Chiral Atropisomeric Metalloporphyrins
FULL PAPER
under nitrogen. The mixture was then cooled to room temperature
under aerobic conditions and the solvent was evaporated at re-
duced pressure. The crude dry product was dissolved in CH2Cl2,
washed with water and dried over Na2SO4. The ferric complex was
recovered by column chromatography (alumina, eluent CH2Cl2/
CH3OH, 90:10), treated with HCl 10% and dried over Na2SO4.
Compound 3a was obtained as a precipitate from heptane in 55%
yield.
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3a: λmax(THF) /nm (ε /dm2 mol–1): 224 (24370), 284 (4033), 339
(3480), 431 (7730), 516 (1073), 591 (254). – CD (THF) /nm (∆ε):
208 (–213.8), 231 (513.0), 288 (–7.5), 310 (9.0), 343 (–40.1), 424
(–73.0), 517 (–7.6), 620 (–10.9). – IR: νFe–Cl ϭ 358 cm–1. –
FABϩMS; m/z: 1494 [M – Cl], 1529 [M ϩ].
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Using the same experimental procedures compounds (2b), (2c) and
(2d) were metallated with Fe(CO)5 to obtain complexes (3b), (3c)
and (3d), respectively.
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3b: λmax(THF) /nm (ε /dm2 mol–1): 229 (30644), 283 (6173), 337
(5066), 377 (4420), 434 (11051), 517 (1600), 589 (462), 660 (437). –
CD (THF) /nm (∆ε): 219 (Ϫ371.1), 233 (698.3), 287 (–17.6), 315
(–39.6), 429 (–60.8), 515 (–7.8). – IR: νFe–Cl ϭ 363 cm–1. –
FABϩMS; m/z: 1494 [M – Cl], 1529 [M ϩ].
L. A. Campbell, T. Kodadek, J.
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3c: λmax(THF) /nm (ε/dm2 mol–1): 228 (26212), 283 (5380), 337
(4278), 376 (3738), 434 (9870), 515 (1338), 590 (369), 659 (320). –
CD (THF) /nm (∆ε): 219 (–342.3), 233 (593.0), 285 (–18.0), 310
(2.3), 340 (–36.5), 428 (–42.3), 517 (–8.6). – IR: νFe–Cl ϭ 363
cm–1. – FABϩMS; m/z: 1494 [M – Cl], 1529 [M ϩ].
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3d: λmax(THF) /nm (ε /dm2 mol–1): 229 (29683), 281 (5900), 337
(4608), 371 (3640), 435 (9513), 514 (1359), 584 (423), 657 (375). –
CD (THF) /nm (∆ε): 207 (–146.7), 221 (269.4), 299 (–9.5), 335
(–27.1), 432 (–45.8), 517 (–5.0). – IR: νFe–Cl ϭ 363 cm–1. – FABϩMS;
m/z: 1494 [M – Cl], 1529.
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Chloro Manganese(III)-5α,10β,15α,20β-tetrakis[2Ј-methoxy-(aS)-
1,1Ј-binaphth-2-yl]porphyrin (4): Compound 4 was prepared from
the corresponding free base porphyrin (2a) and Mn2(CO)10, follow-
ing the same protocol as above (yield 30%). λmax(THF) /nm (ε /
dm2 mol–1) 229 (30763), 282 (5838), 338 (4282), 380 (4220), 405
(4019), 428 (3058), 487 (10125), 591 (1108), 627 (893). – CD
(THF) /nm (∆ε): 233 (384), 297 (–18.9), 333 (–31.9), 392 (–23.2),
483 (–44.9), 560 (1.7), 595 (–0.4), 607 (0.6), 622 (–1.9), 641 (0.1).
– IR: νMn–Cl ϭ 351 cm–1. – FABϩMS; m/z: 1493 [M – Cl], 1528
[M ϩ].
S. Matile, N. Berova, K. Nakanishi, S. Novkova, I. Phili-
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Styrene Oxidations: All reactions were carried out following the
same procedure. A solution of styrene (114 µL, 1 mmol), naph-
thalene (6 mg, 5 ϫ 10–2 mmol) as GC internal standard and the
catalytic precursor 3a–d or 4 (2.5 mg, 1.6 ϫ 10–3 mmol) in dry
CH2Cl2 was stirred under nitrogen shielded from ambient light at
0 °C. To this solution iodosylbenzene[19] (22 mg, 0.1 mmol) was
then added. The mixture was stirred for 3.5 h. Then the solvent
was evaporated and the crude mixture, a brown oil, was passed
through a short silica gel column (Et2O/pentane, 20:80) to eliminate
the catalyst and the remaining mixture was analysed by GC. The
enantiomeric excesses were evaluated by GC using a Cydex B capil-
lary column. The absolute configuration was assigned by compar-
ison with an optically pure standard.
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Received July 30, 1999
[O99479]
Eur. J. Org. Chem. 2000, 1165Ϫ1171
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