1208
D. HOSSAIN AND G. G. LAVOIE
Na2SO4, filtered, and concentrated under reduced pressure to give a brown crude
solid. It was then purified by flash chromatography over silica gel (hexane–acetone
9:1) to give 10 as a white solid (165 mg, 0.342 mmol, 26%) and 11 (180 mg,
0.625 mmol, 50%) Data for 10: mp 118–120 ꢀC; IR (nmax, Nujol): 2950 (m), 2850
1
(m), 1731 (s); H NMR (300 MHz, C6D6): d 6.07 (s, 2H, olefinic), 3.93 (t, J ¼ 1.4,
2H, CHN), 2.48 (s, 2H, bridgehead), 1.32 (d, J ¼ 9.6, 1H, apical), 0.64 (d, J ¼ 9.6,
1H, apical); 13C NMR (C6D6): d 154.9 (C ¼ O), 146.2, 143.0, 139.5, 136.3 (aromatic),
134.4 (olefinic), 60.76 (CHNH), 45.4 (bridgehead), 44.5 (apical); 19F NMR (C6D6):
d ꢁ 141.7, ꢁ145.6, ꢁ154.8, ꢁ161.3, ꢁ162.0; HRMS-ESI (M þ Hþ): calcd. for
C20H8F10N2O, 483.0550; obsd., 483.0522.
cis-endo-N-(Perfluorophenyl)bicyclo[2.2.1]hept-5-ene-2,3-diamine (11).
Compound 2 (200 mg, 1.01 mmol) and K2CO3(836 mg, 6.04 mmol) were suspended
in acetonitrile (5 mL) and stirred at 90 ꢀC for 1 h. After cooling to room temperature,
hexafluorobenzene (592 mg, 3.18 mmol) was added under nitrogen. The suspension
was heated at 90 ꢀC for 36 h. The color of the suspension turned to beige from
off-white. After cooling to room temperature, the reaction mixture was diluted with
H2O (12 mL), extracted with dichloromethane (3 ꢃ 12 mL), and washed with H2O
(2 ꢃ 7 mL). The combined organic phases were dried over anhydrous Na2SO4, fil-
tered, and concentrated under reduced pressure to give a light yellow semisolid. It
was then purified by flash chromatography over silica gel (hexane–EtOAc 7:1) to
give 11 as a light yellow oil (199 mg, 0.685 mmol, 69%). 1H NMR (400 MHz,
C6D6): d 5.94 (s, 1H, olefinic), 5.82 (s, 1H, olefinic), 5.02 (s, 1H, NH), 3.55 (s, 1H,
CHNH), 2.98, 2.92, 2.37 (s, 3H, CHNH2 and bridgehead), 1.28 (d, J ¼ 9.1, 1H,
apical), 0.90 (d, J ¼ 9.1, 1H, apical) ppm; 13C NMR (C6D6): d 136.0, 135.0 (olefinic
C’s), 56.2 (CHNH), 53.0, 49.0, 48.0 (CHNH2 and bridgehead C’s), 45.0 (apical) ppm;
resonances for C6F5 ring could not be assigned due to low intensity. 19F NMR
(C6D6): d ꢁ 161.2 (d, 2 F, ortho), ꢁ165.5 (t, 2 F, meta), ꢁ174.7 (t, 1 F, para) ppm;
HRMS-ESI (M þ Hþ) m=z: calcd. for C13H11F5N2, 291.0921; obsd., 291.0940.
cis-endo-N,N’-Di(perfluorophenyl)bicyclo[2.2.1]hept-5-ene-2,3-diamine
(12). Compound 2 (20 mg, 90 mmol) and K3PO4 (149 mg, 702 mmol) were suspended
in DMSO (1.5 mL) and stirred at 90 ꢀC under nitrogen for 1 h. After cooling to room
temperature, hexafluorobenzene (112 mg, 0.601 mmol) was added, and the suspen-
sion was heated at 100 ꢀC for 48 h. The color of the suspension turned to amber from
beige. The reaction mixture was cooled to room temperature. Water (10 mL) was
added, and the product was extracted with chloroform (3 ꢃ 5 mL). The combined
organic phases were dried over anhydrous Na2SO4, filtered, and concentrated under
reduced pressure to give a yellow solid. This crude solid was then purified by flash
chromatography over silica gel (hexane–EtOAc 15:1) to give 12 as a clear oil
(3.00 mg, 6.60 mmol, 7%). 1H NMR (300 MHz, C6D6): d 5.82 (t, J ¼ 1.7, 2H, olefinic),
3.68 (s, 2H, CHN), 3.33 (br s, 2H, NH), 2.62 (s, 2H, bridgehead), 1.20 (d, J ¼ 9.3,
1H, apical), 0.82 (d, J ¼ 9.3, 1H, apical); 13C NMR (C6D6): d 145.7, 143.2, 139.5,
137.0 (aromatic C’s), 135.0 (olefinic), 67.5 (CHNH), 47.3 (bridgehead), 44.0 (apical);
19F NMR (C6D6): d ꢁ 159.4 (d, 4 F, ortho), ꢁ163.7 (t, 4 F, meta), ꢁ170.4 (t, 2 F,
para); HRMS-ESI (M þ Hþ) m=z: calcd. for C19H10F10N2, 457.0763; obsd.,
457.0749.