JHF = 2.0, 2.0 Hz, 2H), 2.46 (tdd, J = 7.8 Hz, JHF = 2.0, 2.0 Hz,
2H), 2.75 (t, J = 8.2 Hz, 2H), 3.00 (t, J = 7.8 Hz, 2H), 7.17 (d, J
= 7 Hz, 2H), 7.20 (t, J = 7.5 Hz, 1H), 7.26–7.28 (m, 2H), 7.46
(dd, J = 7.0, 1.5 Hz, 1H), 7.63 (ddd, J = 7.3, 7.3, 1.2 Hz, 1H),
7.68 (ddd, J = 7.7, 7.7, 1.7 Hz, 1H), 7.79 (d, J = 8.5 Hz, 1H),
7.83 (d, J = 8.5 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.90 (d, J =
8.0 Hz, 1H), 7.96 (d, J = 8.5 Hz, 1H), 8.03 (dd, J = 7.5, 1.5 Hz,
1H), 8.91 (s, 1H), 9.10 (d, J = 8.5 Hz, 1H); 13C NMR (126
MHz, CDCl3): δ 28.3 (d, JCF = 2 Hz), 28.4 (d, JCF = 3 Hz), 34.0
(dd, JCF = 3, 3 Hz), 34.5 (dd, JCF = 3, 3 Hz), 88.0 (dd, JCF = 13,
13 Hz), 125.8, 126.07, 126.11, 126.3, 126.7, 126.9, 127.05,
127.11, 127.2, 127.4, 127.7, 128.3, 128.4, 128.60, 128.63,
130.3, 130.4, 131.1, 132.0, 133.5, 139.0, 141.1, 153.8 (dd, JCF
= 284, 284 Hz); 19F NMR (470 MHz, CDCl3): δ 67.2 (br d, J =
55 Hz, 1F), 67.3 (br d, J = 55 Hz, 1F); IR (neat): ν 3049, 2954,
2925, 2860, 1747, 1603, 1454, 1219, 843, 771 cm–1; HRMS (EI,
TOF, 60 eV) m/z: calcd for C30H24F2 ([M]+): 422.1853, found:
422.1846.
1H), 7.73–7.80 (m, 3H), 7.87 (d, J = 8.5 Hz, 1H), 7.89 (d, J =
8.5 Hz, 1H), 7.95 (d, J = 7.5 Hz, 1H), 7.96–7.99 (m, 2H), 8.08
(d, J = 7.0 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.92 (d, J = 8.0
Hz, 1H), 9.28 (s, 1H), 9.34 (d, J = 9.0 Hz, 1H), 9.64 (s, 1H);
13C NMR (126 MHz, CDCl3): δ 122.1, 123.1, 125.8, 126.5,
126.8, 127.0, 127.11, 127.14, 127.2, 127.62, 127.65, 127.7,
127.8, 128.0, 128.5, 128.6, 128.7, 129.0, 130.3, 130.5, 130.6,
131.0, 132.13, 132.15, 133.6; IR (neat): ν 1510, 1223, 906, 831,
746 cm–1; HRMS (ESI+, TOF) m/z: calcd for C26H17 ([M+H]+):
329.1330, found: 329.1335.
Dinaphtho[1,2-a:1’,2’-h]anthracene (3e): 1H NMR (500
MHz, CDCl3): δ 7.69 (ddd, J = 8.5, 6.8, 1.4 Hz, 2H), 7.80 (ddd,
J = 8.5, 6.8, 1.4 Hz, 2H), 7.87 (d, J = 8.5 Hz, 2H), 7.91 (d, J =
8.5 Hz, 2H), 8.01 (d, J = 8.0 Hz, 2H), 8.10 (dd, J = 7.0, 1.4 Hz,
2H), 8.11 (d, J = 9.0 Hz, 2H), 9.40 (d, J = 8.0 Hz, 2H), 9.67 (s,
2H); 13C NMR (126 MHz, CDCl3): δ 125.8, 126.7, 126.8,
127.14, 127.19, 127.5, 127.7, 127.9, 128.2, 128.6, 128.7, 130.4,
130.9, 131.7, 133.5.; IR (neat): ν 904, 829, 750, 733, 521 cm–1;
HRMS (ESI+, TOF) m/z: calcd for C30H19 ([M+H]+): 379.1487,
found: 379.1469.
Naphtho[1,2-c]chrysene (3f): 1H NMR (500 MHz,
CDCl3): δ 7.69 (ddd, J = 8.0, 7.0, 1.4 Hz, 2H), 7.76 (ddd, J =
7.0, 7.0, 1.4 Hz, 2H), 7.99 (d, J = 9.8 Hz, 2H), 8.04 (d, J = 7.0
Hz, 2H), 8.14 (d, J = 6.3 Hz, 2H), 8.865 (d, J = 8.2 Hz, 2H),
8.87 (d, J = 6.3 Hz, 2H), 9.01 (d, J = 9.8 Hz, 2H); 13C NMR
(126 MHz, CDCl3): δ 121.9, 123.4, 125.9, 126.59, 126.61,
126.9, 126.9, 128.2, 128.3, 128.6, 130.1, 130.5, 130.9, 131.7;
IR (neat): ν 1595, 1259, 831, 737, 688 cm–1; HRMS (ESI+,
TOF) m/z: calcd for C26H17 ([M+H]+): 329.1330, found:
329.1343.
9-Methylnaphtho[2,1-c]chrysene (3g): 1H NMR (500
MHz, CDCl3): δ 2.90 (s, 3H), 7.19 (ddd, J = 8.2, 7.0, 1.2 Hz,
1H), 7.49 (dd, J = 7.1, 7.1 Hz, 1H), 7.53 (d, J = 9.2 Hz, 1H),
7.64 (dd, J = 7.0, 7.0 Hz, 1H), 7.72 (ddd, J = 7.6, 7.6, 1.1 Hz,
1H), 7.82 (s, 1H), 7.89 (d, J = 7.6 Hz, 1H), 7.91 (d, J = 7.6 Hz,
1H), 8.00 (d, J = 8.5 Hz, 1H), 8.12 (d, J = 4.4 Hz, 1H), 8.14 (d,
J = 4.6 Hz, 1H), 8.20 (d, J = 9.2 Hz, 1H), 8.24 (d, J = 8.5 Hz,
1H), 8.85 (d, J = 7.9 Hz, 1H), 8.87 (d, J = 8.6 Hz, 1H); 13C
NMR (126 MHz, CDCl3): δ 20.3, 122.0, 123.1, 123.4, 124.0,
124.4, 126.2, 126.4, 126.50, 126.52, 126.92, 126.93, 127.2,
127.3, 127.6, 128.2, 128.4, 129.0, 129.3, 129.4, 130.1, 130.4,
131.6, 131.9, 132.0, 132.1, 132.3; IR (neat): ν 2922, 1255, 1034,
835, 750, 733 cm–1; HRMS (ESI+, TOF) m/z: calcd for C27H19
([M+H]+): 343.1487, found: 343.1485; CCDC 1948090.
1-[3-Difluoromethylidene-5-(naphthalen-1-yl)pent-1-yl
]-naphthalene (1f): 1H NMR (500 MHz, CDCl3): δ 2.47 (tdd, J
= 8.3 Hz, JHF = 2.5, 2.5 Hz, 4H), 3.17 (t, J = 8.3 Hz, 4H), 7.30
(d, J = 6.5 Hz, 2H), 7.40 (dd, J = 7.5, 7.5 Hz, 2H), 7.46–7.54
(m, 4H), 7.73 (d, J = 8.0 Hz, 2H), 7.87 (dd, J = 8.0, 1.0 Hz, 2H),
7.99 (d, J = 8.0 Hz, 2H); 13C NMR (126 MHz, CDCl3): δ 28.0,
31.5 (t, JCF = 3 Hz), 88.8 (t, JCF = 17 Hz), 123.4, 125.5, 125.6,
126.0, 126.1, 127.0, 128.9, 131.6, 133.9, 137.3, 153.8 (t, JCF
=
284 Hz); 19F NMR (470 MHz, CDCl3): δ 67.3 (br s); IR (neat):
ν 3055, 2960, 1747, 1512, 1217, 775 cm–1; EA: calcd for
C26H22F2: C, 83.84, H, 5.95%; found: C, 83.57; H, 6.10%.
2-[3-Difluoromethylidene-5-(naphthalen-1-yl)pent-1-yl
]-3-methylnaphthalene (1g): 1H NMR (500 MHz, CDCl3): δ
2.35 (tdd, J = 8.4 Hz, JHF = 2.0 Hz, 2.0 Hz, 2H), 2.45 (s, 3H),
2.48 (tdd, J = 8.4 Hz, JHF = 2.0, 2.0 Hz, 2H), 2.82–2.87 (m, 2H),
3.17–3.23 (m, 2H), 7.32 (d, J = 9.0 Hz, 1H), 7.38–7.41 (m, 3H),
7.47–7.54 (m, 2H), 7.54 (s, 1H), 7.60 (s, 1H), 7.72–7.76 (m,
3H), 7.85–7.89 (m, 1H), 8.02 (d, J = 8.0 Hz, 1H); 13C NMR
(126 MHz, CDCl3): δ 19.6, 27.6 (d, JCF = 3 Hz), 27.9 (d, JCF
=
3 Hz), 31.5 (dd, JCF = 3, 3 Hz), 31.9 (dd, JCF = 3, 3 Hz), 88.7
(dd, JCF = 17, 17 Hz), 123.4, 125.1, 125.3, 125.55, 125.56,
126.0, 126.1, 126.9, 126.9, 127.0, 127.1, 128.2, 128.9, 131.7,
132.3, 132.4, 133.9, 134.5, 137.3, 138.2, 153.8 (dd, JCF = 283,
283 Hz); 19F NMR (470 MHz, CDCl3): δ 67.1 (br d, J = 54 Hz,
1F), 67.3 (br d, J = 54 Hz, 1F); IR (neat): ν 3055, 2954, 1745,
1597, 1261, 1215, 775, 746 cm–1; EA: calcd for C27H24F2: C,
83.91; H, 6.26%, found: C, 83.58; H, 6.44%.
Benzylstannanes 7d and 7e were prepared according to
the reported procedure,27 using a PdCl2(PhCN)2 catalyst, LiCl
(5 equiv), and (n-Bu3Sn)2 (2 equiv).
3-[3-Difluoromethylidene-5-(3-methylnaphthalen-2-yl)
pent-1-yl]phenanthrene (1h): 1H NMR (500 MHz, CDCl3): δ
2.40 (tdd, J = 8.2 Hz, JHF = 2.0, 2.0 Hz, 2H), 2.50 (s, 3H), 2.53
(t, J = 8.0 Hz, JHF = 2.0, 2.0 Hz, 2H), 2.90 (t, J = 8.2 Hz, 2H),
3.04 (t, J = 8.0 Hz, 2H), 7.42 (t, J = 4.5 Hz, 2H), 7.46 (dd, J =
8.1, 1.5 Hz, 1H), 7.58 (s, 1H), 7.62 (t, J = 7.2 Hz, 1H), 7.63 (s,
1H), 7.68 (td, J = 8.3, 1.3 Hz, 1H), 7.70–7.78 (m, 2H), 7.730 (s,
1H), 7.734 (s, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.91 (d, J = 7.9 Hz,
1H), 8.50 (s, 1H), 8.70 (d, J = 8.3 Hz, 1H); 13C NMR (126
MHz, CDCl3): δ 19.5, 27.2, 28.5, 31.7, 34.6, 88.4 (t, JCF = 17
Hz), 121.8, 122.5, 125.1, 125.3, 126.3, 126.4, 126.5, 126.6,
126.7, 126.8, 127.0, 127.3, 128.2, 128.5, 128.6, 130.0, 130.3,
3-[(Tributylstannyl)methyl]phenanthrene (7d): 1H
NMR (500 MHz, CDCl3): δ 0.80–0.89 (m, 15H), 1.21–1.29 (m,
6H), 1.41–1.48 (m, 6H), 2.59 (s, 2H*0.84), 2.59 (d, JHSn = 55.0
Hz, 2H*0.16), 7.26 (dd, J = 8.5, 1.4 Hz, 1H), 7.56 (ddd, J = 8.5,
6.8, 1.4 Hz, 1H), 7.59 (d, J = 8.5 Hz, 1H), 7.61 (ddd, J = 8.3,
6.8, 1.4 Hz, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.70 (d, J = 8.0 Hz,
1H), 7.85 (dd, J = 7.8, 1.4, 1H), 8.28 (s, 1H), 8.62 (d, J = 8.5
Hz, 1H); 13C NMR (126 MHz, CDCl3): δ 10.2, 14.4, 19.9, 28.0,
29.8, 120.2, 123.2, 125.4, 126.7, 126.9, 127.5, 127.7, 129.08,
129.12, 129.12, 130.6, 131.3, 133.0, 143.2; IR (neat): ν 2966,
1427, 1205, 881, 758 cm–1; EA: calcd for C27H38Sn: C, 67.38;
H, 7.96%, found: C, 67.41; H 7.88%.
2-[(Tributylstannyl)methyl][4]helicene (7e): 1H NMR
(500 MHz, CDCl3): δ 0.82 (t, J = 7.3 Hz, 9H), 0.86–0.91 (m,
6H), 1.21–1.29 (m, 6H), 1.42–1.50 (m, 6H), 2.60 (s, 2H*0.86),
2.60 (d, JHSn = 55.0 Hz, 2H*0.16), 7.29 (dd, J = 8.0, 1.5 Hz,
1H), 7.60 (dd, J = 7.5, 7.5 Hz, 1H), 7.65 (dd, J = 7.5, 7.5 Hz,
130.5 132.2, 132.3, 132.4 134.5, 138.2, 139.4, 153.7 (t, JCF
=
283 Hz); 19F NMR (470 MHz, CDCl3): δ 67.3 (s); IR (neat): ν
3053, 2929, 1747, 1454, 1207, 839, 744 cm–1; HRMS (ESI+,
TOF) m/z: calcd for C31H26F2Na ([M+Na]+): 459.1900, found:
459.1894.
Benzo[a]naphtho[1,2-h]anthracene (3d): 1H NMR (500
MHz, CDCl3): δ 7.67 (d, J = 7.0 Hz, 1H), 7.67 (d, J = 8.0 Hz,