at r.t. Then, 40 mL of water was added and the mixture
was extracted with CH2Cl2 (2 × 30 mL). Combined organic layers
were washed with a saturated solution of NaHCO3 and water, dried
over MgSO4, filtered, and concentrated under reduced pressure. The
crude product was purified by column chromatography using EtOAc/
petroleum ether (1:4) as eluent to yield 0.67 g (60%) of 16 as a
colorless oil. 1H NMR (300 MHz, CDCl3): δ 8.02 (s, 1H, CHO), 7.03
(s, 1H, ArH), 6.95 (s, 3H, ArH), 5.06 (s, 1H, NH), 3.80 (t, 3JH,H = 7.4
Hz, 2H, CH2), 3.43 (s, 3H, OCH3), 3.13 (q, 3JH,H = 7.2 Hz, 2H, CH2),
2.30 (s, 3H, CH3), 2.24 (s, 3H, CH3), 2.22 (s, 9H, CH3); 13C{1H}
NMR (101 MHz, CDCl3): δ 163.9, 147.0, 138.3, 136.4, 135.8, 135.3,
135.2, 130.9, 129.7, 127.7, 123.9, 121.0, 85.6, 54.5, 46.7, 45.6, 29.7,
20.9, 20.6, 20.5, 18.3; 19F{1H} NMR (282 MHz, CDCl3): δ 8.26 (s).
Anal. Calcd for C24H28F6N2O2 (%): C, 58.77; H, 5.75; N, 5.71. Found:
C, 58.72; H, 5.81; N, 5.67.
Synthesis of 1-(2-(1,1,1,3,3,3-Hexafluoro-2-methoxypropan-
2-yl)-4,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazolium
Triflate (17). Triflic acid (0.2 g, 1.37 mmol) was added to the solution
of 16 (0.67 g, 1.37 mmol) in toluene (30 mL), and the mixture was
stirred at r.t. for 15 min. Then, triflic anhydride (0.29 g, 1.37 mmol)
was added, and the reaction mixture was heated at 65 °C for 1.5 h.
DIPEA (0.53 g, 4.11 mmol) was added, and the reaction mixture was
heated at 80 °C for another 1.5 h. After cooling to r.t., 30 mL of water
was added and the mixture was extracted with CH2Cl2 (3 × 20 mL).
The combined organic layers were dried using MgSO4, filtered, and
concentrated under reduced pressure. The crude product was
recrystallized from petroleum ether to give 0.82 g (1.33 mmol, 95%)
of 17 as a beige solid. 1H NMR (400 MHz, CDCl3): δ 8.43 (s, 1H, H2I
CH), 7.42 (s, 1H, ArH), 7.31 (s, 1H, ArH), 6.94 (s, 2H, Mes ArH),
Catalyst RuCl2{1-(2-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-
yl)-4,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazol-2-ylidene}-
1
(CH-Ph)(PCy3) (4b). H NMR (600 MHz, C6D6): δ 20.19 (s, 1H,
CHPh), 9.36 (s, 1H, ArH), 7.32 (s, 1H, ArH), 7.25 (s, 1H, ArH), 7.11
(t, JH,H = 7.2 Hz, 1H, ArH), 7.06 (s, 1H, ArH), 6.97 (s, 1H, ArH), 6.94
(s, 1H, ArH), 6.82 (s, 1H, ArH), 5.94 (s, 1H, ArH), 4.04 (s, 3H,
OCH3), 3.91 (m, 1H, H2I CH2CH2), 3.55 (dd, JH,H = 22.0, 10.3 Hz,
1H, H2I CH2CH2), 3.28 (m, 1H, H2I CH2CH2), 3.15 (dd, JH,H = 22.0,
10.3 Hz, 1H, H2I CH2CH2), 2.95 (s, 3H, CH3), 2.68 (s, 3H, CH3),
2.52 (q, JH,P = 11.7 Hz, 3H, PCy3), 2.28 (s, 3H, CH3), 2.21 (s, 3H,
CH3), 1.67 (s, 3H, CH3), 1.59 (m, 16H, PCy3), 1.15 (m, 13H, PCy3),
0.90 (q, JH,P = 12.4 Hz, 3H, PCy3); 13C{1H} NMR (151 MHz, C6D6):
2
2
δ 294.4 (d, JC,P = 117 Hz), 220.3 (d, JC,P = 79 Hz), 152.5, 152.5,
141.8, 140.5, 138.6, 138.5, 138.4, 137.1, 135.9, 134.5, 132.2, 130.5,
130.4, 129.5, 128.8, 128.4, 128.1, 127.3, 125.2, 125.0, 123.2, 123.1, 84.4
2
(quint, JC,F = 26 Hz), 57.3, 53.0, 52.05, 50.02, 31.8, 31.7, 29.8, 29.4,
28.3, 28.22, 28.15, 26.6, 21.2, 21.0, 20.9, 20.7, 20.4; 19F{1H} NMR
(376 MHz, C6D6): δ 14.1 (s), 8.7 (s); 31P{1H} NMR (162 MHz,
C6D6) δ 27.2 (s). Anal. Calcd for C49H65Cl2F6N2OPRu (%): C, 57.98;
H, 6.45; N, 2.76. Found: C, 58.04; H, 6.51; N, 2.67.
General Procedure for Synthesis of Hoveyda-Type Catalysts
5a and 5b. In a flame-dried Schlenk flask, imidazolinium salt (0.98
mmol) was mixed with 35 mL of anhydrous toluene. The resulting
mixture was cooled to 0 °C and degassed three times; then KHMDS
(1.25 mL of 1 M solution in THF, 1.25 mmol) was added to the
mixture under an argon atmosphere. The reaction mixture was stirred
for 30 min at r.t.; then Hoveyda catalyst H-I (0.49 g, 0.82 mmol) was
added and mixture was stirred for 40 min at 80 °C. During this time,
the reaction mixture changed color from brown to green. Once
complete, solvents were removed from the reaction mixture under
reduced pressure, and the resulting substance was purified by column
G
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
chromatography using EtOAc/petroleum ether (1:3) as eluent to yield
Hoveyda-type catalyst as a green solid. Suitable for X-ray crystals of 5a
and 5b were grown by slow diffusion of hexane vapors in CH2Cl2
solution.
REFERENCES
■
(1) (a) Chauvin, Y. Angew. Chem., Int. Ed. 2006, 45, 3740.
(b) Schrock, R. R. Angew. Chem., Int. Ed. 2006, 45, 3748. (c) Grubbs,
R. H. Angew. Chem., Int. Ed. 2006, 45, 3760. (d) Grubbs, R. H.
Handbook of Metathesis; Wiley-VCH: Weinheim, Germany, 2003;
Vols. 1−3. (e) Connon, S. J.; Blechert, S. In Ruthenium Catalysts and
Fine Chemistry; Dixneuf, P. H., Bruneau, C., Eds.; Springer:
Catalyst RuCl2{1-(4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-
yl)-2,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazol-2-ylidene}-
1
(CH-o-iPrO-Ph) (5a). H NMR (600 MHz, C6D6): δ 16.61 (s, 1H,
CHAr), 7.64 (s, 2H, ArH), 7.11 (d, JH,H = 7.4 Hz, 1H, ArH), 7.08 (m,
1H, ArH), 6.87 (s, 2H, ArH), 6.64 (t, JH,H = 7.4 Hz, 1H, ArH), 6.30 (d,
Heidelberg, Germany, 2004; Vol. 11, p 93. (f) Furstner, A. Angew.
̈
3
JH,H = 8.3 Hz, 1H, ArH), 4.46 (sept, JH,H = 6.0 Hz, 1H, OiPr CH),
Chem., Int. Ed. 2000, 39, 3012. (g) Hoveyda, A. H.; Zhugralin, A. R.
Nature 2007, 450, 243. (h) Deshmuhk, P. H.; Blechert, S. Dalton
Trans. 2007, 2479. (i) Astruc, D. New J. Chem. 2005, 29, 42.
(j) Lozano-Vila, A. M.; Monsaert, S.; Bajek, A.; Verpoort, F. Chem. Rev.
2010, 110, 4865. (k) Perfetto, A.; Costabile, C.; Longo, P.; Grisi, F.
Organometallics 2014, 33, 2747. (l) Grela, K., Ed. Olefin Metathesis
Theory and Practice; J. Wiley & Sons: Hoboken, NJ, 2014.
(2) (a) Vougioukalakis, G. C.; Grubbs, R. H. Chem. Rev. 2010, 110,
1746. (b) Samojlowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 2009,
109, 3708. (c) Diesendruck, C. E.; Tzur, E.; Lemcoff, N. G. Eur. J.
Inorg. Chem. 2009, 4185. (d) Fischmeister, C.; Dixneuf, P. H. In
Metathesis Chemistry: From Nanostructure Design to Synthesis of
Advanced Materials; Imamoglu, Y., Dragutan, V., Eds.; Springer:
Dordrecht, The Netherlands, 2007; pp 3−27. (e) Bieniek, M.;
Michrowska, A.; Usanov, D. L.; Grela, K. Chem.Eur. J. 2008, 14, 806.
(3) (a) Bielawski, C. W.; Grubbs, R. H. Prog. Polym. Sci. 2007, 32, 1.
(b) Frenzel, U.; Nuyken, O. J. Polym. Sci., Part A: Polym. Chem. 2002,
40, 2895. (c) Buchmeiser, R. M. Chem. Rev. 2000, 100, 1565.
(d) Leitgeb, A.; Wappel, J.; Slugovc, C. Polymer 2010, 51, 2927.
3.35 (m, 2H, H2I CH2CH2), 3.28 (m, 5H, H2I CH2CH2, OCH3), 2.60
(s, 6H, CH3), 2.43 (s, 6H, CH3), 2.22 (s, 3H, Mes p-CH3), 1.28 (d,
3JH,H = 6.1 Hz, 6H, OiPr CH3); 13C{1H} NMR (151 MHz, C6D6): δ
291.4, 213.2, 152.7, 145.7, 141.4, 138.8, 129.8, 129.3, 128.7, 128.4,
123.4 (q, 1JC,F = 290 Hz), 122.34, 122.27, 113.3, 83.5 (quint, 2JC,F = 28
Hz), 75.2, 54.2, 21.4, 21.1; 19F{1H} NMR (282 MHz, C6D6): δ 7.57
(s). Anal. Calcd for C34H38Cl2F6N2O2Ru (%): C, 51.52; H, 4.83; N,
3.53. Found: C, 51.49; H, 4.86; N, 3.53.
Catalyst RuCl2{1-(2-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-
yl)-2,6-dimethylphenyl)-3-mesityl-4,5-dihydroimidazol-2-ylidene}-
1
(CH-o-iPrO-Ph) (5b). H NMR (400 MHz, C6D6): δ 16.68 (s, 1H,
CHAr), 7.72 (s, 1H, ArH), 7.09 (m, 2H, ArH), 6.98 (d, JH,H = 7.6 Hz,
2H, ArH), 6.74 (s, 1H, ArH), 6.66 (t, JH,H = 7.3 Hz, 1H, ArH), 6.32 (d,
3
JH,H = 8.1 Hz, 1H, ArH), 4.46 (sept, JH,H = 5.7 Hz, 1H, OiPr CH),
4.17 (m, 1H, H2I CH2CH2), 3.78 (s, 3H, OCH3), 3.46 (m, 3H, H2I
CH2CH2), 2.72 (s, 3H, CH3), 2.64 (s, 3H, CH3), 2.49 (s, 3H, CH3),
2.26 (s, 3H, CH3), 2.04 (s, 3H, CH3), 1.29 (dd, JH,H = 12.8, 5.9 Hz,
6H, OiPr CH3); 13C{1H} NMR (151 MHz, C6D6): δ 289.4, 215.3,
153.2, 145.4, 142.9, 140.8, 140.4, 139.7, 138.8, 138.4, 135.7, 134.8,
̀
(e) Gradillas, A.; Perez-Castells, J. Angew. Chem., Int. Ed. 2006, 45,
1
1
129.7, 129.6, 129.3, 123.8 (q, JC,F = 294 Hz), 123.5 (q, JC,F = 290
6086. (f) Conrad, J. C.; Fogg, D. E. Curr. Org. Chem. 2006, 10, 185.
(g) Monfette, S.; Fogg, D. E. Chem. Rev. 2009, 109, 3783. (h) Nolan,
S. P.; Clavier, H. Chem. Soc. Rev. 2010, 39, 3305. (i) Donohe, T. J.;
Fishlock, L. P.; Procopiou, P. A. Chem.Eur. J. 2008, 14, 5716. (j) van
Otterlo, W. A. L.; de Koning, C. B. Chem. Rev. 2009, 109, 3743.
(k) Deraedt, C.; d’Halluin, M.; Astruc, D. Eur. J. Inorg. Chem. 2013,
4881.
2
Hz), 122.2, 122.1, 113.5, 85.0 (quint, JC,F = 28 Hz), 75.3, 58.2, 53.5,
51.1, 21.4, 21.31, 21.29, 21.25, 21.1, 21.0, 20.8; 19F{1H} NMR (376
MHz, C6D6): δ 12.29 (s), 6.70 (s). Anal. Calcd for C34H38Cl2-
F6N2O2Ru (%): C, 51.52; H, 4.83; N, 3.53. Found: C, 51.48; H, 4.85;
N, 3.49.
(4) (a) Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2007, 129,
3824. (b) Keitz, B. K.; Grubbs, R. H. Organometallics 2010, 29, 403.
(c) Stenne, B.; Timperio, J.; Savoie, J.; Dudding, T.; Collins, S. K. Org.
Lett. 2010, 12, 2032. (d) Funk, T. W.; Berlin, J. M.; Grubbs, R. H. J.
Am. Chem. Soc. 2006, 128, 1840. (e) Schmidt, B.; Staude, L. J. Org.
Chem. 2009, 74, 9237. (f) Tiede, S.; Berger, A.; Schlesiger, D.; Rost,
ASSOCIATED CONTENT
■
S
* Supporting Information
1
Copies of H, 13C, 19F, and 31P NMR spectra for all new
compounds, 2D NMR (HMBC) spectra for 4b, and
crystallography data for 5a and 5b. This material is available
free of charge via the Internet at http://pubs.acs.org.
D.; Luhl, A.; Blechert, S. Angew. Chem. 2010, 49, 3972.
̈
(5) (a) Stewart, I. C.; Ung, T.; Pletnev, A. A.; Berlin, J. M.; Grubbs,
R. H.; Schrodi, Y. Org. Lett. 2007, 9, 1589. (b) Berlin, J. M.; Campbell,
K.; Ritter, T.; Funk, T. W.; Chlenov, A.; Grubbs, R. H. Org. Lett. 2007,
9, 1339.
AUTHOR INFORMATION
■
Corresponding Authors
(6) (a) Connon, S. J.; Blechert, S. Bioorg. Med. Chem. Lett. 2002, 12,
1873. (b) Gulajski, L.; Michrowska, A.; Bujok, R.; Grela, K. J. Mol.
Catal. A 2006, 254, 118. (c) Jordan, J. P.; Grubbs, R. H. Angew. Chem.,
Int. Ed. 2007, 46, 5152. (d) Michrowska, A.; Gulajski, L.; Kaczmarska,
Z.; Mennecke, K.; Kirschning, A.; Grela, K. Green Chem. 2006, 8, 685.
(e) Burtscher, D.; Grela, K. Angew. Chem., Int. Ed. 2009, 48, 442.
(f) Jordan, J. P.; Grubbs, R. H. Angew. Chem., Int. Ed. 2007, 46, 5152.
(g) Hong, S. H.; Grubbs, R. H. J. Am. Chem. Soc. 2006, 128, 3508.
(7) Representative examples: (a) Seiders, T. J.; Ward, D. W.; Grubbs,
R. H. Org. Lett. 2001, 3, 3225. (b) Ritter, T.; Day, M. W.; Grubbs, R.
H. J. Am. Chem. Soc. 2006, 128, 11768. (c) Chung, C. K.; Grubbs, R.
H. Org. Lett. 2008, 10, 2693. (d) Kuhn, K. M.; Bourg, J.-B.; Chung, C.
K.; Virgil, S. C.; Grubbs, R. H. J. Am. Chem. Soc. 2009, 131, 5313.
(e) Savoie, T.; Stenne, B.; Collins, S. K. Adv. Synth. Catal. 2009, 351,
1826. (f) Gatti, M.; Vieille-Petit, L.; Luan, X.; Mariz, R.; Drinkel, E.;
Linden, A.; Dorta, R. J. Am. Chem. Soc. 2009, 131, 9498. (g) Vieille-
Petit, L.; Luan, X.; Gatti, M.; Blumentritt, S.; Linden, A.; Clavier, H.;
Nolan, S. P.; Dorta, R. Chem. Commun. 2009, 3783. (h) Grisi, F.;
Costabile, C.; Gallo, E.; Mariconda, A.; Tedesco, C.; Longo, P.
Organometallics 2008, 27, 4649.
*E-mail: christian.bruneau@univ-rennes1.fr (C.B.).
*E-mail: osipov@ineos.ac.ru. Fax: +74991355085 (S.N.O.).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the Joint European
Laboratory “Homogeneous Catalysis for Sustainable Develop-
ment - CH2D” between the Russian Academy of Sciences
(RAS) and CNRS Institute of Chemistry, the Russian
Foundation for Basic Research (grant No. 12-03-93111).
S.M.M. thanks the RAS and the French Embassy in Moscow
for a Ph.D. fellowship.
DEDICATION
■
This paper is dedicated to the memory of Prof. Michael F.
Lappert for his outstanding contribution to organometallic
chemistry.
(8) Tornatzky, J.; Kannenberg, A.; Blechert, S. Dalton Trans. 2012,
41, 8215.
H
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
(9) (a) Hiyama, H. Organofluorine Compounds: Chemistry and
Applications; Springer: Berlin, 2000. (b) Chambers, R. D. Fluorine in
Organic Chemistry; Blackwell Publishing Ltd.: Oxford, U.K., 2004.
(c) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity,
Applications; Wiley-VCH: Weinheim, 2004. (d) Uneyama, K. Organo-
fluorine Chemistry; Blackwell Publishing Ltd.: Oxford, U.K., 2006.
(21) Ablialimov, O.; Kędziorek, M.; Malin
Grela, K. Organometallics 2014, 33, 2160.
́
́
ska, M.; Wozniak, K.;
(22) (a) Furstner, A.; Picquet, M.; Bruneau, C.; Dixneuf, P. H. Chem.
̈
Commun. 1998, 1315. (b) Picquet, M.; Touchard, D.; Bruneau, C.;
Dixneuf, P. H. New J. Chem. 1999, 141.
(23) (a) Osipov, S. N.; Bruneau, C.; Picquet, M.; Kolomiets, A. F.;
Dixneuf, P. H. Chem. Commun. 1998, 2053. (b) Osipov, S. N.;
Artyushin, O. I.; Kolomiets, A. F.; Bruneau, C.; Dixneuf, P. H. Synlett
2000, 1031. (c) Osipov, S. N.; Kobelíkova, N. M.; Shchetnikov, G. T.;
Kolomiest, A. F.; Bruneau, C.; Dixneuf, P. H. Synlett 2001, 621.
(d) Osipov, S. N.; Artyushin, O. I.; Kolomiets, A. F.; Bruneau, C.;
(e) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881.
̈
́ ́
(f) Wang, J.; Sanchez-Rosello, M.; Acena, J. L.; del Pozo, C.;
̃
Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev.
2014, 114, 2432.
(10) (a) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem.
Soc. Rev. 2008, 37, 320. (b) Ojima, I., Ed. Fluorine in Medicinal
Chemistry and Chemical Biology; Wiley-Blackwell: Chichester, U.K.,
2009.
(11) (a) Banks, R. E.; Smart, B. E.; Tatlow, J. C. Organofluorine
Chemistry: Principles and Commercial Applications; Plenum Press: New
York, 1994. (b) Giornal, F.; Pazenok, S.; Rodefeld, L.; Lui, N.; Vors, J.-
P.; Leroux, F. R. J. Fluorine Chem. 2013, 152, 2.
(12) Berger, R.; Resnati, G.; Metrangolo, P.; Weber, E.; Hulliger, J.
Chem. Soc. Rev. 2011, 40, 3496.
(13) (a) Schlosser, M. Angew. Chem., Int. Ed. 1998, 110, 1496.
(b) O’Hagan, D. Chem. Soc. Rev. 2008, 37, 308.
(14) (a) Da Costa, R. C.; Gladysz, J. A. Chem. Commun. 2006, 2619.
(b) Da Costa, R. C.; Gladysz, J. A. Adv. Synth. Catal. 2007, 349, 243.
(c) Tuba, R.; da Costa, R. C.; Bazzi, H. S.; Gladysz, J. A. ACS Catal.
2012, 2, 155. (d) Tuba, R.; Brothers, E. N.; Reibenspies, J. H.; Bazzi,
H. S.; Gladysz, J. A. Inorg. Chem. 2012, 51, 9943.
(15) (a) Matsugi, M.; Curran, D. P. J. Org. Chem. 2005, 70, 1636.
(b) Leach, S.; Cordier, C. J.; Morton, D.; McKierman, G. J.; Warriner,
S.; Nelson, A. J. Org. Chem. 2008, 73, 2753. (c) Morton, D.; Leach, S.;
Cordier, C.; Warriner, S.; Nelson, A. Angew. Chem., Int. Ed. 2009, 48,
104. (d) Matsugi, M.; Kobayashi, Y.; Suzumura, N.; Tsuchiya, Y.;
Picquet, M.; Dixneuf, P. H. Eur. J. Org. Chem. 2001, 3891. (e) Sem
D.; Le Notre, J.; Bruneau, C.; Dixneuf, P. H.; Kolomiets, A. F.; Osipov,
S. N. New. J. Chem. 2001, 25, 16. (f) Eckert, M.; Monnier, F.;
Shchetnikov, G. T.; Titanyuk, I. D.; Osipov, S. N.; Toupet, L.; Derien,
́
eril,
̂
́
S.; Dixneuf, P. H. Org. Lett. 2005, 7, 3741. (g) Vorobyeva, D. V.;
Mailyan, A. K.; Peregudov, A. S.; Karimova, N. M.; Vasilyeva, T. P.;
Bushmarinov, I. S.; Bruneau, C.; Dixneuf, P. H.; Osipov, S. N.
Tetrahedron 2011, 67, 3524. (h) Eckert, M.; Moulin, S.; Monnier, F.;
́
Titanyuk, I. D.; Osipov, S. N.; Roisnel, T.; Derien, S.; Dixneuf, P. H.
Chem.Eur. J. 2011, 17, 9456. (i) Mailyan, A. K.; Krylov, I. M.;
Bruneau, C.; Dixneuf, P. H.; Osipov, S. N. Eur. J. Org. Chem. 2013,
5353.
(24) Similar products were previously described via alkylation of
anilines using gaseous hexafluoroacetone: (a) Gilbert, E. E.; Jones, E.
S.; Sibilia, J. P. J. Org. Chem. 1965, 1001. (b) Chkanikov, N. D.;
Sviridov, V. D.; Zelenin, A. E.; Galakhov, M. V.; Kolomiets, A. F.;
Fokin, A. V. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1990,
39, 323.
(25) Tsimerman, M.; Mallik, D.; Matsuo, T.; Otani, T.; Tamao, K.;
Organ, M. G. Chem. Commun. 2012, 48, 10352.
(26) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew.
Chem., Int. Ed. Engl. 1995, 34, 2039.
Shioiri, T. J. Org. Chem. 2010, 75, 7905. (e) Kvíca
Kelbichova, V.; Babunek, M.; Rybac ova, M.; Kvíca
J.; Brezinova, A. J. Fluorine Chem. 2013, 153, 12. (f) Babunek
Simunek, O.; Hosek, J.; Rybac ova, M.; Cvacka, J.; Brezinova,
la, J. J. Fluorine Chem. 2014, 161, 66. (g) Michalek, F.;
Bannwarth, W. Helv. Chim. Acta 2006, 89, 1030. (h) Andrushko, V.;
̌
la, J.; Schindler, M.;
lova, M.; Cvacka,
, M.;
A.;
(27) Kingsbury, J. S.; Harrity, J. P. A.; Gray, B. L.; Hoveyda, A. H. J.
Am. Chem. Soc. 1999, 121, 791.
́
̌
́
k
̌
́
̌
́
̌
̌
́
̌
(28) (a) Mandal, D.; Gupta, B. D. Organometallics 2006, 25, 3305.
(b) Mandal, D.; Gupta, B. D. Organometallics 2007, 26, 658.
(29) CCDC-1030291 (5a) and CCDC-1030379 (5b) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
(30) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am.
Chem. Soc. 2000, 122, 8168.
(31) Ritter, T.; Hejl, A.; Wenzel, A. G.; Funk, T. W.; Grubbs, R. H.
Organometallics 2006, 25, 5740.
(32) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999,
1, 953.
̌
̌
́
k
̌
́
̌
̌
́
̊
Kvíca
̌
Schwinn, D.; Tzucke, C. C.; Michalek, F.; Horn, J.; Mossner, C.;
̈
Bannwarth, W. Helv. Chim. Acta 2005, 88, 936. (i) Lim, J.; Lee, S. S.;
Ying, J. Y. Chem. Commun. 2008, 4312. (j) Hensle, E. M.; Tobis, J.;
Tiller, J. C.; Bannwarth, W. J. Fluorine Chem. 2008, 129, 968. (k) Yao,
Q.; Zhang, Y. J. Am. Chem. Soc. 2004, 126, 74.
(16) (a) Krause, J.; Nuyken, O.; Wurst, K.; Buchmeiser, M. R.
Chem.Eur. J. 2004, 10, 777. (b) Krause, J.; Nuyken, O.; Buchmeiser,
M. R. Chem.Eur. J. 2004, 10, 2029. (c) Yang, L.; Mayr, M.; Wurst,
K.; Buchmeiser, M. R. Chem.Eur. J. 2004, 10, 5761. (d) Vehlow, K.;
(33) Leuthauβer, S.; Schmidts, V.; Thiele, C. M.; Plenio, H. Chem.
̈
Eur. J. 2008, 14, 5465.
Kohler, K.; Blechert, S.; Dechert, S.; Meyer, F. Eur. J. Inorg. Chem.
̈
(34) (a) Monsaert, S.; Lozano Vila, A. M.; Drozdzak, R.; Van Der
Voort, P.; Verpoort, F. Chem. Soc. Rev. 2009, 38, 3360. (b) Kabro, A.;
Ghattas, G.; Roisnel, T.; Fischmeister, C.; Bruneau, C. Dalton Trans.
2012, 41, 3695. (c) Szadkowska, A.; Gstrein, X.; Burtscher, D.;
Jarzembska, K.; Wozniak, K.; Slugovc, C.; Grela, K. Organometallics
2010, 29, 117. (d) Leitgeb, A.; Abbas, M.; Fischer, C. R.; Poater, A.;
Cavallo, L.; Slugovc, C. Catal. Sci. Technol. 2012, 2, 1640. (e) Rouen,
2005, 2727. (e) Halbach, T. S.; Mix, S.; Fischer, D.; Maechling, S.;
Krause, J. O.; Sievers, C.; Blechert, S.; Nuyken, O.; Buchmeiser, M. R.
J. Org. Chem. 2005, 70, 4687. (f) Mingotaud, A.-F.; Kramer, M.;
̈
Mingotaud, C. J. Mol. Catal. A 2007, 263, 39. (g) Conrad, J. C.;
Parnas, H. H.; Snelgrove, J. L.; Fogg, D. E. J. Am. Chem. Soc. 2005, 127,
11882. (h) Monfette, S.; Camm, K. D.; Gorelsky, S. I.; Fogg, D. E.
Organometallics 2009, 28, 944.
M.; Queval, P.; Falivene, L.; Allard, J.; Toupet, L.; Crev
́
isy, C.; Caijo,
́
(17) (a) Fustero, S.; Simon-Fuentes, A.; Barrio, P.; Haufe, G. Chem.
Rev. 2014, DOI: 10.1021/cr500182a. (b) Siano, V.; d’Auria, I.; Grisi,
F.; Costabile, C.; Longo, P. Cent. Eur. J. Chem. 2011, 9, 605.
F.; Basle,
́
O.; Cavallo, L.; Mauduit, M. Chem.Eur. J. 2014, 20, 13716.
(18) Furstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann,
̈
C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem.Eur. J. 2001, 7,
3236.
(19) (a) Ritter, T.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc.
2006, 128, 11768. (b) Anderson, D. R.; O’Leary, D. J.; Grubbs, R. H.
Chem.Eur. J. 2008, 14, 7536.
(20) (a) Berlin, J. M.; Campbell, K.; Ritter, T.; Funk, T. W.; Chlenov,
A.; Grubbs, R. H. Org. Lett. 2007, 9, 1339. (b) Vougioukalakis, G. C.;
Grubbs, R. H. Organometallics 2007, 26, 2469. (c) Vougioukalakis, G.
C.; Grubbs, R. H. Chem.Eur. J. 2008, 14, 7545.
I
DOI: 10.1021/om501077w
Organometallics XXXX, XXX, XXX−XXX