Synthesis, crystal structure, catalytic dimerization and S–H insertion of new porphyrin diazoketones

Article abstract of DOI:10.1016/j.molstruc.2018.03.108

Porphyrin diazoketones were synthesized from the corresponding porphyrin acetyl chloride by treatment with trimethylsilyldiazomethane in 60–80% yield. The solid-state structure of one of the two bis-diazo derivatives (trans isomer) was determined by singl

Full text of DOI:10.1016/j.molstruc.2018.03.108

Accepted Manuscript
Synthesis, crystal structure, catalytic dimerization and S-H insertion of new
porphyrin diazoketones
Daniel Carrié, Thierry Roisnel, Gérard Simonneaux
PII:
S0022-2860(18)30405-8
10.1016/j.molstruc.2018.03.108
MOLSTR 25047
DOI:
Reference:
To appear in:
Journal of Molecular Structure
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Revised Date:
Accepted Date:
21 February 2018
23 March 2018
25 March 2018
Please cite this article as: Daniel Carrié, Thierry Roisnel, Gérard Simonneaux, Synthesis, crystal
structure, catalytic dimerization and S-H insertion of new porphyrin diazoketones, Journal of
Molecular Structure (2018), doi: 10.1016/j.molstruc.2018.03.108
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Graphical Abstract
Synthesis, crystal structure, catalytic dimerization and S-H insertion of new
porphyrin diazoketones
Daniel Carriéa, Thierry Roisnela and Gérard Simonneauxa,*
aUniv Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France
e-mail address : gerard.simonneaux@univ-rennes1.fr

ACCEPTED MANUSCRIPT
Synthesis, crystal structure, catalytic dimerization and S-H insertion of new
porphyrin diazoketones
Daniel Carriéa, Thierry Roisnela and Gérard Simonneauxa,*
aUniv Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France
e-mail address : gerard.simonneaux@univ-rennes1.fr
ABSTRACT
Porphyrin diazoketones were synthesized from the corresponding porphyrin acetyl chloride by
treatment with trimethylsilyldiazomethane in 60-80% yield. The solid-state structure of one of
the two bis-diazo derivatives (trans isomer) was determined by single-crystal X-ray diffraction
analysis. Thiol insertion and cis-selectivity in the coupling reactions of porphyrin diazoketones
catalyzed by ruthenium porphyrin were observed.
Keywords : porphyrin diazoketones ; X-ray molecular structure ; dimerization ;
S-H insertion
1. Introduction
Among various functional groups, diazo derivatives are particularly attractive due to their
high reactivities. Thus  -diazoketones are of large interest due to their application in organic
synthesis because these are intermediates in a range of chemical transformations, including
dipolar cycloaddition, cyclopropanations and the homologation of carboxylic acid known as
the Arndt-Eistert reaction [1].
Owing to the fruitful development of the synthesis of porphyrins, porphyrin chemists have
gained a variety of potent tools to create various types of porphyrin-based materials that are
difficult to prepare through conventional organic chemistry [2]. Functionalization reactions of
meso-tetra-aryl-substituted porphyrins have been largely developed for the preparation of many
porphyrin molecules which are essential for photodynamic therapy, bioimaging probes,
molecular wires and so forth [3]. Therefore to achieve these fascinating functions, design and
synthesis of structurally diverse molecules are essential. Surprisingly, simple diazoketone
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substituted meso-tetraphenyl-porphyrin have not been yet prepared. As part of a program
investigating porphyrin diazocarbonyl methodologies [4-8], we have studied the
functionalization of tetraarylporphyrin using trimethylsilyldiazomethane as reactive
intermediates. Herein we report the synthesis of several diazoketone functionalized porphyrins
and their chemical reactivity.
N
N
N
N
CO
Ru
Figure 1. Tetramesitylporphyrin ruthenium carbon monoxide (TMPRuCO).
2. Experimental
2.1 General
All reactions were performed under argon. Solvents were distilled from an appropriate
drying agent prior to use: CH2Cl2 from CaH2. Commercially available reagents were used
without further purification unless otherwise stated. All reactions were monitored by TLC with
Merck precoated aluminum foil sheets (Silica gel 60 with fluorescent indicator UV254).
Compounds were visualized with UV light at 254 nm. Column chromatographies were carried
1
13
out using silica gel from Merck (0.063−0.200 mm). H NMR and C NMR in CDCl3 were
recorded using Bruker (Advance 400dpx spectrometer) at 400 MHz and 125 MHz, respectively.
High resolution mass spectra were recorded on a Thermo-Fisher Q-Exactive (Q-Tof 2)
spectrometer in ESI positif mode at the CRMPO at Rennes.
5-(4-carbomethoxyphenyl)-10,15,20-triphenylporphyrin and the corresponding acid were
prepared from the method reported by Mishra [9]. Disubstituted tetraarylporphyrins were
prepared as previously reported [10].
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2.2. Synthesis
2.2.1 Preparation of mono-diazo compound 1
Hydrolysis of 5-(4-methoxycarbonylphenyl)10,15,20-triphenylporphyrin (150 mg, 0.223
mmol) was carried out with NaOH (400 mg, 10 mmol) in 2 mL of ethanol and 10 mL of toluene
at 70 °C for 2 h. After evaporating the ethanol, 1N HCl aqueous solution was added until the
pH was less than 5. After filtration of the precipitate, the solid was washed with water. Then
the solid was dried for one night at 80 °C. The purple solid was dissolved in 2 mL of thionyl
chloride and refluxed overnight. After removing SOCl2 under reduced pressure and drying, the
acid chloride was used to react with triethylamine dissolved in 8 mL of tetrahydrofuran.
Trimethylsilyldiazomethane (2 equiv) was then added at 0 °C for 1 h. After stirring for two
days at room temperature, the solution was then evaporated, dissolved in CH2Cl2 and purified
though a silica gel column (CH2Cl2). Yield 75%.1H NMR (400 MHz, CD2Cl2): δ 8.92 (s broad,
6H), 8.86 (s broad, 2H), 8.31 (AB syst., 2H), 8.27 (m, 6H), 8.11 (AB syst., 2H), 7.97-7.65 (m,
13
9H), 6.24 (s, 1H, CHN2) ppm. C NMR: δ 185.9 (C=O), 146.6, 142.0, 136.1, 134.7, 134.5,
131.3, 127.8, 126.7, 125.0, 120.5, 118.5, 54.1 CHN2) ppm. UV-vis (CH2Cl2): max/nm (log ) =
419 (5.18), 515 (3.87), 550 (3.42), 590 (3.41), 646 (3.36).Mass (ESI) (m/z): calculated for
C46H31N6O [M+H]+: 683.25538, found: 683.2553.
2.2.2. Preparation of trans bis-diazocompound 2
The preparation from the corresponding trans bis-diazoester derivative, is similar to the
preparation of 1, excepted that 4 equivalents of trimethylsilyldiazomethane were used. 1H NMR
(400 MHz, CD2Cl2) : δ 9.01-8.82 (m, 8H,  pyrrole ), 8.39-9.30 (m, 4H),8.30-8.21 (m, 4H, CH),
8.21-8.14 (m, 4H, CH), 7.93-7.72 (m, 6H), 6.25(s, 2H, CHN2), -2.79 (s (broad), 2H, NH).UV-
vis (CH2Cl2) max/nm (log ) = 420 (5.07), 515 (3.75), 550 (3.37), 591 (3.15), 6.46 (3.02). Mass
(ESI) (m/z): calculated for C48H31N8O2 [M+H]+: 751.25645, found: 751.2561. Microcrystals of
2 suitable for X-ray structure analysis were obtained by recrystallization from CH2Cl2/pentane
(1:1).
2.2.3. Preparation of cis bis-diazo compound 3
The preparation, from the corresponding cis bis-diazoester derivative, is similar to the
preparation of 1, excepted that 4 equivalents of trimethylsilyldiazomethane were used. 1H NMR
(400 MHz, CD2Cl2): δ 9.10 - 8.75 (m, 8H,  pyrrole), 8.36 - 8.34 ( m, 4H), 8.27 - 8.23 (AB
syst., 4H), 8.19 - 8.17 (AB syst., 4H) , 7.85 - 7.82 ( m, 6H), 6.25 ( s, 2H, CHN2 ), -2.78 (s, 2H,
3

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NH).13C NMR (101 MHz, Methylene chloride-d2) selected data: δ 185.93 (CO), 134.75, 134.51,
131.33-130.91, 126.76, 125.06, 54.32 (CHN2). UV-vis (CH2Cl2): max/nm (log ) 420 (5.30), 515
(4.02), 550(3.68), 591(3.47), 646(3.32). Mass (ESI) (m/z): calculated for C48H31N8O2 [M+H]+:
751.25645, found: 751.2563.
2.2.4. Synthesis of dimer 4
To a distilled toluene solution (10 mL) containing 1 mg of TMPRuCO, 68.7 mg (0.1 mmol) of
1 dissolved in 20 ml of toluene was added under argon. The mixture was stirred for 24h at room
temperature. The solution was then evaporated and purified by chromatography on silica gel
column (CH2Cl2) to give 65.3 mg of 4 (Yield = 80 %). 1H NMR (400 MHz, CD2Cl2) : δ 9.05-
8.83 (m, 16H,  pyrrole), 8.52-8.42 (m, 8H), 8.30-8.15( m, 12H), 7.90-7.67 ( m, 18H), 7.62 (s,
2H, COCH), -2.77 (s (broad), 4H, NH). UV-vis (CH2Cl2) max/nm (log ) = 420 (5.72), 514
(4.32), 550 (3.92), 590 (3.56), 644 (3.22). Mass (ESI) (m/z): calculated for C92H61N8O2
[M+H]+:1309.4912, found: 1309.4897.
2.2.5 Zinc insertion in 4.
To a saturated solution of zinc diacetate (20 ml), 100 mg of 4 was added progressively at room
temperature. The mixture was stirred for 2h at room temperature. After purification by
chromatography on silica gel column (CH2Cl2), compound 5 was obtained in quantitative yield.
1H NMR (400 MHz, CD2Cl2): δ 9.05-8.92 (m, 16H,  pyrrole), 8.52-8.40 (m, 8H), 8.30-8.15 (
m, 12H), 7.90-7.65 ( m, 18H), 7.56 (s, 2H, COCH). UV-vis (CH2Cl2): max/nm (log ) = 423
64
(5.65), 551 (4.46), 593 (3.90). Mass (ESI) (m/z): calculated for C92H56N8O2 Zn2 [M+.]:
1432.31036, found: 1432.3092.
2.2.6. Reaction of 1 with thiophenol.
To a distilled toluene solution (20 mL) containing 1 mg of TMPRuCO and 84.7 mg (0.12 mmol)
of 1, 100 l of PhSH was slowly added under argon. The mixture was stirred for 24h at room
temperature. The solution was then evaporated and purified by chromatography on silica gel
column (CH2Cl2) to give 72.9 mg of 6 (Yield = 78 %). 1H NMR (400 MHz, CD2Cl2) : ):  9.05-
8.80 (m, 8H,  pyrrole), 8.42-8.32 (broad s, 4H), 8.31-8.20 (m, 6H), 7.91-7.75 (m, 9H), 7.65-
7.55 (m, 2H), 7.49-7.39 (m, 2H), 7.39-7.30 (m,1H), 4.60 (s, 2H, CH2S), -2.79 (s, 2H, NH). UV-
vis (CH2Cl2): max/nm (log ) = 417 (5.54), 514 (4.21), 549 (3.90), 592 (3.75), 647 (3.47). Mass
(ESI) (m/z): calculated for C52H37N4OS [M+H] +: 765.26826, found: 765.2679.
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2.3
X-ray structure determination
X-ray crystallographic study: (C48H30N8O2); M = 750.80. D8 VENTURE Bruker AXS
diffractometer, Mo-Kα radiation (λ = 0.71073 Å), T = 150 K; Orthorhombic P 21 21 2
(I.T.#18), a = 19.1655(7), b = 23.7406(11), c = 9.4608(4) Å, V = 4304.7(3) Å3. Z = 4, d = 1.158
g.cm-3, μ = 0.074 mm-1. The structure was solved by dual-space algorithm using the SHELXT
program,[11] and then refined with full-matrix least-square methods based on
F2(SHELXL).[12] The contribution of the disordered solvents to the structure factors was
calculated by the PLATON SQUEEZE procedure[13] and then taken into account in the final
SHELXL-2014 least-square refinement. All non-hydrogen atoms were refined with anisotropic
atomic displacement parameters. H atoms were finally included in their calculated positions
and treated as riding on their parent atom with constrained thermal parameters. A final
refinement on F2 with 9847 unique intensities and 523 parameters converged at ωR(F2) =
0.1704 (R(F) = 0.0706) for 6164 observed reflections with I > 2σ(I) and ωR(F2) = 0.1914 (R(F)
= 0.1150) for all independent reflections. Crystallographic data for the structure in this paper
have been deposited with the Cambridge Crystallographic Data Centre as supplementary
publication nos. CCDC 1560098.
Table 1
Selected bond distances and bond angles of compound 2.
Bond Distances (Å)
C29-N30
N30-N31
C27-C29
C27-O28
1.314(7)
1.124(6)
1.419(8)
1.232(7)
C49-N50
N50-N51
C47-C49
C47-O48
1.306(8)
1.124(7)
1.455(8)
1.212(6)
Bond Angles (°)
C29-N30-N31
177.1(6)
C49-N50-N51
177.5(8)
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C27-C29-N30
C29-C27-O28
C24-C27-O28
115.6(5)
C47-C49-N50
C49-C47-O48
C44-C47-O48
114.9(6)
121.4(5)
122.2(5)
123.5(5)
119.6(5)
3. Results and discussions
3.1 Synthesis
1) NaOH/Toluene/EtOH
NH
N
N
O
O
NH
N
N
O
2) HCl 1N
CH3
HN
OH
HN
= 70°C
SOCl2
= 80°C
THF/NEt3/
trimethylsilyldiazomethane
NH
N
N
O
NH
N
O
Cl
N2
HN
HC
HN
N
= 0°C
1
Scheme 1. General pathway for the synthesis of porphyrin diazoketone derivatives.
For the synthesis of porphyrin diazoketones, it was first decided to use
trimethylsilyldiazomethane as a substitute of diazomethane because the latter is not only highly
toxic but also explosive. Trimethylsilyldiazomethane (TMSCHN2) has been previously used in
the preparation of a variety of diazoketones from the corresponding acyl chloride by treatment
with trimethylsilyldiazomethane [1, 14, 15]. Herein, we successfully adapted this recent method
with porphyrin acyl chlorides that were prepared from esters. Thus, the acid was readily
available from 5-(4-carbomethoxyphenyl)-10,15,20-triphenylporphyrin, from the method
reported by Mishra [9]. Conversion of this acid to its acyl chloride with thionyl chloride gave a
quasi-quantitative yield. The porphyrin acyl chloride was then allowed to react with 2
equivalents of TMSCHN2 in the presence of an excess of triethylamine dissolved in THF at low
temperature (0°C). The expected porphyrin diazoketone 1 was obtained with 75% yield after 2
days. The structural assignment of porphyrin diazoketone 1 was based on mass spectrometry
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studies and proton NMR studies. The most noticeable feature in the 1H NMR spectrum was the
signal corresponding to the resonances of the diazo proton (CHN2) that appears as a singlet at
6.25 ppm. The assignment of the pyrrolic protons and corresponding carbons was achieved
1
through 2D NMR (COSY, HMBC and HSQC) ( 8.4-8.6 ppm). The H NMR spectrum also
showed AB signals corresponding to the aromatic ring bearing the diazo group (  and
8.31 ppm ).
Figure 2. ORTEP structure of porphyrin diazoketone compound 2 with the atom labeling of
diazo ketone groups (Hydrogen atoms removed for clarity, except N-H of the porphyrin ring).
3.2 Description of crystal structure
Recently diazocarbonyl compounds have attracted much attention not only as highly useful
reagents for organic synthesis but also as monomers for polymerization. Diazocarbonyl
compounds can be regarded as promising monomers when they are used as a monomer for
polycondensation in a form of bis(diazocarbonyl) compounds [16]. Actually, it was recently
reported the first example of polycondensation of some bis(diazoketone)s with aromatic diols,
where the initial objective of the examination was to utilize insertion of carbene derived from
diazoketone into OH of the diol to obtain poly(ether ketone)s [16]. Consequently we also
decided to investigate the synthesis of the trans and cis bis-diazoketones, noted 2 and 3,
respectively, these two compounds being prepared from the corresponding porphyrin bis-esters.
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To better characterize the diazo group and to assure the regioselectivity, an X-ray structure
determination of one of the bis-diazo isomer was undertaken (compound 2). The X-ray structure
of monocrystals confirms the opposite situation of the two diazo groups (see Figure 2). Bis-
diazoketone 2 was the first porphyrinic diazo compound to have its structure investigated by
X-ray diffraction analysis. The interatomic C-N (1.311 (8) and 1.313 (8)) Å and N--N (1.124
(7) and 1.120 (7) Å)) distances for 2 (Table 1) are however quite similar to the bond length
distances for 2-diazo-3oxochlorins (1.318 (4) and 1.135 (4) Å) [17].
NH
N
N
O
2
N2
HC
HN
TMPRuCO/THF
NH
N
NH
N
N
O O
N
HN
HN
Scheme 2. Coupling reaction of porphyrin diazoketones.
3.3 Chemical Reactivity
Selective intermolecular coupling reactions of diazo derivatives to form cis-alkenes have been
previously reported. Diazoesters and diazoketones [18-20] have been generally coupled using
various catalytic systems. Metalloporphyrins have also been used to get the cis selectivity [21-
23]. To evaluate the reactivity of porphyrin diazoketone compound 1, its ruthenium-catalyzed
homocoupling was first examined in dichloromethane (see Scheme 2) at room temperature by
using tetra-mesitylporphyrin ruthenium carbon monoxide (Figure 1) as catalyst. The dimer was
formed with 80% yield after 24h at room temperature with complete cis stereoselectivity. The
structural assignment of the porphyrin dimer 4 was based on mass spectrometry studies and
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1
proton NMR studies. The most noticeable feature in the H NMR spectrum was the signal
corresponding to the resonances of the olefinic proton (CH=) that appears as a singlet at 7.62
ppm. Zn metal was also inserted in the porphyrin core of 4 using a saturate solution of zinc
diacetate in methanol. After 20 min of stirring at room temperature, the zinc porphyrin dimer 5
was obtained in a quantitative yield.
Since peptidyl diazomethyl ketones appeared to be specific inactivators of cysteine proteinases
[24] insertion of diazoporphyrin ketone into S-H bonds, catalyzed by tetramesitylporphyrin
ruthenium was essayed (Scheme 3). Treatment of thiophenol with diazoporphyrin 1 catalyzed
by the ruthenium complex (Figure 1) gave the expected insertion of the diazo derivative into
the S-H bond to get 6 in 78% yield.
NH
N
NH
N
N
N
O
O
PhSH
N2
S
HN
TMPRuCO
HN
1
6
Scheme 3. Insertion of porphyrin diazoketone 1 into thiophenol.
4. Conclusions
The synthesis and reactivity of new porphyrin diazoketones occurs with good yields offering
for the first time a general access to these original porphyrins. Diazo compounds in the
functionalization of porphyrin macrocycles are still rare [25]. Thus the catalytic dimerization
and S-H insertion were easily obtained and could offer new opportunity. An X-ray structure
of a porphyrin bis-diazoketone confirms their opposite geometry. All the new derivatives
were identified by NMR and mass spectral analyses (see experimental section).
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References
[1] T. Ye, M.A. McKervey, Organic synthesis with -diazocarbonyl compounds, Chem. Rev. 94 (1994)
1091-1160.
[2] S. Hiroto, Y. Miyake, H. Shinokubo, Synthesis and Functionalization of Porphyrins through
Organometallic Methodologies, Chemical Reviews 117(4) (2017) 2910-3043.
[3] K. Kadish, K.M. Smith, R.E. Guilard, The Porphyrin Handbook (Vols. 1-10), The Porphyrin Handbook;
Academic Press: Boston, MA, 2000, Vol. 1-10. (2000).
[4] E. Galardon, P. Le Maux, G. Simonneaux, Cyclopropanation of alkenes, N-H and S-H insertion of
ethyl diazoacetate by Ruthenium porphyrin complexes, Tetrahedron 56 (2000) 615-621.
[5] G. Simonneaux, P. Le Maux, Optically active ruthenium porphyrins: chiral recognition and
asymmetric catalysis, Coord. Chem. Rev. 228 (2002) 43-60.
[6] I. Nicolas, T. Roisnel, P. Le Maux, G. Simonneaux, Asymmetric intermolecular cyclopropanation
of alkenes by diazoketones catalyzed by Halterman iron porphyrins, Tetrahedron Lett. 50 (2009)
5149-5151.
[7] P. Le Maux, I. Nicolas, S. Chevance, G. Simonneaux, Chemical reactivity of 6-diazo-5-oxo-l-
norleucine (DON) catalyzed by metalloporphyrins (Fe,Ru), Tetrahedron 66(25) (2010) 4462-4468.
[8] D. Carrie, H. Srour, P. Le Maux, G. Simonneaux, Synthesis and chemical reactivity of new zinc
porphyrin diazoacetates catalyzed by ruthenium and iron porphyrins, Tetrahedron Lett. 57(10) (2016)
1179-1182.
[9] B. Mishra, K.P.C. Shekar, A. Kumar, S. Phukan, S. Mitra, D. Kumar, Facile synthesis, characterization
and fluorescence studies of novel porphyrin appended thiazoles, J.Heterocyclic Chem. 50 (2013) 125-
128.
[10] J.A. Anton, P.A. Loach, synthesis of mono,Di, and trisubstituted tetraarylporphyrins, J.
Heterocyclic. Chem. 12 (1975) 573-576.
[11] G.M. Sheldrick, SHELXT – Integrated space-group and crystal-structure determination, Acta Cryst.
A71 (2015) 3-8.
[12] G.M. Sheldrick, Crystal structure refinement with SHELXL, Acta Cryst. C71 (2015) 3-8.
[13] A.L. Spek, PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to
the calculated structure factors, Acta Cryst. C71 (2015) 9-18.
[14] T. Aoyama, T. Shioiri, New methods and reagents in organic synthesis. 8.
Trimethylsilyldiazomethane. A new, stable, and safe reagent for the classical arndt-eistert synthesis,
Tetrahedron Lett. 21(46) (1980) 4461-4462.
[15] J. Cesar, M. Sollner Dolenc, Trimethylsilyldiazomethane in the preparation of diazoketones via
mixed anhydride and coupling reagent methods: a new approach to the Arndt-Eister synthesis,
Tetrahedron Lett. 42 (2001) 7099-7102.
[16] E. Ihara, Y. Hara, T. Itoh, K. Inoue, Three-Component Polycondensation of Bis(diazoketone) with
Dicarboxylic Acids and Cyclic Ethers: Synthesis of New Types of Poly(ester ether ketone)s,
Macromolecules 44(15) (2011) 5955-5960.
[17] T. Köpke, M. Pink, J.M. Zaleski, A Facile Synthesis of 2-Diazo-3-oxochlorins by Lewis Acid Activation:
Selective Modification of p-Electron Conjugated Macrocycles Synlett 14 (2006) 2183-2186.
[18] W. Baratta, A. Del Zotto, P. Rigo, cis-enediones from diazocarbonyl catalyzed by RuClC5H5PPh2,
Chem. Commun. (1997) 2163-2164.
[19] A. Del Zotto, W. Baratta, G. Verardo, P. Rigo, Functionalised cis-Alkenes from the Stereoselective
Decomposition of Diazo Compounds, Catalysed by [RuCl(ç5-C5H5)(PPh3)2], Eur. J. Org. Chem. (2000)
2795-2801.
10

ACCEPTED MANUSCRIPT
[20] D.M. Hodgson, D. Angrish, intermolecular coupling of diazoacetate using Grubbs, Chem. Eur. J. 13
(2007) 3470-3479.
[21] J.P. Collman, E. Rose, G.D. Venburg, Reactivity of Ruthenium 5,10,15,20-Tetramesitylporphyrin
towards Diazoesters: Formation of olefins, J. Chem. Soc., Chem. Commun. (1993) 934-935.
[22] G.Y. Li, C.M. Che, Highly Selective Intra- and Intermolecular Coupling Reactions of Diazo
Compounds to Form cis-Alkenes Using a Ruthenium Porphyrin Catalyst, Org. Lett. 6 (2004) 1621-1623.
[23] L.K. Baumann, H.M. Mbuvi, G. Du, L.K. Woo, Iron Porphyrin Catalyzed NH Insertion Reactions with
Ethyl Diazoacetate, Organometallics 26(16) (2007) 3995-4002.
[24] E. Shaw, Peptidyl diazomethanes as inhibitors of cysteine and serine proteinases, Methods
Enzymol. 244 (1994) 649-656.
[25] A.T.P.C. Gomes, M.G.P.M.S. Neves, J.A.S. Cavaleiro, Diazo compounds in the functionalization of
porphyrin macrocycles, J. Porph. Phtalocyan. 15 (2011) 835-847.
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The solid-state structure of a trans (bis-diazoketone) porphyrin was determined by crystal X-ray
diffraction analysis
Cis selectivity is observed for catalytic dimerization of porphyrin diazoketones
Thiol insertion of porphyrin diazoketone is catalyzed by ruthenium porphyrin