Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

Article abstract of DOI:10.1039/d0dt04090h

Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)₈Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80-100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)₈Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.

Full text of DOI:10.1039/d0dt04090h

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DOI: 10.1039/D0DT04090H
ARTICLE
Selective carbene transfer to amines and olefins catalyzed by
ruthenium phthalocyanine complexes with donor substituents
Received 00th January
20xx,
Lucie P. Cailler,a Andrey P. Kroitor,b Alexander G. Martynov,*b Yulia G. Gorbunova,*b,c and Alexander
B. Sorokin*a
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate
(EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first
time. It was revealed that ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient
catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically
80-100 %) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst
shows a rare efficiency in the carbene insertion to amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine
concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-
substituted glycine derivatives with up to quantitative yields and turnover numbers achieving 2000. High selectivity, large
substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient
catalysts for the carbene insertion to amines.
to 98 % e.e., 35000 turnovers and 2550 h-1 turnover frequency11
and perform site-selective functionalization of C(sp3)-H bonds.12
Myoglobin reconstructed with ruthenium mesoporphyrin IX
Introduction
In recent years, catalytic carbene transfer reactions have
emerged as powerful synthetic approach in organic chemistry.1
Due to high versatility of this synthetic strategy involving metal
carbene complexes, a large range of elaborated compounds can
be prepared via cyclopropanation of olefins and carbene
insertion into C-H, N-H, O-H and other bonds. Among different
transition metal complexes, the porphyrin complexes of iron,2
iridium,3 ruthenium,4 osmium,5 rhodium6 and cobalt7 exhibit
particularly interesting catalytic properties in these reactions.8
Since a seminal work by Arnold and co-workers on the efficient
application of engineered cytochrome P-450 for the
cyclopropanation of olefins,9 extremely efficient and versatile
bio-catalysts for cyclopropanation and carbene insertion into N-
H, C-H, S-H, Si-H and B-H bonds have been developed by a direct
evolution of several hemoproteins bearing iron porphyrin active
site.10 Alternative approach to artificial metalloenzymes which
are highly efficient in carbene transfer reactions was proposed
by Hartwig and co-workers.11,12 Reconstituted cytochrome P-
450 enzyme CYP119 containing an iridium porphyrin in place of
iron site catalyzed insertion of carbenes into C-H bonds with up
catalyzed cyclopropanation of vinyl anisole and aniline N-H
insertion with 350 and 520 turnover numbers, respectively.13 All
these examples demonstrate that efficient catalysts for carbene
transfer reactions can be achieved by the appropriate variation
of the transition metal and supporting ligands. In quest for new
carbene transfer catalysts, the reactivity of several complexes
supported by non-heme ligands has been evaluated.14 It should
be noted that related porphyrinoid complexes such as
corroles,15 phthalocyanines,16 porphyrazines17 have been still
under-investigated in carbene transfer reactions as compared
to porphyrin complexes despite their promising catalytic
properties in these reactions. For instance, Aviv and Gross
showed superior catalytic activity of iron corroles in the large-
scope carbene insertion to the amine N-H bonds under practical
reaction conditions (0.1 mol% catalyst loading, single addition
of reagents under air) with high product yields within short
reaction time. This high catalytic efficiency of iron corroles
suggests that other over-looked porphyrin-like complexes
deserve a more careful evaluation in the carbene transfer
reactions.
In our ongoing project on the investigation of the catalytic
properties of phthalocyanine complexes in cyclopropanation
and carbene insertion into X-H bonds,18 we decided to evaluate
ruthenium phthalocyanine complexes for following reasons.
First, their ruthenium porphyrin counterparts have been shown
to catalyze cyclopropanation of olefins with high turnover
frequencies via the formation of metal carbene complexes using
diazo compounds as carbene precursors.4 Their reactivity was
influenced by the nature of the porphyrin substituents and by
the presence and nature of axial ligand(s).4a Metal carbene
intermediates can react either with olefins to form cyclopropyl
derivatives or with diazo precursors, e.g., with ethyl
a. Univ. Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON,
2 av. A. Einstein, 69626 Villeurbanne, France
E-mail: alexander.sorokin@ircelyon.univ-lyon1.fr
b. A. N. Frumkin Institute of Physical Chemistry and Electrochemistry,
Russian Academy of Sciences,
Leniskii pr., 31, bldg.. 4, 119071 Moscow, Russia
c. E-mail: martynov.alexandre@gmail.com
d. N. S. Kurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences,
Leniskii pr., 31, 11991 Moscow, Russia
E-mail: yulia@igic.ras.ru
Electronic Supplementary Information (ESI) available: [Experimental details for
catalytic reactions, characterization of catalysts and products]. See
DOI: 10.1039/x0xx00000x
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diazoacetate (EDA) to generate diethyl maleate (DEM) and insertion to aromatic and aliphatic amines.18b At 0.1 mol%
View Article Online
diethyl fumarate (DEF). To limit the formation of these side EDA catalyst loading and 1.2:1 EDA/substratDeOrIa: t1i0o.10th39e/sDe0DreTa0c4t0i9o0nHs
dimerization products occurring with most of metal complexes, occurred with turnover numbers of 680-1000 and 580-1000,
the reactions are often performed using an excess of substrate. respectively, at 90°C. Hence, it would be of interest to probe
Although in the presence of limiting amount of EDA a higher reactivity of the mononuclear counterpart. Herein, we report
selectivity in carbene insertion product can be achieved, the the evaluation of three mononuclear ruthenium
yields based on substrate can be very low when using the phthalocyanine complexes (Figure 1) in cyclopropanation of a
substrate/carbene precursor ratio of 2:1,4a,4d 5:1,14a,19,20 large range of styrene derivatives and aliphatic olefins as well as
10:12a,15c or even 20:1.2c The reaction selectivity can be also carbene insertion into N-H bonds of aromatic, aliphatic and
improved using slow addition of diazo compound to the heterocyclic amines.
reaction mixture by syringe pump.
OBu
Compared to cyclopropanation reactions, the N-H carbene
tBu
BuO
CO
N
CO
N
OBu
OBu
tBu
insertion to amines catalyzed by ruthenium complexes have
been less investigated.21,22 Simonneaux et al. reported the
activity of (TMP)Ru(CO) (TMP = tetramesitylporphyrin) in
intermolecular carbene N-H insertion to aryl and alkylamines
with 63-81% yields based on EDA. Because of strong
coordination of ruthenium center with amines, a mixture of EDA
and amine in 1:1.5 ratio was slowly added over 2.5 h to catalyst
solution and up to 18 h were necessary to complete reactions.21
Che and co-workers published the carbene insertion into N-H
bonds of primary arylamines in aqueous media with water
soluble glycosylated ruthenium porphyrin.22 Using a 1:2
EDA/amine ratio with 1 mol% catalyst loading allowed avoiding
complex poisoning and 76-91 % yields of -aminoacid
derivatives were obtained after 10 h. This protocol was
successfully applied to alkylate the N-terminus of peptides and
to mediate N-terminal modification of proteins.22
N
N
N
N
N
N
N
Ru
N
Ru
N
N
N
N
BuO
BuO
N
N
tBu
OBu
tBu
OBu
[(tBu)4Pc]Ru(CO)
[(BuO)8Pc]Ru(CO)
OMes
CO
MesO
OMes
OMes
N
N
N
N
N
Ru
N
N
MesO
MesO
N
O
OMes
Mes
[(MesO)8Pc]Ru(CO)
Figure 1. Structures of complexes evaluated in carbene transfer reactions.
Results and Discussion
Cyclopropanation of olefins
Three carbonyl ruthenium phthalocyanine complexes with
different substitution patterns were prepared and
characterized as previously described (Figure 1).18b,26 Their
activity was initially evaluated in the cyclopropanation of
styrene by EDA (Table 1). To favor cyclopropanation reaction
over competing dimerization of EDA to diethyl fumarate and
diethyl maleate, one eq. of EDA was added to a 1 M styrene
solution containing 1 mM catalyst during 2 h under argon at 25
°C. Among the three complexes, [(BuO)8Pc]Ru(CO) was found to
provide a higher yield of cyclopropanation product and limited
amount of side products owing to EDA dimerization. Thus, the
[(BuO)8Pc]Ru(CO) complex has been further studied to evaluate
a scope of olefin cyclopropanation using 1.2 eq. of EDA as
carbene precursor. The reaction was successfully extended to
styrene derivatives bearing electron-donating or electron-
Along with ruthenium porphyrins, a large range of different
ruthenium complexes were shown to be effective
cyclopropanation catalysts in combination with diazo
compounds.23 While mononuclear ruthenium phthalocyanines
(RuPc) have been mainly used as oxidation catalysis,24a their
evaluation in carbene transfer reactions has been limited by
only one study of cyclopropanation of olefins.16a Among a range
of metal phthalocyanine complexes studied in cyclopropanation
of styrene, RuIIPcF16 (PcF16 = hexadecafluorophthalocyanine)
showed the highest product yields achieving 80 % with
catalyst:styrene:EDA ratio of 1:500:750 after 4 h at 25°C upon
slow EDA addition over 2 h. Cyclopropanation of seven styrene
derivatives resulted in lower products yields with 3.2:1 - 5.8:1
trans/cis ratios. Two examples of intramolecular
cyclopropanation of diazo compounds bearing aromatic and
aliphatic olefin fragments were also provided. Noteworthy, the
[RuIIIPc]Cl complex was less efficient in styrene
cyclopropanation to afford a 59 % product yield with a 1.9:1
trans/cis selectivity.16a This study suggests that the catalytic
efficiency depends on the properties of the phthalocyanine
ligand, in particular, on the nature of substituents determining
its electronic properties.25 While metal phthalocyanine
complexes are prominent catalysts for many reactions,24 their
applications in catalytic carbene transfer reactions are
surprisingly scarse.16,18 Motivated by remarkable catalytic
properties of single-atom bridged binuclear phthalocyanine
complexes,24b-24e we have recently studied µ-carbido
diruthenium phthalocyanine complex in combination with EDA
in cyclopropanation of aromatic olefins and in carbene
Table 1. Cyclopropanation of styrene by EDA catalyzed by ruthenium
phthalocyanines. a
Side process of catalytic
EDA dimerization
CO2Et
EtO2C
Catalyst
N2
OEt
+
+
H
CO2Et
trans
CO2Et
cis
Ph
Ph
O
1 mM, 0.1 mol%
CH2Cl2, 25°C, Ar
1 M
1.2 eq.
slow addition
2 | J. Name., 2012, 00, 1-3
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ARTICLE
Only very electron-deficient pentafluorostyrene afforded a
moderate cyclopropanation yield of 44 % (Table 2, entry 5). The
Cyclopropanation
yield,
%
View Article Online
DOI: 10.1039/D0DT04090H
EDA dimerization
Entry
Catalyst
trans/cis yield, mmol (%) c
b
cyclopropanation reaction is sensitive to steric factor. The
presence of the ortho methyl substituents in 2,4,6-
trimethylstyrene led to a 70 % product yield (Table 2, entry 10).
Methyl group of trans--methylstyrene strongly influenced on
the selectivity to provide only trans isomer but the yield
dropped to 32 % (Table 2, entry 11). On the other hand, the
presence of methyl or phenyl group in the -position of styrene
vinyl group does not hinder the reactivity and results in the
product yields of 85 and 100 %, respectively (Table 2, entries
12,13). These results are in line with a late transition state
typical of ruthenium complexes supported by electron-rich
1
2
3
[(MesO)8Pc]Ru(CO)
[(tBu)4Pc]Ru(CO) d
[(BuO)8Pc]Ru(CO)
38
76
82
5.2:1
5.3:1
4.9:1
0.014 (7)
0.058 (24)
0.020 (10)
a Conditions: styrene (0.4 mmol), catalyst (0.1 mol%), EDA (slow addition of
0.4 mmol as a 2 M solution in CH2Cl2, 0.10 mL/h, addition time – 2 h), CH2Cl2
(0.4 mL), argon, 25°C, 2.5 h. b Yields determined by 1H NMR are based on
styrene. c Yields of DEM and DEF were determined by 1H NMR (EDA amount
consumed for dimerization, %). d 0.48 mmol of EDA.
withdrawing substituents. A large range of olefins was typically
converted to corresponding cyclopropyl derivatives with 83-100
% yields (Table 2).
macrocycles. Indeed,
a trans/cis ratio observed with
[(BuO)8Pc]Ru(CO) (4.9:1 - 7.3:1) is in general higher than that
obtained with the electron-poor [RuPcF16] (3.2:1 - 5.8:1).16a For
instance, cyclopropanation of aniline and p-methoxyaniline by
[(BuO)8Pc]Ru(CO) and [RuPcF16] proceeds with trans/cis ratios
of 4.8/3.2 and 7.3/4.8, respectively. Interestingly, styrenes
Table 2. Substrate scope for the cyclopropanation of styrene derivatives by EDA
a
catalyzed by [(BuO)8Pc]Ru(CO)
.
Side process of catalytic
EDA dimerization
CO2Et
CO2Et
EtO2C
bering
electron
donating
substituents
undergo
R2
R2
[(OBu)8Pc]Ru(CO)
N2
R1
cyclopropanation with a higher trans:cis ratio. This trend is
opposite to that previously published in case of ruthenium
porphyrins.4d
OEt
+
R1
Ar
R1
Ar
R2
H
CO2Et
cis
Ar
+
O
1 mM, 0.1 mol%
CH2Cl2, 25°C, Ar
1 M
1.2 eq.
trans
slow addition
Aliphatic olefins having neighboring -donating
heteroatoms or double bonds are also amenable to
cyclopropanation (Table 3).
EDA
Cyclopropanation
dimerization
yield, mmol
(%) c
Entry
Substrate
yield, % b trans/cis
Table 3. Cyclopropanation of aliphatic olefins by EDA catalyzed by
(BuO)8Pc]Ru(CO). a
1
2
3
4
5
6
89
99
4.8:1
4:1
0.029 (12)
0.038 (16)
0.058 (24)
0.036 (15)
0.080 (33)
0.029 (12)
[
Cyclopropanation
EDA
F
dimerization
yield, mmol
(%) c
Entry
Substrate
yield, % b
trans/cis
90
4.9:1
4.9:1
3.0:1
7.3:1
Cl
86
O
1
2
86
2.4:1
4:1
0.014 (6)
AcO
F5
78, 7 d
0.048 (20)
0.178 (74)
44
53:30:15:1 e
100
3
26
2.1:1
MeO
tBu
4
5
4 f, 2 g
0
_
-
0.228 (95)
7
8
9
96
83
88
6.1:1
4.9:1
7.3:1
0.017 (7)
0.046 (19)
0.048 (20)
0.240 (100)
a Conditions: olefin (0.4 mmol), catalyst (0.1 mol%), EDA (slow addition of
0.48 mmol as a 2 M solution in CH2Cl2, 0.10 mL/h, addition time – 2 h), CH2Cl2
(0.4 mL), argon, 25°C, 2.5 h. b Yields determined by 1H NMR are based on
10
11
12
70
32
85
1.6:1
100:0
3.0:1
0. 067 (28)
0.080 (33)
0.029 (12)
1
olefin. c Yields of DEM and DEF were determined by H NMR (EDA amount
consumed for dimerization, %). d Dicyclopropanated product. e Ratio of
stereoisomers of dicyclopropanated product determines by GC-MS.
f Cyclopropanation product. g Allylic C-H insertion product.
n-Butylvinylether afforded a 86 % yield of cyclopropanation
product (Table 3, entry 1). Diene with conjugated double bonds,
2,3-dimethyl-1,3-butadiene, furnished both mono- and di-
cyclopropanation products with 78 and 7 % yields, respectively
(Table 3, entry 2). The cyclopropanation of allylbenzene
resulted in a 26 % yield (Table 3, entry 3). Thus, the presence of
aryl, vinyl or ether groups adjacent to the double bond favors
its cyclopropanation due to stabilization of the partial positive
charge developed in the late transition state at the -carbon
13
100
-
0.038 (16)
a Conditions: olefin (0.4 mmol), catalyst (0.1 mol%), EDA (slow addition of
0.48 mmol as a 2 M solution in CH2Cl2, 0.10 mL/h, addition time – 2 h), CH2Cl2
(0.4 mL), argon, 25°C, 2.5 h. b Yields determined by 1H NMR are based on
olefin. c Yields of DEM and DEF were determined by H NMR (EDA amount
consumed for dimerization, %).
1
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J. Name., 2013, 00, 1-3 | 3
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atom of the olefin.[2a] Cyclopropanation of internal and
branched olefins was inefficient most likely owing to a hindered
approach of the double bond to the active carbene complex.
Cyclohexene was cyclopropanated with only 4 % yield whereas
2,3-dimethyl-2-butene did not react at all (Table 3, entries 4,5).
The carbene insertion to the allylic C-H bond of cyclohexene
occurred with a 2 % yield. In case of less reactive olefins, the
products of EDA dimerization were formed with high yields. The
aliphatic olefins exhibit in general a lower trans selectivity of
cyclopropanation compared with styrene derivatives most
probably due to the higher flexibility.
The scope of diazo compounds was also evaluated (Table 4).
Butyl diazoacetate (BDA), ethyl diazophenylacetate (EDPA) and
trimethylsilyl diazomethane (TMSD) were tested as carbene
precursors in combination with [(BuO)8Pc]Ru(CO) for
cyclopropanation of styrene.
Table 5. Reaction of EDA with aniline catalyzed by [(BuO)8Pc]Ru(CO). a
View Article Online
DOI: 10.1039/D0DT04090H
Side process of catalytic
EDA dimerization
CO2Et
(traces)
EtO2C
N2
CO2Et
H
CO2Et
N CO2Et
OEt
[(BuO)8Pc]Ru(CO)
H
N
O
+
+
0.5 mM (0.05 mol%)
CH2Cl2, 25°C, Ar
Product of single
Product of double
NH-insertion
(traces)
NH2
NH-insertion
(yield - 96%)
N-H insertion,
yield (%) b
Catalyst
EDA
Entry
Solvent
loading,
mol%
0.1
0.05
0.05
0.05
0.01
0.05
0.05
dimerization
yield, %c
single
94
89
double
0
0
1
2
3 d
4 e
5 f
6
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH3CN
PhCH3
0.1
0.1
0.1
0.6
0
96
2
96
4
12
66
0.6
4
5
0
Table 4. Cyclopropanation of styrene by different diazo carbene precursors catalyzed by
[(BuO)8Pc]Ru(CO). a
7
42
0.1
a Conditions: aniline (0.5 mmol), catalyst (0.05-0.1 mol%), CH2Cl2 (0.5 mL), EDA (0.5
mmol), argon, 40°C, 1 h. b Yields determined by 1H NMR are based on aniline.
c Yields of DEM and DEF determined by 1H NMR are based on the starting EDA.
d 0.55 mmol EDA. e 1.1 mmol of EDA was added. f reaction time was 4h.
N2
N2
N2
N2
SiMe3
OEt
OBu
OEt
H
H
Ph
H
O
O
O
EDA
BDA
EDPA
TMSD
Cyclopropanation
Entry
Diazo precursor
T, °C
At a 1:1 aniline : EDA ratio, the reaction was completed
within 1h at 40°C. Importantly, the dimerization of EDA did not
compete with N-H insertion and further reactions were carried
out in a one-pot fashion without the need for slow EDA
addition. Among the solvents tested, CH2Cl2 provided higher
yield and selectivity to mono-insertion product whereas CH3CN
and PhCH3 were less efficient (Table 5).
yield, % b
trans:cis ratio
4.8:1
1
2
3
4
5
EDA
BDAc,d
EDPA
TMSDc,e
TMSDf
25
35
25
35
70
89
53
1.9:1
traces
traces
69
n.d.
n.d.
1.6:1
a Conditions: styrene (0.4 mmol), catalyst (0.1 mol%), 0.48 mmol of diazo
compound was slowly added to reaction mixture as a 2 M solution in CH2Cl2, 0.10
Noteworthy, the catalyst loading can be reduced from 0.1 to
mL/h, addition time – 2 h), CH2Cl2 (0.4 mL), argon, 25°C, 2.5 h. b Yields determined 0.05 mol% without notable decrease of the product yield, from
by 1H NMR are based on olefin. c The reaction was set at 25°C for 2h and then
94 to 89 %, respectively (Table 5, entries 1,2). Using of 1.1 eq.
EDA restored a high catalytic efficiency and the yield of N-
phenyl glycine ester achieved 96 % corresponding to turnover
heated at 35°C overnight. d A 15 % BDA solution in toluene was added over 2h at
0.163 mL/h rate. e A 2 M TMSD solution in hexane was added. f Overnight.
number (TON) of 1920. Further decrease of the catalyst amount
The reaction tolerates the presence of bulky group at ester
to 0.01 mol% resulted in sharp drop of the yield to only 12 %
moiety. Butyl diazoacetate provided a 53 % cyclopropanation
(TON=1200). Quite remarkably, [(BuO)8Pc]Ru(CO) shows
yield with a 66:34 trans/cis ratio (Table 4, entry 2). In contrast,
excellent selectivity toward the product of single N-H insertion
the presence of bulky phenyl group in ethyl diazophenylacetate
and
only trace amount of double insertion product
prevented the efficient cyclopropanation of styrene.
Trimethylsilyl diazomethane was not efficient at 35°C because
of its electron-rich nature which makes a substrate nucleophilic
attack at carbene species difficult. However, when the reaction
was carried out at 70°C, corresponding cyclopropanation
products were obtained with 69 % yield (Table 4, entry 5). Thus,
among the diazo compounds tested, readily available EDA
showed the most promising results in cyclopropanation of
olefins and has been further evaluated in combination with
[(BuO)8Pc]Ru(CO) in the reaction with amines.
PhN(CH2COOEt)2 was detected (Table 5, entries 1-2). Even in
the presence of 2 eq. EDA, a 96 % yield of PhNHCH2COOEt was
obtained along with only 4 % of the double insertion product
(Table 5, entry 4). Dichloromethane solvent provided much
better results with respect to CH3CN and PhCH3 (Table 5, entries
6,7). Compared to cyclopropanation of olefins, a slow addition
of EDA was not necessary because of the high selectivity to
single N-H insertion and almost quantitative product yield was
obtained using 0.05 mol% catalyst loading. Therefore, we have
further explored
a substrate scope using 0.05 mol%
[(BuO)8Pc]Ru(CO) in CH2Cl2 and 1.1 eq. EDA added in one
portion at 40 °C.
A wide range of aromatic, heterocyclic and aliphatic amines
was selectively transformed to substituted glycine derivatives
RNHCH2COOEt with R = aryl, heterocycle or alkyl group (Table
6).
Carbene insertion to N-H bonds of amines
Under reaction conditions used for cyclopropanation of olefins
(1 M substrate, 0.1 mol% catalyst loading, 25°C), the reaction of
EDA with aniline was slow. Thus, the reaction conditions for
carbene N-H insertion were initially optimized using aniline as a
reference substrate (Table 5).
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View Article Online
DOI: 10.1039/D0DT04090H
Table 6. Carbene N-H insertion to aromatic, heterocyclic and aliphatic amines mediated by [(BuO)8Pc]Ru(CO) – EDA system. a
Side process of catalytic
EDA dimerization
CO2Et
(traces)
EtO2C
N2
OEt
CO2Et
CO2Et
CO2Et
H
R1 N
R2
R1 N
[(BuO)8Pc]Ru(CO)
O
+
+
0.5 mM (0.05 mol%)
CH2Cl2, 25°C, Ar
Product of double
R2
H
Product of single
NH-insertion
N
NH-insertion (R2 = H)
R1
N-H insertion yields, % b
TON c
EDA dimerization
Entry
1
Substrate
NH2
Reaction time
1h
yield, % d
single
double
96
2
2000
2060
2300
2020
0.1
NH2
2
3
4
90
90
95
4
10
3
2h
1h
1h
0
0
MeO
NH2
NH2
NH2
0.2
Cl
F
5
6
95
93
3
2
2020
1940
1h
0
0
NH2
70 min
F
CF3
NH2
7
91
3
1940
70 min
1
CF3
NH2
8
9
77
92
<1
8
1560
2160
105 min
10 min
9
F5
NH2
0.5
iPr
NH2
10
>99
traces
2000
10 min
0.6
iPr
NH2
11
12
>99
90
traces
4
2000
2000
30 min
25 min
0
tBu
NH2
0.3
H
N
13
44
-
880
30 min
0.5
NH2
14
15
16
17
56
43
23
23
0
0
1120
860
4h
2h
0
0
0
0
N
N
NH2
NH2
NH2
S
e
f
N N
S
10
23
860
2h
N N
S
1380
20h
f
H
N
18
19
77
30
-
-
1540
600
20 min
4h
21
0
O
NH
g
20
21
17 h
5 i
540
20h
18
0
NH
NH2
56 (5)
27 (0.5)
2200
20h (2h)
a Conditions: 0.5 mmol amine, 0.55 mmol EDA, 0.05 mol% catalyst, 0.5 mL CH2Cl2, argon, 40°C. b Yields determined by 1H NMR are based on amine. c Total TON is defined
as (mmol of single insertion product + 2 x mmol of double insertion product) / mmol of catalyst. d Yields of DEM and DEF determined by 1H NMR are based on the starting
EDA. e unidentified product was additionally obtained with 9 % yield. f reaction mixture was diluted by factor 2. g A mixture of morpholine (1 eq.) and EDA (1.1 eq.) was
slowly added to catalyst solution. h Product of α-C-H insertion, isolated yield. I Product of double 2,5-C-H insertion, isolated yield.
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/D0DT04090H
Aniline derivatives bearing electron-donating and electron- catalysts27-29 and iron porphyrin complex.30 A recent detailed
withdrawing groups afforded excellent yields of corresponding study by Pérez and co-workers showed that copper
glycine derivatives, between 77 and 100 % (Table 6, entries 1- hydrotrispyrazolylborate complex (1 mol% catalyst loading)
12). In particular, anilines with electron-donor substituents in catalyzed C-H functionalization of pyrroles by EDA using a 5:1
ortho position(s) provided quantitative product yields within substrate/EDA ratio.27 Under reaction conditions used for the
short reaction time of 10-30 min (Table 6, entries 10, 11) with reaction with amines (0.05 mol% [(BuO)8Pc]Ru(CO) loading, 1.1
turnover frequency (TOF) up to 200 cycles per minute. Even eq. EDA), pyrrole afforded two products after 20 h with m/z
very electron- deficient pentafluoroaniline offered a yield of 77 values corresponding to single (m/z=153) and double (m/z=239)
% (Table 6, entry 8). To the best of our knowledge, this is the insertion of carbene into pyrrole (Table 6, entry 20). These
highest yield of carbene N-H insertion to such a difficult compounds were isolated by column chromatography with 17
substrate. Noteworthy, p-aminostryrene, possessing both and 5 % yields, respectively, and were identified as ethyl
olefin and amino group as reactive sites, reacted selectively on pyrrole-2-acetate and diethyl pyrrole-2,5-diacetate on the basis
its amino site (Table 6, entry 12). Secondary N-methylaniline of their 1H and 13C NMR spectra.27-29 (Scheme 1).
was also amenable to N-H insertion though with a lower yield
CO2Et
CO2Et
of 44 % (Table 6, entry 13).
N2
[(BuO)8Pc]Ru(CO)
CO2Et
CO2Et
18 %
OEt
+
+
+
H
NH
1 M
NH
17 %
NH
We next evaluated the reactivity of [(BuO)8Pc]Ru(CO)
toward heteroaromatic amines. Amino-substituted pyridine,
thiazoline and thiadiazole derivatives provided moderate
product yields (23-56 %) and EDA was not completely consumed
(Table 6, entries 14-17). No EDA dimerization was observed
even if the reaction was allowed to run for a longer time.
Because of the strong coordination with metal complexes
which inhibits catalytic site, in particular, when high
amine/catalyst ratio is used, aliphatic amines are often
considered as difficult substrates. Indeed, the reaction with
cyclopropylamine was very slow providing only 5 % yield after 2
h. Nevertheless, the cyclopropylamine was converted to mono-
and double N-H insertion products with 56 and 27 % yields,
respectively, after 20h (Table 6, entry 21). Under standard
conditions, conversions of 2-methoxyethylamine and
morpholine were very low even after 20h (12% yield of
morpholine derivative). However, slow addition of the mixture
of EDA and morpholine to the catalyst solution during 4 h
O
0.5 mM (0.05 mol%)
CH2Cl2, 40°C, Ar
1 pot, 0.5 mL scale
20 h
CO2Et
5 %
1.1 M
Scheme 1. Reaction of pyrrole with EDA catalyzed by [(BuO)8Pc]Ru(CO).
Thus, [(BuO)8Pc]Ru(CO) mediates the selective insertion of
carbene derived from EDA into C-H bond of pyrrole. Although
such a reactivity has been previously described,27,28,30 to our
knowledge, a double C-H carbene insertion to pyrrole has not
been reported.
Finally, to further confirm the practical character of this
catalytic system, a gram scale reaction was carried out with 6
mmol of aniline and 6 mmol of EDA in the presence of 0.05
mol% [(BuO)8Pc]Ru(CO). N-Phenylglycine ethyl ester was
obtained with 89 % isolated yield (0.95 g).
allowed obtaining the glycine ester bearing morpholine group Conclusion
with 30 yield (Table 6, entry 19). By contrast,
a
%
This study represents the first detailed investigation of the
catalytic properties of electron-rich ruthenium phthalocyanines
in carbene transfer reactions. First, three complexes were
evaluated in the cyclopropanation of styrene. The most
electron-rich and the less hindered [(BuO)8Pc]Ru(CO) was the
most efficient providing a 89 % cyclopropanation yield using 1.2
eq. EDA with respect to olefin and 0.1 mol% catalyst loading at
25°C. The reaction scope was extended to aromatic olefins
diisopropylamine afforded a 77 % yield of N-H insertion within
20 min, most probably because of less strong coordination of
this hindered amine to the metal center (Table 6, entry 18).
Noteworthy, in this case the EDA dimerization byproducts were
formed in 21 % yield. This is the only example of the notable
side carbene dimerization performed by the [(BuO)8Pc]Ru(CO)
– EDA system in the reaction with amines.
This observation shows that the properties of amine and its
coordination to ruthenium center can play an important role in
the outcome of the reaction. The amine nature may have
impact on its coordination behavior toward the metal center
and on its ability to attack the electrophilic metal-carbene
intermediate thus influencing on the reaction selectivity for N-
H insertion vs carbene dimerization.
bearing
electron-donating
or
electron-withdrawing
substituents and to aliphatic olefins with conjugated double
bonds or donating heteroatom. Using low catalyst loading
and close to equimolecular substrate/EDA ratio, high
cyclopropanation yields (typically 80-100 %) and high TON (up
to 1000) have been achieved.
The [(BuO)8Pc]Ru(CO) complex is a particularly efficient
catalyst for the carbene insertion to amine N-H bonds. The
reaction can be carried out under practical conditions: (i) a very
low catalyst loading (0.05 mol%); (ii) high starting amine
concentration (1 M); (iii) 1.1 EDA eq. with respect to substrate
and (iv) EDA can be added in one portion without need of slow
The reaction with pyrrole represents a particular case
because of several possible reaction sites. The carbene group
can be inserted to N-H, C-H or C-H or cyclopropanate the
double bond. In contrast to N-protected pyrroles,
functionalization of 1H-pyrroles by metal-catalyzed carbene
transfer have been rarely described involving copper based
6 | J. Name., 2012, 00, 1-3
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addition by syringe pump. In contrast to many published
catalysts, [(BuO)8Pc]Ru(CO) efficiently mediates the carbene Carbene N-H insertion of amines
insertion to amine under very high amine/catalyst ratio of
View Article Online
DOI: 10.1039/D0DT04090H
EDA (91 µL, 0.5 mmol, 1,1 eq.) was added to a solution of amine
(1 M, 0.5 mmol, 1 eq.) and [(BuO)8Pc]Ru(CO) (0.5 mM, 2.5.10-4
mmol, 0.05 mol%) in 0.5 mL of dichloromethane under argon
atmosphere at 40°C. The reaction mixture was magnetically
stirred for 10 min-20 h at 40°C. Reaction products were
2000:1 showing no inactivation of the catalysts by strong amine
coordination. A variety of aromatic, heterocyclic and aliphatic
amines were selectively converted to substituted glycine
derivatives with up to quantitative yields and turnover numbers
achieving 2000. Of particular importance is the high selectivity
of [(BuO)8Pc]Ru(CO) to single N-H insertion even in the presence
of 2-fold excess of EDA. In the previous study, µ-carbido dimeric
complex on the same ruthenium octabutylpthalocyanine
platform could efficiently catalyzed N-H amine insertion and
cyclopropanation of olefins by EDA only at 90°C. In addition, a
mixture of single and double N-H insertion was obtained.
Interestingly, [(BuO)8Pc]Ru(CO) carried out cyclopropanation of
aniline and p-methoxyaniline with higher trans/cis ratios of 4.8
and 7.3 compared with its µ-carbido dimeric counterpart (2.3
and 3.0, respectively). Thus, [(BuO)8Pc]Ru(CO) exhibits a higher
reactivity and selectivity in these carbene transfer reactions
compared to its µ-carbido binuclear congener providing an
access to a wide scope of cyclopropane and glycine derivatives
under practical reaction conditions.
1
analyzed by H NMR (CDCl3) using CH2Br2 as internal standard
and by GC-MS (See Supplementary Information). The products
of several reactions were purified and isolated using PuriFlash
XS 420 system (Interchim) at PF-15SIHP flash columns
(cyclohexane/ethyl acetate).
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by Agence Nationale de Recherches,
France (grant ANR-16-CE29-0018-01). AGM is grateful to the
French Embassy in Moscow for financial support. LPG is
indebted to Ministère de L’Education Nationale, de
l’Enseignement Supérieur et de la Recherche, France for the
PhD fellowship. Synthesis of catalysts was supported by the
Ministry of Science and Higher Education of the Russian
Federation, analytical mesurements were partially performed
using equipment of CKP FMI IPCE RAS.
Experimental Section
Ruthenium phthalocyanine complexes were prepared as
previously described18b,26. Ethyl diazoacetatate containing ~ 13
wt% of dichloromethane was purchased from Sigma-Aldrich.
Olefins and amines were obtained from Alfa Aesar or Sigma-
Aldrich and were used as received.
Notes and references
The UV-vis spectra of ruthenium phthalocyanine solutions
were
recorded
with
Agilent
8453
diode-array
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Cyclopropanation of olefins
All olefins were filtered through basic alumina and silica before
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30 L. K. Baumann, H. M. Mbuvi, G. Du and L. K. Woo,
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DOI: 10.1039/D0DT04090H
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DOI: 10.1039/D0DT04090H
R'
H(R)
+
N H
(R)H
R'
N
CO2Et
NH-insertion
N2
CO2Et
BuO
BuO
OBu
CO
N
OBu
N
N
N
N
Ru
0.05-0.1 mol.%
of the catalyst
OBu
N
N
N
BuO
BuO
OBu
Cyclo-
propanation
+
CO2Et
N2
R
R
CO2Et
Ruthenium phthalocyanine complex efficiently catalyzes cyclopropanation of olefins (15 substrates) and single carbene
insertion to N-H bonds of aromatic, heteroaromatic and aliphatic amines (20 substrates) with high selectivity and
practical reaction conditions.