Organometallics
Article
CDCl3): δ 7.97 (d, J = 8.0 Hz, 1H), 7.87−7.84 (m, 2H), 7.60−7.50
(m, 2H), 7.31 (d, J = 8.0 Hz, 1H), 3.56 (db, 1H), 3.41 (db, 1H), 2.55
(b, 1H), 2.43 (b, 1H), 1.81−1.76 (m, 2H), 1.43−1.35 (m, 2H), 1.07
(db, 1H), 0.89 (db, 1H). 13C NMR (100 MHz, CDCl3): δ 143.3,
142.0, 133.2, 129.5, 129.0, 128.0, 126.0, 124.7, 122.4, 121.0, 50.1,
49.3, 35.91, 35.87, 31.9, 28.1, 28.0.
exo-5-Methoxy-6b,7,8,9,10,10a-hexahydro-7,10-methanobenzo-
[a]biphenylene (3b). The title compound was prepared according to
the general procedure IV and purified by flash chromatography
(hexanes) as a colorless oil (98 mg, 98%). 1H NMR (400 MHz,
CDCl3): δ 8.56 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.69−
7.59 (m, 2H), 6.77 (s, 1H), 4.11 (s, 3H), 3.57 (db, 1H), 3.44 (db,
1H), 2.60 (b, 1H), 2.48 (b, 1H), 1.87−1.84 (m, 2H), 1.47−1.44 (m,
2H), 1.15 (db, 1H), 1.01 (db, 1H). 13C NMR (100 MHz, CDCl3): δ
156.4, 143.0, 133.5, 130.1, 126.7, 125.9, 124.2, 123.7, 122.3, 99.7,
55.8, 50.3, 49.1, 36.2, 35.9, 32.0, 28.4, 28.1. HRMS (ESI, m/z): [M +
H]+ calcdfor C18H19O 251.1436, found 251.1430.
exo-5-Chloro-6b,7,8,9,10,10a-hexahydro-7,10-methanobenzo-
[a]biphenylene (3c). The title compound was prepared according to
the general procedure IV and purified by flash chromatography
(hexanes) as a colorless oil (99 mg, 97%). 1H NMR (400 MHz,
CDCl3): δ 8.30−8.28 (m, 1H), 7.68−7.65 (m, 1H), 7.47−7.44 (m,
2H), 7.26 (s, 1H), 3.34 (db, 1H), 3.21 (db, 1H), 2.35 (b, 1H), 2.23
(b, 1H), 1.62−1.58 (m, 2H), 1.24−1.15 (m, 2H), 0.90 (db, 1H), 0.71
(db, 1H). 13C NMR (100 MHz, CDCl3): δ 142.9, 141.3, 131.5, 130.6,
130.2, 126.8, 126.02, 125.95, 122.9, 121.8, 50.4, 49.4, 35.94, 35.86,
31.9, 28.1, 28.0. HRMS (ESI, m/z): [M + H]+ calcd for C17H16Cl:
255.0941, found 255.0937.
exo-6b,7,8,9,10,10a-Hexahydro-7,10-methanobenzo[3,4]-
cyclobuta[1,2-f]quinoline (3d). The title compound was prepared
according to the general procedure IV and purified by flash
chromatography (hexanes) as a colorless oil (80 mg, 90%). 1H
NMR (400 MHz, CDCl3): δ 8.85 (dd, J1 = 2.0 Hz, J2 = 4.4 Hz, 1H),
8.04 (db, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.41 (d, J = 8.4 Hz, 1H), 7.35
(dd, J1 = 4.4 Hz, J2 = 8.4 Hz, 1H), 3.41 (db, 1H), 3.30 (db, 1H), 2.39
(b, 1H), 2.32 (b, 1H), 1.68−1.65 (m, 2H), 1.28−1.25 (m, 2H), 0.96
(db, 1H), 0.70 (db, 1H). 13C NMR (100 MHz, CDCl3): δ 149.2,
148.3, 144.0, 141.8, 130.7, 129.7, 124.6, 124.1, 121.0, 50.1, 49.0, 36.0,
35.8, 31.8, 28.0, 27.9. HRMS (ESI, m/z): [M + H]+ calcd for
C16H16N 222.1283, found 222.1275.
exo-1,2,3,4,4a,10b-Hexahydro-1,4-methanobenzo[b]-
biphenylene (3e).9i The title compound was prepared according to
the general procedure IV and purified by flash chromatography
(hexanes) as a white solid (83 mg, 94%). 1H NMR (400 MHz,
CDCl3): δ 7.81−7.79 (m, 2H), 7.42 (s, 2H), 7.41−7.38 (m, 2H), 3.37
(b, 2H), 2.41 (b, 2H), 1.64 (db, 2H), 1.28−1.26 (m, 2H), 1.04−0.96
(m, 2H). 13C NMR (100 MHz, CDCl3): δ 145.8, 134.2, 128.1, 124.5,
119.7, 50.4, 37.7, 32.4, 27.9.
exo-6-Methoxy-1,2,3,4,4a,8b-hexahydro-1,4-methanobipheny-
lene (3f).9i The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as a
colorless oil (77 mg, 96%). 1H NMR (400 MHz, CDCl3): δ 6.91 (d, J
= 8.0 Hz, 1H), 6.75 (dd, J1 = 2.0 Hz, J2 = 8.0 Hz, 1H), 6.61 (d, J = 2.0
Hz, 1H), 3.78 (s, 3H), 3.11 (b, 2H), 2.24 (b, 2H), 1.60−1.58 (m,
2H), 1.18−1.16 (m, 2H), 0.96 (db, 1H), 0.87 (db, 1H). 13C NMR
(100 MHz, CDCl3): δ 159.7, 147.3, 138.3, 122.9, 113.7, 107.7, 55.4,
49.7, 49.6, 36.9, 36.6, 32.0, 27.9, 27.8.
exo-6-(tert-Butyl)-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphe-
nylene (3g).9i The title compound was prepared according to the
general procedure IV and purified by flash chromatography (hexanes)
as a colorless oil (88 mg, 97%). 1H NMR (400 MHz, CDCl3): δ 7.31
(d, J = 6.8 Hz, 1H), 7.11 (s, 1H), 7.00 (d, J = 8.0 Hz, 1H), 3.21 (db,
2H), 2.33 (b, 2H), 1.66 (db, 2H), 1.37 (s, 9H), 1.25−1.23 (m, 2H),
1.02 (db, 1H), 0.94 (db, 1H). 13C NMR (100 MHz, CDCl3): δ 150.5,
146.3, 143.6, 124.4, 121.6, 118.9, 50.5, 50.2, 36.9, 36.8, 35.2, 32.3,
32.0, 28.1 (two overlapping signals).
exo-5-Phenyl-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphenylene
(3h).9g The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as a
colorless oil (66 mg, 90%). 1H NMR (400 MHz, CDCl3): δ 7.31 (d, J
= 7.2 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H), 7.12 (s, 1H), 3.44 (b, 2H),
2.63 (s, 3H), 2.55 (b, 2H), 1.90−1.88 (m, 2H), 1.49−1.46 (m, 2H),
1.27−1.20 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 146.7, 143.6,
136.9, 128.2, 122.8, 121.9, 50.4, 50.2, 37.01, 36.95, 32.3, 28.23, 28.17,
22.4.
exo-5-Methyl-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphenylene
(3i).9i The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as a
colorless oil (70 mg, 95%). 1H NMR (400 MHz, CDCl3): δ 7.18 (dd,
J1 = 7.6 Hz, J2 = 7.2 Hz, 1H), 7.05 (d, J = 7.6 Hz, 1H), 6.89 (d, J = 7.2
Hz, 1H), 3.22 (dd, J1 = 3.6 Hz, J2 = 7.6 Hz, 2H), 2.37 (b, 1H), 2.33
(b, 1H), 2.26 (s, 3H), 1.70−1.65 (m, 2H), 1.29−1.23 (m, 2H), 1.04
(db, 1H), 0.93 (db, 1H). 13C NMR (100 MHz, CDCl3): δ 146.1,
145.0, 132.0, 127.9, 127.6, 119.1, 49.8, 49.6, 36.5, 35.8, 32.1, 27.91,
27.85, 16.6.
exo-5-Phenyl-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphenylene
(3j).9g The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as a
white solid (92 mg, 93%). 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J
= 7.2 Hz, 2H), 7.49−7.41 (m, 3H), 7.33−7.27 (m, 2H), 6.96 (d, J =
7.2 Hz, 1H), 3.45 (db, 1H), 3.23 (db, 1H), 2.36 (b, 1H), 2.32 (b,
1H), 1.62 (db, 2H), 1.26−1.22 (m, 2H), 1.00−0.94 (m, 2H). 13C
NMR (100 MHz, CDCl3): δ 147.2, 143.4, 138.3, 134.6, 128.7 (two
overlapping signals), 128.2, 127.2, 126.9 (two overlapping signals),
124.8, 120.8, 51.5, 50.1, 36.7, 36.2, 32.1, 27.89, 27.85.
exo-1,2,3,4,4a,8b-Hexahydro-1,4-methanobiphenylene (3k).9i
The title compound was prepared according to the general procedure
IV and purified by flash chromatography (hexanes) as a colorless oil
1
(65 mg, 96%). H NMR (400 MHz, CDCl3): δ 7.33−7.31 (m, 2H),
7.14−7.12 (m, 2H), 3.31 (b, 2H), 2.40 (b, 2H), 1.73 (db, 2H), 1.33−
1.30 (m, 2H), 1.10 (db, 1H), 1.00 (db, 1H). 13C NMR (100 MHz,
CDCl3): δ 146.6, 127.2, 121.9, 50.5, 36.7, 32.0, 27.9.
exo-6-Fluoro-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphenylene
(3l).9f The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as a
1
colorless oil (71 mg, 95%). H NMR (400 MHz, CDCl3): δ 6.97−
6.87 (m, 2H), 6.75 (dd, J1 = 2.0 Hz, J1 = 8.0 Hz, 1H), 3.15 (b, 2H),
2.28 (db, 2H), 1.65−1.59 (m, 2H), 1.23−1.17 (m, 2H), 1.00 (db,
1H), 0.87 (db, 1H). 13C NMR (100 MHz, CDCl3): δ 164.1, 161.7,
147.61, 147.55, 141.55, 141.52, 123.4, 123.3, 114.5, 114.3, 109.8,
109.6, 49.55, 49.51, 36.7, 36.4, 31.8, 27.74, 27.65.
exo-1,2,3,4,4a,8b-Hexahydro-1,4-methanobiphenylene-6-car-
bonitrile (3m).9f The title compound was prepared according to the
general procedure IV and purified by flash chromatography (hexanes)
as a colorless oil (69 mg, 89%). 1H NMR (400 MHz, CDCl3): δ 7.52
(dd, J1 = 1.2 Hz, J1 = 7.6 Hz, 1H), 7.28 (s, 1H), 7.11 (d, J = 7.6 Hz,
1H), 3.27−3.24 (m, 2H), 2.33 (db, 2H), 1.65−1.63 (m, 2H), 1.23−
1.21 (m, 2H), 1.03 (db, 1H), 0.81 (db, 1H). 13C NMR (100 MHz,
CDCl3): δ 152.1, 147.3, 131.9, 125.3, 122.8, 119.8, 110.8, 51.0, 50.4,
36.5 (2 overlapping signals), 31.9, 27.6, 27.5.
exo-6-Nitro-1,2,3,4,4a,8b-hexahydro-1,4-methanobiphenylene
(3n).9f The title compound was prepared according to the general
procedure IV and purified by flash chromatography (hexanes) as
yellow oil (48 mg, 56%). 1H NMR (400 MHz, CDCl3): δ 8.13 (dd, J1
= 2.0 Hz, J1 = 8.0 Hz, 1H), 7.84 (d, J = 1.6 Hz, 1H), 7.12 (d, J = 8.0
Hz, 1H), 3.25 (b, 2H), 2.34 (b, 2H), 1.66−1.60 (m, 2H), 1.24−1.19
(m, 2H), 1.02 (db, 1H), 0.79 (db, 1H). 13C NMR (100 MHz,
CDCl3): δ 154.4, 148.1, 147.3, 123.6, 122.7, 117.5, 50.5, 49.9, 36.6,
36.5, 31.9, 27.6, 27.5.
exo-7-Allyl-5-methoxy-1,2,3,4,4a,8b-hexahydro-1,4-methanobi-
phenylene (3o). The title compound was prepared according to the
general procedure IV and purified by flash chromatography (hexanes)
as a colorless oil (87 mg, 91%). 1H NMR (400 MHz, CDCl3): δ 6.52
(s, 1H), 6.47 (s, 1H), 5.99−5.89 (m, 1H), 5.09−5.02 (m, 2H), 3.88
(s, 3H), 3.31 (d, J = 6.8 Hz, 2H), 3.26 (db, 1H), 3.12 (db, 1H), 2.30
(db, 1H), 2.25 (db, 1H), 1.62−1.59 (m, 2H), 1.21−1.16 (m, 2H),
1.04−0.99 (m, 2H). 13C NMR (100 MHz, CDCl3): δ 153.4, 148.6,
141.5, 137.8, 126.5, 119.8, 115.5, 114.8, 114.1, 56.4, 50.2, 49.8, 40.7,
38.0, 36.6, 31.8, 27.8. HRMS (ESI, m/z): [M + H]+ calcd for
C17H21O 241.1592, found 241.1582.
E
Organometallics XXXX, XXX, XXX−XXX