6
964
Z. Abada et al. / Tetrahedron Letters 53 (2012) 6961–6964
Ph
Acknowledgments
Ph
OH
Ph
O
PhMgBr
THF
Thanks are due to K. Leblanc for her help in chromatography
analyses, and for mass spectrometry analyses. We wish to thank
J.C. Jullian (Châtenay-Malabry) for NMR experiments.
NH
N
N
N
-
78°C
N
HN
Ar
then 0°C
OMe
N
O
Ph
O
O
HO Ph
Ph
Supplementary data
NH
N
N
15d 78%
N
HN
1
Supplementary data ( H NMR spectra and experimental data of
O
Ar
compounds 1–8, 14c, 15c, 16c, 17c, 15d, 15f, and 18f) associated
O
MeO
HO
Ar
5c: Ar=Ph
8c: Ar=3,4,5-OMephenyl
O
O
N
NH
N
N
NaOH
1
1
N
DCM
MeOH
HN
References and notes
O
O
OH
Ar
1. (a) Groves, J. T.; Han, Y.-Z.. In Cytochrome P-450 Structure Mechanism and
Biochemistry; de Montellano, R. R. Ortiz, Ed.; Plenum Press: New York, 1995; (b)
Meunier, B.; De Visser, S. P.; Shaik, S. Chem. Rev. 2004, 104, 3947.
1
5f: Ar=Ph
52%
1
8f: Ar=3,4,5-OMephenyl 50%
2
3
4
.
.
.
Rose, E.; Quelquejeu, M.; Pandian, R. P.; Lecas-Nawrocka, A.; Vilar, A.; Ricart, G.;
Collman, J. P.; Wang, Z.; Straumanis, A. Polyhedron 2000, 19, 581.
Akagah, B.; Lormier, A. T.; Alain Fournet, A.; Figadère, B. Org. Biomol. Chem.
Scheme 3. Synthesis of diverse functionalized chiral porphyrins.
2
008, 6, 4494–4497.
Rose, E.; Andrioletti, B.; Zrig, S.; Quelquejeu, M. Chem. Soc. Rev. 2005, 34, 573–
83.
5. Abada, Z.; Ferrié, L.; Akagah, B.; Lormier, A. T.; Figadère, B. Tetrahedron Lett.
011, 52, 3175–3178.
5
remained unsuccessful. Indeed, the kinetic of equilibration be-
tween the and ,b isomers seems to be slow enough to allow
2
a
,a
a
6
7
.
.
Shen, D. M.; Liu, C.; Chen, Q. Y. J. Org. Chem. 2006, 71, 6508.
(a) Gao, G.-Y.; Chen, Y.; Zhang, X. P. Org. Lett. 2004, 6(11), 1837–1840; (b)
Klapars, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124(25), 7421–
us to separate them by TLC (2–4 min duration) whereas using a
column chromatography (>30 min) is long enough to able the
equilibration of the two atropisomers. A temperature NMR study
was achieved in order to confirm this hypothesis (Fig. 1). Proton
NMR spectrum simplifies nicely at higher temperature and b-pyr-
rolic, aromatic, and methoxy proton signals are clearly coalescing
while increasing the temperature. Only N–CH signals of the amide
moiety at 5.6 ppm still remain separated at 130 °C although they
are closer than at room temperature.
It is important to note that pyrroglutamate moiety in diarylpor-
phyrins 14c–18c can be further functionalized by many readily
available compounds allowing access to more complex porphyrins
with original structures. Therefore, phenyl magnesium bromide
was added selectively on the ester moiety to give porphyrin 15d
7428; (c) Audisio, D.; Messaoudi, S.; Alami, M. Tetrahedron Lett. 2007, 48, 6928–
6932.
8
.
.
(a) Liu, C.; Shen, D. M.; Chen, Q. Y. Eur. J. Org. Chem. 2006, 2703; (b) Liu, C.; Chen,
Q. Y. Synlett 2005, 8, 1306; (c) Liu, C.; Chen, Q. Y. Eur. J. Org. Chem. 2005, 3680;
(
d) Gao, G. Y.; Colvin, A. J.; Chen, Y.; Zhang, X. P. J. Org. Chem. 2004, 69, 8886; (e)
Gao, G. Y.; Chen, Y.; Zhang, X. P. Org. Lett. 1837, 2004, 6; (f) Gao, G. Y.; Colvin, A.
J.; Chen, Y.; Zhang, X. P. Org. Lett. 2003, 5, 3261; (g) Gao, G. Y.; Chen, Y.; Zhang,
X. P. J. Org. Chem. 2003, 68, 6215; (h) Chen, Y.; Zhang, X. P. J. Org. Chem. 2003, 68,
4432.
9
(a)Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A., Diederich, F., Eds.;
Wiley: Weinheim, 2004; (b) Montgomery, T. Angew. Chem., Int. Ed. 2004, 43,
3890–3908; (c) Li, Z.; Fu, Y.; Liu, L.; Guo, Q.-X. Chin. J. Org. Chem. 2005, 25,
1508–1529; d) Prim, D.; Campagne, J. M.; Joseph, D.; Andrioletti, B. Tetrahedron
2002, 58, 2041–2075.D.
1
0. (a) Mathre, D. J.; Johnes, T. K.; Xavier, L. C.; Blacklock, T. J.; Reamer, R. A.;
Mohan, J. J.; Jones, E. T. T.; Hoogsteen, K.; Baum, M. W.; Grabowski, E. J. J. J. Org.
Chem. 1991, 56, 751; b) Kanth, J. V. B.; Peryasamy, M. Tetrahedron 1993, 49,
1
6
in 78% yield (Scheme 3). This protocol is an alternative to the fail-
ing cross-coupling between 7 and 12 or 13. Thus, methyl ester can
be cleaved by saponification, affording diacides 15f and 18f in 52%
and 50%, respectively. Further functionalization into amide or es-
ter function could be then envisioned.
5127–5132.D.
1
1
1. A mixture of starting material and debrominated compound was recovered.
2. It is important to stress that alternative conditions to palladium (Ni or Cu
catalysis) did not produce expected products either: Liu, C.; Shen, D. M.; Chen,
Q.-Y. J. Org. Chem. 2007, 72, 2732–2736.
1
7
13. Balaban, M. C.; Chappaz-Gillot, C.; Canard, G.; Fuhr, O.; Roussel, C.; Balaban, T.
In conclusion, we synthesized new chiral porphyrins includ-
ing C–N-meso substituted ones. Methyl pyrroglutamate appeared
to be the best candidate for Buchwald–Hartwig type cross cou-
pling reaction affording the expected adduct in 94% yield. More
bulky substrates did not react under these reaction conditions.
S. Tetrahedron 2009, 65, 3733–3739.
14. (a) Freitag, R. A.; Mercer-Smith, J. A.; Whitten, D. G. J. Am. Chem. Soc. 1981, 103,
226; (b) Crossley, M. J.; Field, L. D.; Forster, A. J.; Harding, M. M.; Sternhell, S. J.
1
Am. Chem. Soc. 1987, 109, 341; (c) Hatano, K.; Azai, K.; Kobu, T.; Tamai, S. Bull.
Chem. Soc. Jpn. 1981, 54, 3518; (d) Miyamoto, T. K.; Hasegawa, T.; Takagi, S.;
Sasaki, Y. Chem. Lett. 1983, 1181; (e) Hanato, K.; Kowasaki, K.; Munakata, S.;
Iitaka, Y. Bull. Chem. Soc. Jpn. 1985, 60, 1985; (f) Freitag, R. A.; Whitten, D. G. J.
Phys. Chem. 1983, 87, 3918.
For porphyrins containing two chiral moieties, a mixture of
a,b
and atropisomers was obtained, nevertheless the kinetic of
a,a
1
5. (a) Rose, E.; Quelquejeu, M.; Pochet, C.; Julien, N.; Kossanyi, A.; Hamon, L. J. Org.
Chem. 1993, 58, 5030–5031; (b) Rose, E.; Cardon-Pilotaz, A.; Quelquejeu, M.;
Bernard, N.; Kossanyi, A. J. Org. Chem. 1995, 60, 3919–3920.
6. Deskus, J.; Fan, D.; Smith, M. B. Synth. Commun. 1998, 28, 1649–1660.
7. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Chemistry, Third
edition; John Wiley & Sons: New York, 1999.
equilibration is sufficiently high to unable their physical separa-
tion for characterization. Ester function of pyrroglutamate can be
further transformed to give new chiral porphyrins. Utilization of
these new chiral porphyrins will be reported in due course.
1
1