Non-peripherally substituted metallophthalocyanines catalyzed diastereoselective carbonyl-ylide reactions: Synthesis and DFT calculations

Article abstract of DOI:10.1016/j.tet.2020.131892

Many catalysts are used to control the chemo-selectivity, diastereoselectivity, and enantioselectivity in carbenoid reactions. In this work, the [4 + 1] carbonyl-ylide reaction of dimethyl diazomalonate with α-ionone and the [3 + 2] carbonyl-ylide reaction of dimethyl diazomalonate with thiophene-2-carbaldehyde were chosen to obtain enriched diastereomeric products with the synthesized metallophthalocyanine compounds as catalysts. Four metallophthalocyanines (MPcs) including two neopenthoxy substituted and two novel fenchoxy substituted on non-peripheral positions of phthalocyanine ring were synthesized. Their catalytic activities were also compared with several common catalysts. Our results showed that in both reactions copper-Pc with neopentyl is the most effective catalyst to obtain diastereoselective results with diastereomeric product ratios of 30:70 and 10:90. DFT calculations also performed to explain the effect of the catalyst in diastereoselectivity. The calculations were in good agreement with the experimental results and assisted in understanding the selectivity.

Full text of DOI:10.1016/j.tet.2020.131892

Tetrahedron 80 (2021) 131892
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Non-peripherally substituted metallophthalocyanines catalyzed
diastereoselective carbonyl-ylide reactions: Synthesis and DFT
calculations
Fusun Seyma Gungor*, B. Sebnem Sesalan, Nurcan Senyurt Tuzun, Yilmaz Ozkilic,
Olcay Anac
Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry, 34469, Maslak, Istanbul, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Many catalysts are used to control the chemo-selectivity, diastereoselectivity, and enantioselectivity in
Received 8 October 2020
Received in revised form
15 December 2020
Accepted 16 December 2020
Available online 4 January 2021
carbenoid reactions. In this work, the [4 þ 1] carbonyl-ylide reaction of dimethyl diazomalonate with
a-
ionone and the [3 2] carbonyl-ylide reaction of dimethyl diazomalonate with thiophene-2-
þ
carbaldehyde were chosen to obtain enriched diastereomeric products with the synthesized metal-
lophthalocyanine compounds as catalysts. Four metallophthalocyanines (MPcs) including two neo-
penthoxy substituted and two novel fenchoxy substituted on non-peripheral positions of phthalocyanine
ring were synthesized. Their catalytic activities were also compared with several common catalysts. Our
results showed that in both reactions copper-Pc with neopentyl is the most effective catalyst to obtain
diastereoselective results with diastereomeric product ratios of 30:70 and 10:90. DFT calculations also
performed to explain the effect of the catalyst in diastereoselectivity. The calculations were in good
agreement with the experimental results and assisted in understanding the selectivity.
© 2020 Elsevier Ltd. All rights reserved.
Keywords:
Metallophthalocyanine
Cycloaddition
Carbene
Ylide
DFT
1. Introduction
functionalized 2,3-dihydrofurans successfully.
We also obtained dioxolanes from Cu(acac)2 catalyzed [3 þ 2]
Dihydrofurans and dioxolanes are important heterocycles in
natural product chemistry and many different synthetic pathways
have been reported for their synthesis [1]. While [4 þ 1] ring
closure of the carbonyl ylide formed by carbene reaction in catalytic
conditions is one of the synthetic approaches of dihydrofurans
[2e3], [3 þ 2] ring closure of the carbonyl ylide is a convenient way
of producing of dioxolanes [1i, 2d-e]. Among wide variety of these
catalytic reactions, transition metal-catalyzed methods are more
popular compared to others since they can be performed under
relatively mild conditions. Hence, these catalysts were successfully
applied in many reactions such as insertions, additions, ylide for-
mations and rearrangements [2a].
ring closure of the carbonyl ylide derived from thiophene-2-
carbaldehyde [2d].
In the last decade, phthalocyanines (Pcs) and metal-
lophthalocyanines (MPcs) have attracted great attention in carbene
transfer reactions particularly in cyclopropanation as transition
metal-catalysts [5]. Zhou et al. performed one of the first studies in
this area [5a] and reported the cyclopropanation reactions of sty-
rene derivatives and ethyl diazoacetate in the presence of modified
phthalocyanines. Moreover, the use of metallophthalocyanine as
heterogeneous catalyst for the cyclopropanation of olefins with
trimethylsilyldiazomethane was reported concomitantly [5b]. In
there report, silylcyclopropanes were obtained stereoselectively for
the first time. Later, Ventura et al. studied the reactions of olefins
and methylphenyldiazoacetate as donor-acceptor carbene source
with metallophthalocyanine catalyst [5c]. Moreover, the cyclo-
propanation of aromatic olefins and carbene insertion into the NeH
bonds of aromatic and aliphatic amines in the presences of Ru(ıv)
binuclear phthalocyanines were investigated [5d].
Accordingly, we studied the formal 1,5-electrocyclic reaction of
carbonyl ylides derived from a,b-unsaturated ketones, esters, di-
esters, and enaminones by using Cu(acac)2/Rh2(OAc)4 as catalysts
[2c, 4a-h]. In these reactions, we obtained dihydrofurans and multi-
Although some metallophthalocyanine catalyzed cyclo-
propanations were reported previously, [4 þ 1] and [3 þ 2]-ring
* Corresponding author.
E-mail address: gungorfus@itu.edu.tr (F.S. Gungor).
https://doi.org/10.1016/j.tet.2020.131892
0040-4020/© 2020 Elsevier Ltd. All rights reserved.

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
closures of the carbonyl ylide to obtain dihydrofurans and dioxo-
lanes have never been reported. In continuation to our works [2c-d,
4], we studied the activity of MPc as a catalyst in [4 þ 1] and [3 þ 2]
cycloaddition reactions via carbonyl-ylide intermediate by selected
two models of carbenoid reactions. For this purpose, copper- and
nickel-Pcs, substituted with non-peripherally fenchoxy as novel
MPcs and neopentoxy MPcs were synthesized according to a
modified procedure reported in the literature. In addition, DFT
calculations were performed to explain the structural effects that
led to diastereoselectivity in the model reactions.
2. Results and discussion
In this study, a-ionone (1) and dimethyl diazomalonate (2) were
reacted to obtain one diastereomeric product excessively in the
presence of a series of catalysts, which include MPcs (7e10)
(Scheme 1).
First of all, MPc complexes (7e10) were synthesized by the
cyclotetramerization of 3-fenchoxy-phthalonitrile (5) and 3-
neopentoxy-phthalonitrile (6) in the presence of metal salts
(Cu(acac)2 or Ni(OAc)2) in n-pentanol (Scheme 2). Catalyst 7 and 8
were obtained for the first time in this study. However, 1(4), 8(11),
15(18), 22(25)-tetrakis(3-neopentoxy) phthalo-cyaninato nick-
el(II)/copper (II) (9/10) were synthesized by Chen et al. in 2012 [6].
Having synthesized the MPc catalyts, our reported Cu(acac)2
Scheme 2. Synthesis of MPcs (7e10).
understand the catalytic effect of MPcs, Ni and Cu-Pc complexes
were used as catalysts in the same carbene transformation reaction.
When Ni-Pc was used as catalyst (entries 7, 8, 10 and 11), it was
slightly more efficient than the standard catalysts used (entries
1e6). Among the trials, entry 12 with 10 had the most satisfying
catalytic activity with a ratio of 30:70 diastereomeric excess.
However, in the case of the catalyst 8, substituted with fenchoxy
group, the consumption of the diazo reagent was limited possibly
due to the bulky side group effect on MPc.
In order to increase the substrate scope with respect to dia-
stereoselective reaction effect of catalyst 10, we performed the
Cu(acac)2-catalyzed carbonyl-ylide ring closure reaction of thio-
phene-2-carbaldehyde (11) and dimethyl diazomalonate in recent
study [2d] (Scheme 3). While this reported study with Cu(acac)2
had yielded diastereomeric dioxolanes 12 with a non-selective way
the new attempt with catalyst 10 gave diastereoselective dioxo-
lanes mixture with a ratio of 10:90 diastereomeric excess.
In order to understand the benefits of the catalyst system and
the experimentally observed product distribution between di-
astereomers 3a (3S, 10R and 3R, 10S) and 3b (3R, 10R and 3S, 10S), DFT
calculations were carried out for the cyclization step of the reaction
involving 10. Although the calculations presented herein only
include the 3S, 10R vs. 3R, 10R cases, these results can be extended to
the remaining mirror-image products, 3R, 10S vs. 3S, 10S for both 3a
and 3b due to the racemic nature of the reactant.
catalyzed carbonyl-ylide reaction of a-ionone and dimethyl diazo-
malonate [2c] was also re-studied in the presence of several com-
mon catalysts, including the MPcs that have not been used
previously in this reaction. To understand the product distribution
(chemo-selectivity) and also diastereoselectivity in the reaction,
various parameters (rate of reactants, reaction time etc.) were
examined (Table 1).
Dihydrofuran (3) and furofuran (4) derivatives were formed in a
ratio of 77:33 with a diastereoselectivity of 3a:3b ¼ 42:58,
respectively, from our previous reaction of a-ionone and dimethyl
diazomalonate in the presence of Cu(acac)2 under the conditions of
entry 1, Table 1 [2c]. For this catalyst, we re-designed the procedure
so that the formation of furofuran compound (4) was prevented by
controlled dropping of the diazo compound slowly (entry 2,
Table 1). Thus, increasing the amount of a-ionone was not sufficient
alone in order to give any significant difference for preventing the
formation of furofuran (4) (entries 1 and 2, Table 1).
According to the literature, in the presence of excess diazo
compound, Tang et al. have used CuCl:AgSbF6 with chiral additives
to increase diastereoselectivity [3b]. However, in our results (en-
tries 5 and 6) with similar conditions to that study, no significant
diastereoselectivity improvement was observed. Then, to
To find the most populated conformational state of the copper
complexed Pc system, an extended conformational analysis was
conducted. As can be seen from Fig.1, there are mainly four possible
conformers relative to the Cu-Pc plane: all of the four neopentyl
substituents oriented on one side of the plane of Pc (10a); one
leaning above the Pc plane and the others leaning below (10b); two
adjacent substituents leaning up and the others down (10c); two
substituents on one of the diagonal axis of the Pc plane directed
above and the others below the Pc plane (10d).
Clearly, 10d is the most stable conformer by approximately
3 kcal/mol relative to the other conformers and therefore, the re-
action must preferentially take place on its two distinct surfaces.
As a start, a Cu-carbene complex is modelled. Today, it is well-
known that these reactions start with the diazo-decomposition
leading to metal-carbene complexes and this is the rate
Scheme 1. Chemoselective/diastereoselective reaction of
a-ionone and dimethyl
diazomalonate [2c].
2

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
Table 1
Product ratios of reactions of
a
-ionone (1) and dimethyl diazomalonate (2)a.
Catalyst (equiv)b
Entry
Reaction time (hour)
Ratio 1:2c
3:4d
3a:3b (d.r.)e
1
2
3
4
5
Cu(acac)2 (0.007)
Cu(acac)2 (0.007)
CuCl (0.007)
Rh2(OAc)4 (0.007)
CuCl:AgSbF6 (0.025:0.029)
Chiral add:2,20-isopropylydene-bis[(4S)-4-phenyl-2-oxazoline (0.032)
3
24
8
9
8
1.5:1
1:1
1.5:1
1.5:1
1:1.5
77:33
100:0
100:0
100:0
100:0
42:58 [2c]
42:58 [2c]
45:55
46:54
38:62
6
CuCl:AgSbF6 (0.025:0.029)
Chiral add:2,20-bipyridine (0.032)
7 (0.007)
7 (0.007)
8 (0.007)
9 (0.007)
9 (0.007)
10 (0.007)
8
1:1.5
100:0
40:60
7
8
9
10
11
12
48
52
100
32
27
9
1.5:1
1:1
1.5:1
1.5:1
2:1
100:0
100:0
100:0
100:0
100:0
100:0
37:63
35:65
40:60f
40:60
38:62
30:70
1.5:1
a
Reaction conditions: Substrate (1.5 equiv.) and catalyst (0.007 equiv.) in 10 mL of benzene, and dimethyl diazomalonate (1 equiv.) in 1 mL of benzene, reflux under N2
(details in given supporting information).
b
Diazo compound was used as 1 equivalent.
c
mmol ratio of 1 and 2.
d
Determined by 1H NMR spectroscopy.
e
d.r. is diastereomeric ratio of 3 was determined 1H NMR spectroscopy.
f
Diazo compound did not consume completely.
Fig. 2. The three-dimensional geometry of 10d-carbene.
carbene structure (Fig. 2) is much longer than the Cu(acac)2
analogue from our earlier report (1.771 Å) [4e]. However, the
donor-acceptor energies between 10d and carbene carbon,
exhibited by the NBO analysis show strong interactions in between,
mostly from the carbene carbon to Cu. (See supporting information
Scheme 3. The reactions of thiophene-2-carbaldehyde and dimethyl diazomalonate.
for details).
Once a-ionone is added, a carbonyl-ylide intermediate is known
to occur (Scheme 4). The carbene carbon of this ylide can attack the
present olefinic carbon atom via two modes, yielding a tetrahedral
carbon with different stereocenters. Additionally, the cyclization
step can take place on both sides of the Pc ring. As can be seen in
Fig. 1, energetically, these two faces must cause a variation during
the cyclization reaction since they are stereochemically different
due to the alignment of the neopentyl substituents (See supple-
mentary material in Fig. S1). Thus, we have considered the align-
ments of the a-ionone on the up and down faces of the Pc planes
and the reactions were modelled on both faces of 10d (Schemes 5
and 6) for formation of both S,R and R,R products.
With the substrate a-ionone, pre-reactant complexes will form
(10d-up and 10d-down in Schemes 5 and 6, respectively). Since the
pre-reactant complex 10d-up is the most stable structure, all the
energies of Schemes 5 and 6 are reported relative to this structure.
Once the a-ionone interacts with the Cu-carbene and forms a ylide,
Fig. 1. Possible conformers of 10. The energies are presented relative to 10d.
the distance between the carbene carbon and copper center
extended to 3.10 Å in both up and down structures. This result
implies that the binding of the substrate carbonyl oxygen to the
carbene carbon weakens its interaction with the copper center
appreciably so that the new ylide fragment obtained above/below
the Cu-Pc plane binds to the catalyst system via the van der Waals
interaction originating from both carbene carbon-copper center
determining step as we have shown in our earlier reports with DFT
calculations [4e, 7]. The planar structure of the Pc ring does not
allow a convential Cu]C interaction as seen with other geometri-
cally free ligands. Thus, the C(carbene)-Cu distance of 2.47 Å in 10d-
3

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
Scheme 4. Formation of 3a and 3b.
and the stacking interactions. In the proceeding sections of the
cyclization reactions, these interactions are continuously weakened
due the destruction of the carbene character of the carbon atoms as
the carbon-copper center distances extend to 3.40 Å, 3.21 Å, 3.38 Å,
3.25 Å in the TS-up-SR, TS-up-RR, TS-down-SR and TS-down-RR
transition state structures, respectively. Eventually, these in-
teractions vanish as these distances further extend to 4.32 Å, 3.91 Å,
4.13 Å and 4.26 Å in the product structures, namely, SR-up, RR-up,
SR-down and RR-down, respectively.
The effect of copper was reported to initiate the diazo decom-
position and formation of metal carbenoid. At the same time,
copper facilitated the cyclization by bringing the reacting sites to
geometrically available position. The geometries of the transition
state structures show that the presence of the neopentyl groups in
this system can make a directional effect by holding them in a
proper 3-dimensional geometry in space. This suggest that the non/
peripheral substituents can be varied so that the desired in-
teractions can be built between the substrate and the substituents
to dominate only one mode of cyclization.
cyclization step. According to the computations conducted in this
study, the catalyst provides a van der Waals surface to the pre-
reaction structure of the cyclization step. Additionally, the bulky
neopentyl groups have directed the positioning of the a-ionone and
the dimethyl diazomalonate groups, which played a directional role
in the diastereoselectivity.
These results show that the MPcs incorporate the synergistic
effect of the electrophilicity of Cu and the high electron donating
ability of Pc ring, which has a potential to design catalysts for
stereoselective synthesis. This study has shown that further efforts
on MPcs with suitable peripheral/non-peripheral substituents can
lead to new catalysts for stereoselective carbenoid reactions in
future studies.
4. Experimental section
4.1. Materials and methods
3. Conclusion
All solvents and reactants are commercially available. Dimethyl
diazomalonate (2) (dmdm) was prepared according to literature
[8]. All reactions of diazo compounds and substrates were carried
out under nitrogen atmosphere. A rotary evaporator equipped with
a water condenser and attached to a vacuum system was used to
concentrate in vacuo. UVevisible spectra were measured with a
Shimadzu UV-1601 double beam spectrometer. 1H NMR, and 13C
NMR spectra were recorded on Agilent VNMRS 500/125 MHz,
In this study, a series of MPc complexes substituted non-
peripherally with fenchoxy and neopentoxy moieties were
employed as catalysts in a designed and known metal-carbenoid
reaction. The Pc’s with fenchoxy group have been synthesized for
the first time. These metal complexes were used in the reaction of
a
-ionone (1) and dimethyl diazomalonate (2), along with a series of
common catalysts. Among these catalysts, 1(4), 8(11), 15(18),
22(25)-tetrakis(3-neopentoxy) phthalocyaninato copper (II) (10)
gave better yields with enriched diastereomeric excess, leading to
respectively. Chemical shifts (d) are reported in ppm with respect to
the internal standard tetramethylsilane (TMS). Splitting patterns
were described as follows: s (singlet), d (doublet), t (triplet), q
(quartet), m (multiplet), and br (broad signal). GC-MS analyses
were performed on a Thermo Finnigan trace dsq instrument
formation of one diastereomer (3b). In the reaction of
a thiophene-
2-carbaldehyde (11) and dimethyl diazomalonate (2) with catalyst
10 also resulted enriched diastereomeric excess similarly.
equipped with
a
flame ionization detector. 5% Phenyl
Herein, we present the first successful attempts that utilize MPc
as a catalyst in [4 þ 1] and 3 þ 2] cycloaddition reactions. DFT
calculations were performed to explain the benefits of the catalyst
system and the structural effects that led to diastereoselectivity in
this [4 þ 1] reaction. With the calculations, the experimentally
observed product distribution was reproduced and explained by
the steric effects caused by the pendant group during the
polysilphenylene-siloxane capillary column (TR-5MS) was used
with helium as the carrier gas. Temperature program is as follows:
Start 100 ꢀC then 5 min isothermal, ramp 20ꢀ/min; final 290 ꢀC and
then 10 min isothermal. Retention times (tR) are reported in min.
ESI-MS analysis were performed on Bruker Micro TOF-ESI/MS.
Melting points were recorded on Buchi Melting Points B-540
apparatus.
4

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
Scheme 5. The cyclization modelled for the approach of the substrates from the upper side of 10d. Energies are not to scale. R ¼ CH2C(CH3)3, E ¼ CO2CH3. 3D version of this scheme
is given in Fig. S2 in supporting information.
4.2. General procedure 1 for synthesis of ligands (5e6)
equal portions. Reaction was monitored by TLC. After completion of
reaction, the reaction mixture was poured onto water and extracted
with dichloromethane (2 ꢁ 50 mL), and diethyl ether (1 ꢁ 50 mL),
respectively. Organic phases were collected and dried over Na2SO4.
The solvent was removed under reduced pressure and the crude
3-Nitrophthalonitrile (7 mmol) and alcohol (5 mmol) were
dissolved in 15 mL dry DMSO under nitrogen atmosphere. Then dry
K2CO3 (4 g, 23 mmol) was added to reaction flask during 2 h in
5

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
Scheme 6. The cyclization reaction modelled for the approach of the substrates below the Pc plane of 10d. Energies are not to scale. R ¼ CH2C(CH3)3, E ¼ CO2CH3. 3D version of this
scheme is given in Fig. S3 in supporting information.
product was purified by column chromatography.
1.14 (s, 3H), 0.88 (s, 3H); 13C NMR (125 MHz, CDCl3)
d 162.5, 134.2,
124.6, 117.8, 117.1, 115.4, 113.1, 105.3, 92.5, 49.8, 48.9, 41.3, 40.3, 30.5,
26.3, 25.6, 20.5, 19.8;
4.2.1. 3-Fenchoxy-phthalonitrile (5)
According to general procedure 1, 3-nitrophthalonitrile (1.20 g,
7 mmol) and (þ)-fenchol (0.77 g, 5 mmol) were dissolved in 15 mL
dry DMSO under nitrogen atmosphere. After work-up, crude
product was purified by silica column chromatography (30% ethyl
acetate/hexane) to give compound 5 was obtained as a white solid,
4.2.2. 3-Neopentoxy-phthalonitrile (6)
According to general procedure 1, 3-nitrophthalonitrile (1.20 g,
7 mmol) and neopentanol (0.44 g, 5 mmol) were dissolved in 15 mL
dry DMSO under nitrogen atmosphere. After work-up, crude
product was purified by silica column chromatography (20% ethyl
acetate:petroleum ether) to give compound 6 as a grey solid, m.p.:
m.p.: 110e113 ꢀC; tR ¼ 13.2; 1H NMR (500 MHz, CDCl3)
d 7.59 (dd,
3
5
3JH,H ¼ 8.6/7.7, 1H), 7.31 (dd, JH,H ¼ 7.7, JH,H ¼ 0.7, 1H), 7.22 (d,
3JH,H ¼ 8.6, 1H), 4.04 (d, 4JH,H ¼ 1.5, 1H), 2.18e2.12 (m, 1H), 1.84 (m,
1H), 1.63 (dq, 2JH,H ¼ 10.6, 4JH,H ¼ 4.0e1.7, 1H), 1.56 (m, 1H), 1.54 (m,
1H), 1.30 (dd, 2JH,H ¼ 10.7, 3JH,H ¼ 1.3, 1H), 1.21 (s, 3H), 1.20 (m, 1H),
120e121.5 ꢀC; tR ¼ 11.95; 1H NMR (500 MHz, CDCl3)
d 7.62 (t,
3JH,H ¼ 8.2, 1H), 7.34 (d, 3JH,H ¼ 7.7, 1H), 7.22 (d, 3JH,H ¼ 8.7, 1H), 3.76
(s, 2H), 1.11 (s, 9H).
6

F.S. Gungor, B.S. Sesalan, N.S. Tuzun et al.
Tetrahedron 80 (2021) 131892
4.3. General procedure 2 for synthesis of MPc (7e10)
4.4. General procedure for metal-carbenoid reactions
A mixture of ligand (0.35 mmol, 4 equiv.) and metal salt
(0.0875 mmol, 1 equiv.) in 1 mL n-pentanol in Schlenk tube was
heated at 80 ꢀC under nitrogen atmosphere. 1e2 drops of 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) were added to the reaction
mixture and heated at 140e145 ꢀC for 24 h. After cooling down to
room temperature, methanol was added to the reaction mixture,
and then the mixture was filtered. The precipitate was purified by
chromatography.
The reaction of substrate (1 and 11) and dimethyl diazomalonate
(2) was performed according to our previous work [2c, 2d].
Experimental details were given in supplementary material.
4.5. Computational details
Gaussian 16, Revision A.03 software [9] was utilized for the DFT
calculations. Due to large number of electrons in the computational
system, geometry optimizations and frequency calculations in the
unrestricted doublet multiplicity state were carried out with
LANL2DZ [10] effective core potential for copper and 6-31G(d) basis
set for the rest of the atoms, using M06-L functional [11], which has
been successful with Cu catalyst in our earlier report [12]. Then, to
refine the energies, single point calculations were carried out with
the 6-311 þ G(2d, 2p) basis set for the atoms other than copper and
with PCM solvation scheme [13] to represent the solvent benzene
in a continuum model. Every transition state reported in this study
has one imaginary frequency belonging to the reaction coordinate.
Intermediate states belonging to the located transition states were
obtained utilizing intrinsic reaction coordinate [14] (IRC) calcula-
tions. The reported energies are electronic energies from single
point calculations (high level). In the figures, hydrogens are omitted
for clarity while reported distances are in the units of Å.
4.3.1. 1(4), 8(11), 15(18), 22(25)-tetrakis(3-fenchoxy)
phthalocyaninato nickel (II) (7)
According to general procedure 2, 0.1 g (0.35 mmol) 3-fenchoxy-
phthalonitrile (5) and 0.015 g (0.0875 mmol) Ni(OAc)2 was reacted
in 1 mL n-pentanol at 140e145 ꢀC for 24 h in the presence of 1e2
drops of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). After work-up,
precipitate was dissolved in dichloromethane and purified by p-
TLC (silica plate, 10% methanol:dichlorometane). Compound 7 was
obtained as blue-green solid (13 mg, 10.5%); UVeVis (CH2Cl2): lmax
nm (log ε) ¼ 318.5 (4.33), 631 (3.24), 703.5 (3.97); FTIR [nmax]: 2992,
2866, 1589, 1489, 1325 cmꢂ1 1H NMR (500 MHz, CDCl3)
; d 9.17 (d,
3JH,H ¼ 7.8, 1H), 7.98 (t, 3JH,H ¼ 7.7, 1H), 7.59 (d, 3JH,H ¼ 7.8, 1H), 4.68
(s, 1H), 2.30e2.24 (m, 1H), 1.99 (bs, 1H), 1.92e1.81 (m, 3H),
1.29e1.21 (m, 6H), 0.88e0.80 (m, 5H); FAB-MS (m/z, %): 1178 (Mþ,
100), 1194 (17), 1211 (11).
Declaration of competing interest
4.3.2. 1(4), 8(11), 15(18), 22(25)-tetrakis(3-fenchoxy)
phthalocyaninato copper (II) (8)
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
According to general procedure 2, 0.1 g (0.35 mmol) 3-fenchoxy-
phthalonitrile (5) was treated with 0.022 g (0.085 mmol) Cu(acac)2
in 1 mL n-pentanol in the presence of 1e2 drops of 1,8-diazabicyclo
[5.4.0]undec-7-ene (DBU). After work-up, precipitate was dissolved
in dichloromethane and purified by silica column chromatography
Acknowledgements
Istanbul Technical University Scientific Research Fund sup-
ported this work (Project No: 39424). The authors acknowledge the
National High Performance Computing Centre at ITU (grant no.
5004722017) for computational sources.
(10% dichloromethane:methanol). Compound
8 was as dark
greenish blue solid (33 mg, 26.8%); UVeVis (CH2Cl2): lmax, nm
(log ε) ¼ 320 (3.87), 640.5 (3.65), 713 (4.34); FTIR [nmax/cmꢂ1]:
2965, 2935, 2700, 1589, 1487, 1261, 1243 cmꢂ1; FAB-MS (m/z, %):
1181 (Mþ ꢂ 2, 100), 1200 (11), 1216 (11).
Appendix A. Supplementary data
4.3.3. 1(4), 8(11), 15(18), 22(25)-tetrakis(3-neopentoxy)
phthalocyaninato nickel (II) (9)
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2020.131892.
According to general procedure 2, 0.1 g (0.46 mmol) 3-
neopentoxy phthalonitrile (6) was reacted with 0.02
g
(0.115 mmol) Ni(OAc)2 in 1 mL n-pentanol in the presence of 1e2
drops of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). After work-up,
precipitate was washed with methanol, hexane, and diethyl ether
respectively. The product dried in vacuo. Compound 9 was obtained
as mazerine blue solid (15 mg, 4%); UVeVis (CH2Cl2): lmax, nm
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8