PAPER
Functionalized Pyrenes via Electrocyclization
3691
Di-tert-Butyl {[7-(Benzyloxy)-2-methoxypyrene-1,3-
diyl]bis(methylene)}dicarbamate (6c)
(ArCH), 129.1 (ArCq), 129.6 (ArCH), 131.5 (ArCq), 133.0 (ArCq),
135.2 (ArCH), 141.8 (ArCq), 156.3 (-CONH-).
Prepared as described for 6a using 5c.
HRMS (ESI+): m/z [M + Na]+ calcd for C35H46O5N2SiI2Na:
Yield: 211 mg (63%); colorless solid; mp 204–205 °C; Rf = 0.34
879.1158; found: 879.1181.
(CH2Cl2–EtOAc, 9:1).
1H NMR (400 MHz, CDCl3): d = 1.47 [s, 18 H, -C(CH3)3], 4.00 (s,
3 H, -OCH3), 4.92 (m, 2 H, -CH2NH-), 5.02 (m, 4 H, -CH2NH-),
5.38 (s, 2 H, -OCH2-), 7.38 (m, 1 H, BnH), 7.45 (m, 2 H, BnH), 7.57
(m, 2 H, BnH), 7.81 (s, 2 H, ArH), 8.07 (d, 3J = 9.3 Hz, 2 H, ArH),
8.33 (d, 3J = 9.3 Hz, 2 H, ArH).
Acknowledgment
This work was supported by the Engineering and Physical Sciences
Research Council (grant EP/D060192/1).
13C NMR (125 MHz, CDCl3, 298 K): d = 28.4 [-C(CH3)3], 36.2
(-CH2NH-), 63.6 (-OCH3), 70.5 (-OCH2Bn), 79.5 [-C(CH3)3], 112.1
(ArCH), 120.1 (ArCq), 122.6 (ArCq), 123.9 (ArCq), 125.3 (ArCq),
127.6 (ArCH), 128.1 (ArCH), 128.3 (ArCq), 128.7 (ArCH), 129.9
(ArCq), 131.9 (ArCH), 136.9 (ArCH), 155.1 (ArCq), 155.6 (ArCq),
156.9 (-CONH-).
Supporting Information for this article is available online at
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HRMS (ESI+): m/z [M + Na]+ calcd for C36H40N2O6Na: 619.2779;
found: 619.2795.
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Di-tert-Butyl {[4¢-(tert-Butyldimethylsilyloxymethyl)-2¢,6¢-
bis(iodoethynyl)-(1,1¢-biphenyl)-3,5-diyl]bis(methylene)}dicar-
bamate (7d)
To a solution of 5d (50 mg, 82.6 mmol) dissolved in anhydrous
CH2Cl2 was added I2 (46 mg, 180 mmol, 2.2 equiv) and DMAP (22
mg, 180 mmol, 2.2 equiv), and the reaction mixture was heated at
40 °C for 6 h. The solution was partitioned between CH2Cl2 (20
mL) and sat. aq Na2S2O3 (20 mL). The aqueous phase was re-ex-
tracted with CH2Cl2 (2 × 30 mL) and the combined organic layers
were washed with brine (10 mL), dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude residue was puri-
fied by flash chromatography (CH2Cl2–EtOAc, 19:1) and then
washed with hexane (5 mL) and filtered to give 7d.
Yield: 63 mg (89%); colorless solid; mp 138–139 °C; Rf = 0.27
(CH2Cl2–EtOAc, 9:1).
1H NMR (400 MHz, CDCl3): d = 0.13 [s, 6 H, -Si(CH3)2], 0.96 [s,
9 H, -SiC(CH3)3], 1.49 [s, 18 H, -OC(CH3)3], 4.40 (m, 4 H, -CH2NH-),
4.68 (s, 2 H, -CH2O-), 4.82 (m, 2 H, -CH2NH-), 7.22 (m, 1 H, ArH),
7.35 (m, 2 H, ArH), 7.46 (s, 2 H, ArH).
13C NMR (125 MHz, CDCl3): d = –5.3 [-Si(CH3)2], 18.4 (-SiC-),
26.0 [-SiC(CH3)3], 28.5 [-C(CH3)3], 44.7 (-CH2NH-), 63.9 (-CH2O-),
79.5 [-C(CH3)3], 80.7 (-CCI), 93.2 (-CCI), 122.8 (ArCH), 126.3
(ArCH), 128.7 (ArCq), 131.5 (ArCH), 138.0 (ArCq), 138.3 (ArCq),
140.6 (ArCq), 145.5 (ArCq), 155.9 (-CONH).
HRMS (ESI+): m/z [M + Na]+ calcd for C35H46O5N2SiI2Na:
879.1158; found: 879.1123.
Di-tert-Butyl {[7-(tert-Butyldimethylsilyloxymethyl)-5,9-di-
iodopyrene-1,3-diyl]bis(methylene)}dicarbamate (8d)
To a solution of 7d (32 mg, 37.3 mmol) dissolved in anhydrous tol-
uene (5 mL), was added AuCl (3.5 mg, 14.9 mmol, 0.4 equiv) and
the mixture was degassed, purged with argon and stirred at r.t. for
16 h. The solution was then concentrated under reduced pressure
and purified by flash chromatography (CH2Cl2–EtOAc, 19:1) to
give 8d.
Yield: 12 mg (38%); pale-yellow solid; mp 176–177 °C; Rf = 0.40
(CH2Cl2–EtOAc, 9:1).
1H NMR (400 MHz, CDCl3, 298 K): d = 0.25 [s, 6 H, -Si(CH3)2],
1.09 [s, 9 H, -SiC(CH3)3], 1.53 [s, 18 H, -OC(CH3)3], 4.97 (m, 4 H,
-CH2NH-), 5.04 (m, 2 H, -CH2NH-), 5.27 (s, 2 H, -CH2O-), 7.88 (s,
1 H, CHa), 8.50 (s, 2 H, CHc), 8.89 (s, 2 H, CHb).
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Acta Chem. Scand. 1969, 23, 567.
13C NMR (125 MHz, CD2Cl2): d = –4.8 [-Si(CH3)2], 18.9 (-SiC-),
26.5 [-SiC(CH3)3], 28.8 [-C(CH3)3], 43.1 (-CH2NH2-), 65.2 (-CH2O-),
80.2 [-C(CH3)3], 100.3 (ArCq), 123.8 (ArCq), 124.7 (ArCq), 126.6
Synthesis 2010, No. 21, 3686–3692 © Thieme Stuttgart · New York