SYNTHETIC METHOD
J = 17.9 Hz, 1F). HRMS (APCI+): calcd. for C21H3Br2F12O,
19F NMR (565 MHz, CDCl3): δ –139.3 (m, 1F), À139.5 (dd,
J = 62.0 Hz, 19.1 Hz, 1F), À141.5 (dd, J = 63.2 Hz, 17.9 Hz, 1F),
À142.9 (t, J = 16.7 Hz, 1F), À143.0 (t, J = 15.5 Hz, 1F), À145.0
(dtm, J = 62.0 Hz, 16.1 Hz, 1F), À145.3 (dtm, J = 62.0 Hz,
16.1 Hz, 1F), À153.5 (t, J = 17.9 Hz, 1F), À154.3 (tm,
J = 15.5 Hz, 1F), À154.9 (tm, J = 17.9 Hz, 1F), À156.3 (m, 1F),
À157.7 (t, J = 19.1 Hz, 1F). HRMS (ESI-): calcd. for
C21H2BrF12O, [M-H]-: 576.9103; found: 576.9103. IR (neat,
cmÀ1): 3578, 1647, 1527, 1495, 1458, 1388, 1185, 1114, 1075,
1022, 994, 927, 869, 820.
[M]+: 655.8275; found: 655.8275. IR (neat, cmÀ1): 1667,
1647, 1527, 1507, 1496, 1472, 1458, 1439, 1412, 1375, 1339,
1249, 1187, 1084, 1025, 1000, 942, 836, 820. mp: 210°C. Anal.
calcd. for C21H3Br2F12O: C, 38.33; H, 0.31; Br, 24.29; F, 34.65.
found: C, 38.05; H, 0.43; Br, 24.25; F, 34.46.
1,2,5,6,7,8,9,10,11,12,13,14-Dodecafluoro-4H-benzo[f] naph-
tha[2,1-c]chromene (15a). An anhydrous DMF (4 mL) sus-
pension
of
1-bromo-2-((1-bromo-3,4,5,6,7,8-hexafluoro-
naphthalen-2-yl)methoxy)-3,4,5,6,7,8-hexafluoronaphthalene
(14a) (526 mg, 0.8 mmol, 1.0 equiv.) and freshly activated
copper powder (508 mg, 8 mmol, 10 equiv.) was heated at
150°C. After being stirred for 2.5 h, the reaction mixture
was filtered via a pad of Celite. The filtrate was dissolved in
Et2O (15 mL) and washed with 1 M HCl aq. (~10 mL × 3) and
brine (~10 mL). The combined organic layer was dried over
Na2SO4 and concentrated under reduced pressure after filtra-
tion to give 1,2,5,6,7,8,9,10,11,12,13,14-dodecafluoro-4H-
1-Bromo-2-(((1-bromonaphthalen-2-yl)oxy)methyl)-3,4,5,6,7,8-
hexafluoronaphthalene (14b). To a THF (37 mL) solution of (1-
bromo-3,4,5,6,7,8-hexafluoronaphthalen-2-yl) methanol (13)
(1.3 g, 3.7 mmol, 1.0 equiv.), 1-bromonaphthalen-2-ol
(990 mg, 4.4 mmol, 1.2 equiv.) and PPh3 (1.2 g, 4.4 mmol, 1.2
equiv.) was added DIAD (953 μL, 4.4 mmol, 1.2 equiv.). The
reaction mixture was stirred for 1 h. The resulting suspension
was concentrated under reduced pressure. The residual
crude was dissolved in MeOH (20 mL) and purified by filtra-
tion to give the product 1-bromo-2-(((1-bromonaphthalen-2-
1
benzo[f]naphtha [2,1-c]chromene (15a) as a white solid. H
NMR (600 MHz, acetone-d6): δ 5.93 (d, J = 13.8 Hz, 1H), 5.15
(d, J = 13.8 Hz, 1H). 13C NMR (151 MHz, acetone-d6): δ 148.8
(d, J = 13 Hz), 145.0 (dm, J = 269 Hz), 143.6 (dm, J = 254 Hz, 3
peaks were overlapped), 143.2 (dm, J = 257 Hz), 141.8 (dm,
J = 260 Hz), 141.6 (dm, J = 250 Hz), 140.4 (dd, J = 251 Hz,
15 Hz), 138.9 (dm, J = 260 Hz, 3 peaks were overlapped),
137.8 (dt, J = 250 Hz, 16 Hz), 127.9 (d, J = 17 Hz), 120, 116.2
(m), 115.9 (m), 113.1, 112.0 (m), 107.2 (m), 65.0. 19F NMR
(565 MHz, acetone-d6): δ –137.7 (m, 1F), À139.0 (m, 1F),
À141.2 (dd, J = 66.8 Hz, 16.7 Hz, 1F), À145.3 (dd, J = 68.0 Hz,
17.9 Hz, 1F), À146.7 (m, 1F), À147.7 (dtm, J = 66.8 Hz,
15.5 Hz, 1F), À147.9 (dtm, J = 66.8 Hz, 15.5 Hz, 1F), À157.7
(t, J = 19.1 Hz, 1F), À157.8 (m, 1F), À158.3 (tm, J = 16.7 Hz,
1F), À158.4 (tm, J = 17.9 Hz, 1F), À160.5 (t, J = 19.1 Hz, 1F).
HRMS (ESI-): calcd. for C21H2F12O, [M+I]-: 624.8964; found:
624.8963. IR (neat, cmÀ1): 1668, 1645, 1532, 1500, 1457,
1438, 1410, 1380, 1345, 1248, 1172, 1118, 1090, 1077, 1026,
1009, 988, 972, 898, 853. mp: 220–222°C.
yl)oxy)methyl)-3,4,5,6,7,8-hexafluoronaphthalene
(14b)
(1.7 g, 3.1 mmol, 83% yield) as a white solid. 1H NMR
(600 MHz, CDCl3): δ 8.23 (d, J = 8.6 Hz, 1H), 7.85 (d,
J = 8.9 Hz, 1H), 7.82 (d, J = 8.3 Hz, 1H), 7.59 (tm, J = 7.7 Hz,
1H), 7.45 (tm, J = 7.5 Hz, 1H), 7.44 (d, J = 8.9 Hz, 1H), 5.61 (d,
J = 2.8 Hz, 2H). 13C NMR could not be measured due to low
solubility in any solvent. 19F NMR (565 MHz, CDCl3): δ –
136.2 (m, 1F), À136.4 (tm, J = 16.7 Hz, 1F), À142.6 (ddm,
J = 69.1 Hz, 16.7 Hz, 1F), À144.9 (dtm, J = 69.1 Hz, 17.6 Hz,
1F), À152.4 (t, J = 17.9 Hz, 1F), À153.6 (tm, J = 19.1 Hz, 1F).
HRMS (APCI+): calcd. for C21H8Br2F6O, [M]+: 547.8841;
found: 547.8841. IR (neat, cmÀ1): 2924, 2854, 1748, 1715,
1698, 1667, 1647, 1625, 1594, 1559, 1544, 1527, 1507, 1496,
1458, 1421, 1375, 1348, 1339, 1261, 1252, 1240, 1181, 1045,
1025, 998, 906, 824. mp: 238°C. Anal. calcd. for C21H8Br2F6O:
C, 45.85; H, 1.47; Br, 29.05; F, 20.72. found: C, 46.00; H, 1.47;
Br, 29.12; F, 20.69.
2’-(Bromomethyl)-3,3’,4,4’,5,5’,6,6’,7,7’,8,8’-dodecafluoro-[1,1’-
5,6,7,8,9,10-Hexafluoro-4H-benzo[f]naphtha[2,1-c]chromene
(15b). An anhydrous DMF (30 mL) suspension of 1-bromo-
2-(((1-bromonaphthalen-2-yl)oxy)methyl)-3,4,5,6,7,8-
binaphthalen]-2-ol (16a)43
. To a CH2Cl2 (2.4 mL) solution of
1,2,5,6,7,8,9,10,11,12,13,14-dodecafluoro-4H-benzo[f] naphtha
[2,1-c]chromene (15a) was added BBr3 (227 μL, 2.4 mmol,
3.0 equiv.) and the resulting mixture was stirred at 40°C for
18 h. After being cooled at À78°C, the resulting solution
was carefully diluted with EtOH. The reaction mixture was
quenched with H2O and extracted with CH2Cl2 (~10 mL × 2).
The combined CH2Cl2 extracts were washed with brine
(~10 mL), dried over Na2SO4, and concentrated under re-
duced pressure after filtration. The residual crude was puri-
fied by silica gel column chromatography (0–15% EtOAc in
hexane as an eluent) to give the product 2’-(bromomethyl)-
3,3’,4,4’,5,5’,6,6’,7,7’,8,8’-dodecafluoro-[1,1’-binaphthalen]-2-ol
(16a) (339 mg, 0.58 mmol, 73% yield in 2 steps) as a brown
hexafluoro naphthalene (14b) (3.3 g, 6 mmol, 1.0 equiv.) and
freshly activated copper powder (3.8 g, 60 mmol, 10 equiv.)
was heated at 150°C. After being stirred for 2.5 h, the reaction
mixture was filtered via a pad of Celite. The filtrate was dis-
solved in Et2O (~50 mL) and washed with 1 M HCl aq.
(~50 mL × 3) and brine (~50 mL). The combined organic layer
was dried over Na2SO4 and concentrated under reduced pres-
sure after filtration to give 5,6,7,8,9,10-hexafluoro-4H-benzo[f]
naphtha[2,1-c]chromene (15b) as a white solid. 1H NMR
(600 MHz, CDCl3): δ 7.86 (m, 2H), 7.41 (m, 2H), 7.34 (m,
2H), 5.59 (d, J = 13.8 Hz, 1H), 4.74 (d, J = 13.8 Hz, 1H). 13C
NMR (151 MHz, CDCl3): δ 155.1, 150.0 (d, J = 12 Hz), 142.8
(dm, J = 259 Hz), 142.5 (dm, J = 253 Hz), 141.2 (dm,
J = 259 Hz), 139.2 (dm, J = 257 Hz, 2 peaks were overlapped),
131.7 (d, J = 7 Hz), 131.4, 129.8, 128.7, 128.6 (d, J = 17 Hz),
126.9, 124.5, 122.8 (d, J = 6 Hz), 122.1, 117.9, 117.6, 114.7 (d,
J = 13 Hz), 112.2 (m), 63.9. 19F NMR (565 MHz, CDCl3): δ –
128.7 (t, J = 16.7 Hz, 1F), À144.7 (dd, J = 62.0 Hz, 19.1 Hz,
1F), À145.5 (d, J = 19.1 Hz, 1F), À146.0 (dtm, J = 62.0 Hz,
15.5 Hz, 1F), À155.5 (t, J = 19.1 Hz, 1F), À156.4 (tm,
J = 19.1 Hz, 1F). HRMS (ESI-): calcd. for C21H8F6O, [M+H]+:
1
oil. H NMR (600 MHz, CDCl3): δ 5.97 (bs, 1H), 4.27 (dd,
J = 10.5 Hz, 1.5 Hz, 1H), 4.15 (dd, J = 10.5 Hz, 2.2 Hz, 1H). 13C
NMR (151 MHz, acetone-d6): δ 146.6 (dd, J = 251 Hz, 12 Hz),
145.2 (dm, J = 251 Hz), 145.2 (d, J = 14 Hz), 144.0 (dm,
J = 249 Hz), 143.5 (dm, J = 244 Hz), 142.4 (dm, J = 246 Hz),
141.6 (dm, J = 251 Hz), 141.5 (dm, J = 255 Hz), 140.8 (dm,
J = 248 Hz), 139.4 (dm, J = 251 Hz, 3 peaks were overlapped),
137.3 (dt, J = 250 Hz, 14 Hz), 129.4 (d, J = 14 Hz), 126.4, 117.2
(m), 116.4 (m), 112.0 (tm, J = 9 Hz), 110.8, 106.3 (m), 22.2.
Chirality DOI 10.1002/chir