Reduction of Strained Polycycles: Pyrene Anion Strain
A R T I C L E S
δH (THF-d8, 260 K, brown-red) 6.83 (s, 1H, H14), 6.71 (t, 1H, H19),
6.60 (d, 1H, H18), 6.51 (d, 1H, H20), 6.17 (d, 2H, H10), 5.11 (d, 2H,
H9), 4.82 (s, 2H, H8), 2.57 (t, 1H, H16), 2.39 (s, 2H, JC,H ) 162.33
Hz, JH,*H ) 8.66 Hz, H1), 2.27 (t, 1H, H11), 2.20 (t, 1H, H17), 1.54 (t,
1H, H12) ppm. δC (THF-d8, 260 K) 146.95 (C10b), 146.09 (C13),
145.13 (C8a), 140.64 (C15), 140.52 (C7), 136.47 (C10c), 133.46 (C14),
126.23 (C19), 125.77 (C18), 125.58 (C10), 125.43 (C20), 118.07
(C10a), 108.47 (C8), 101.63 (C9), 39.92 (C16), 39.59 (C17), 33.71
(C1), 33.12 (C12), 32.97 (C11), 30.10 (C2). δLi (THF-d8, 260 K) -0.20
ppm.
1H, H12), 1.08 (m, 1H, H18′), 0.89 (m, 1H, H17′/H12′), 0.88 (m, 1H,
H17), 0.87 (m, 1H, H12′/H17′), 0.74 (m, 1H, H13′), 0.61 (m, 1H, H13),
0.28 (m, 2H, H15′ and 16), 0.10 (m, 3H, H14, H15, and H16′), -0.11
(m, 1H, H14′) ppm. δC (THF-d8, 220 K) 142.56 (C5a), 141.31 (C8a),
136.95 (C7), 136.75 (C10b), 134.98 (C10c), 131.27 (C10), 129.42 (C4),
126.30 (C3), 112.20 (C6), 112.20 (C3a), 109.64 (C8), 108.94 (C9),
108.31 (C10a), 108.31 (C2), 102.43 (C5), 52.98 (C1), 40.63 (C11),
37.57 (C19), 34.06 (C14), 33.60 (C16), 32.41 (C15), 30.66 (C18), 29.87
(C12), 27.02 (C17), 26.75 (C13) ppm.
5b/2Li+: The ∆Gq for the dynamic process was measured to be
8.6 ( 0.2 kcal/mol.
3b/2K+: The ∆Gq for the dynamic process was measured to be 8.9
( 0.2 kcal/mol.
δH (THF-d8, 165 K, brown-red) 7.98 (b, 2H, H14), 4.61 (b, 1H,
H15′), 3.55 (H13′), 2.61 (s, 2H, H4/H10), 2.58 (b, H14′), 2.50 (s, 2H,
H4/H10), 2.43 (b, 1H, H15), 2.14 (b, 4H, H12′ and H13), 1.95 (b, 2H,
H12), 1.57 (s, 2H, H1/H3), 1.29 (s, 2H, H1/H3), 0.96 (b, 2H, H11),
0.83 (b, 2H, H11′) ppm. δC (THF-d8, 165 K) 151.91 (C10b), 144.28
(C3a/C10a), 143.40 (C3a/C10a), 137.46 (C2), 108.53 (C3/C4), 107.68
(C3/C4), 98.04 (C1/C3), 83.74 (C1/C3), 38.12 (C11), 37.89 (C14),
36.20 (C15), 32.77 (C12), 29.39 (C13) ppm. δLi (THF-d8, 165 K) 1.98
ppm. Carbon atoms C10b and C2 were assigned according to the 13C
NMR of 1b. The differentiation between hydrogen and carbon atoms
C1 and C3 (also C4 and C10) is not possible.
δH (THF-d8, 273 K, brown) 6.85 (s, 1H, H14), 6.76 (t, 1H, H19),
6.64 (d, 1H, H18), 6.55 (d, 1H, H20), 6.25 (d, 1H, H10), 5.18 (d, 1H,
H9), 4.86 (s, 1H, H8), 2.60 (t, 1H, H16), 2.42 (s, 1H, JC,H ) 163.64
Hz, JH,*H ) 8.12 Hz, H1), 2.33 (t, 1H, H11), 2.22 (t, 1H, H17), 1.60 (t,
1H, H12) ppm. δC (THF-d8, 273 K) 146.78 (C10b), 145.90 (C13),
145.13 (C8a), 142.29 (C7), 140.37 (C15), 136.03 (C10c), 133.13 (C14),
126.59 (C19), 126.26 (C10), 125.63 (C18), 125.60 (C20), 118.98
(C10a), 108.27 (C8), 102.14 (C9), 39.72 (C16), 39.50 (C17), 33.80
(C1), 33.18 (C12), 32.85 (C11), 30.30 (C2) ppm.
4a/2Li+: δH (THF-d8, 273 K, wine-red) 6.58 (d, 1H, H4), 5.94 (dd,
2H, H9 and H10), 5.84 (s, 1H, H3), 5.76 (s, 1H, H8), 5.69 (s, 1H, H6),
5.67 (d, 1H, H5), 3.24 (s, 1H, H1, JC,H ) 130.92 Hz, JH,*H ) 10.61
Hz), 2.45 (dd, 1H, H18), 2.22 (d, 1H, H11), 1.83 (dt, 1H, H18′), 1.60
(m, 2H, H11′ and H17′), 1.03 (dd, 1H, H12), 0.86 (m, 2H, H16 and
H17′), 0.63 (dd, 1H, H16′), 0.38 (dd, 1H, H12′), 0.23 (dd, 1H, H14),
-0.01 (m, 2H, H13′ and H15′), -0.26 (dd, 1H, H13), -0.50 (dd, 1H,
H14′), -0.82 (dd, 1H, H15) ppm. δC (THF-d8, 273 K) 143.39 (C5a),
139.78 (C8a), 138.59 (C10b), 135.69 (C7), 135.31 (C10c), 131.15 (C4),
129.77 (C10), 129.13 (C3), 114.21 (C8), 111.57 (C3a), 110.16 (C6),
109.52 (C9), 108.51 (C10a), 103.31 (C2), 102.76 (C5), 49.07 (C1),
40.84 (C11), 38.37 (C18), 33.40 (C15), 32.23 (C12), 32.08 (C17), 31.91
(C14), 27.81 (C16), 27.13 (C13) ppm. δLi (THF-d8, 273 K) -0.70 ppm.
4a/2K+: δH (THF-d8, 240 K, wine-red) 6.66 (d, 1H, H4), 5.98 (d,
1H, H9), 5.88 (d, 1H, H10), 5.87 (s, 1H, H3), 5.83 (s, 1H, H8), 5.82
5b/2K+: The ∆Gq for the dynamic process was measured to be 8.6
( 0.2 kcal/mol.
δH (THF-d8, 170 K, blue) 9.93 (b, 2H, H14), 8.65 (b, 1H, H15′),
4.01 (b, 2H, H13′), 3.22 (b, 2H, H14′), 2.89 (b, 1H, H15), 2.41 (b, 2H,
H13), 2.34 (b, 2H, H12′), 2.04 (b, 2H, H12), 1.89 (s, 2H, H4/H10),
1.83 (s, 2H, H4/H10), 0.99 (s, 2H, H1/H3), 0.89 (s, 2H, H1/H3), 0.64
(b, 2H, H11), 0.56 (b, 2H, H11′) ppm. δC (THF-d8, 170 K) 156.66
(C10b), 145.02 (C3a/C10a), 144.60 (C3a/C10a), 141.70 (C2), 107.71
(C3/C4), 106.89 (C3/C4), 98.47 (C1/C3), 89.71 (C1/C3), 39.17 (C14),
37.89 (C11), 37.34 (C15), 33.77 (C13), 30.60 (C12) ppm. Carbon atoms
C10b and C2 were assigned according to the 13C NMR of 1b. The
differentiation between hydrogen and carbon atoms C1 and C3 (also
C4 and C10) is not possible.
5c/2Li+: δH (THF-d8, 273 K, dark-blue) 6.33 (d, 1H, H4), 6.24 (d,
1H, H10), 6.05 (d, 1H, H9), 5.78 (s, 1H, H3), 5.77 (s, 1H, H8), 5.59
(s, 1H, H6), 5.58 (d, 1H, H5), 2.83 (s, 1H, JC,H ) 122.36 Hz, H1),
2.38 (m, 1H, H19), 2.08 (m, 1H, H11), 1.98 (m, 1H, H19′), 1.90 (m,
1H, H11′), 1.42 (m, 1H, H18′), 1.27 (m, 1H, H12), 1.14 (m, 1H, H18),
0.89 (m, 1H, H17′), 0.86 (m, 3H, H12, H17 and H17′), 0.68 (m, 1H,
H13), 0.53 (m, 1H, H13′), 0.26 (m, 1H, H15), 0.21 (m, 1H, H14′),
0.18 (m, 1H, H16), 0.07 (m, 2H, H15′ and H16′), 0.03 (m, 1H, H14)
ppm. δC (THF-d8, 273 K) 142.25 (C5a), 141.40 (C8a), 136.23 (C10b),
136.08 (C7), 135.15 (C10c), 129.76 (C4), 128.03 (C10), 126.99 (C3),
112.99 (C6), 111.26 (C3a), 110.45 (C8), 110.16 (C9), 108.33 (C10a),
104.05 (C2), 103.55 (C5), 48.95 (C1), 39.54 (C11), 37.54 (C19), 33.80
(C14), 33.51 (C16), 32.50 (C15), 30.80 (C18), 30.62 (C12), 27.15
(C17), 26.61 (C13) ppm. δLi (THF-d8, 273 K) 0.05 ppm.
(s, 1H, H6), 5.81 (d, 1H, H5), 3.49 (s, 1H, JC,H ) 130.58 Hz, JH,*H
)
11.14 Hz, H1), 2.46 (dd, 1H, H18), 2.28 (d, 1H, H11), 1.86 (m, 1H,
H18′), 1.62 (d, 1H, H11′), 1.57 (d, 1H, H17′), 1.03 (d, 1H, H12), 0.85
(m, 1H, H15), 0.81 (m, 1H, H17′), 0.62 (t, 1H, H15′), 0.41 (dd, 1H,
H12′), 0.27 (d, 1H, H13), -0.03 (m, 1H, H14 and H16), -0.38 (d,
1H, H16′), -0.44 (d, 1H, H13′), -1.04 (dd, 1H, H14′) ppm. δC (THF-
d8, 240 K) 142.87 (C5a), 140.17 (C8a), 138.85 (C10b), 136.09 (C7),
134.97 (C10c), 131.54 (C4), 129.85 (C3), 129.36 (C10), 114.89 (C8),
111.74 (C6), 111.24 (C3a), 109.14 (C9), 107.15 (C10a), 104.51 (C5),
103.57 (C2), 49.85 (C1), 40.69 (C11), 38.17 (C18), 32.48 (C14), 32.11
(C12), 31.96 (C17), 31.51 (C13), 27.76 (C15), 27.12 (C16) ppm.
5a/2Li+: δH (THF-d8, 240 K, wine-red) 6.33 (d, 1H, H4), 5.84 (s,
1H, H3), 5.81 (d, 1H, H10), 5.76 (d, 1H, H9), 5.58 (s, 1H, H8), 5.51
(d, 1H, H5), 5.45 (s, 1H, H6), 3.27 (s, 1H, JC,H ) 130.64 Hz, JH,*H
)
5c/2K+: δH (THF-d8, 298 K, dark-blue) 6.40 (d, 1H, H4), 6.35 (d,
1H, H10), 6.14 (d, 1H, H9), 5.87 (s, 1H, H3), 5.79 (s, 1H, H8), 5.63
(d, 1H, H5), 5.61 (s, 1H, H6), 3.17 (s, 1H, JC,H ) 122.96 Hz, H1),
2.38 (m, H19), 2.14 (m, H11), 2.03 (m, H19′), 1.93 (m, H11′), 1.47
(m, H18′), 1.30 (m, H12), 1.15 (m, H 18), 0.97 (m, H17′), 0.90 (m,
H12′), 0.85 (m, H17), 0.77 (m, H13′), 0.58 (m, H13), 0.36 (m, H15′),
0.24 (m, H16′), 0.20 (m, H14′), 0.16 (m, H15), 0.14 (m, H16), -0.02
(m, H14) ppm. δC (THF-d8, 298 K) 142.64 (C5a), 141.98 (C8a), 138.30
(C7), 136.31 (C10b), 135.03 (C10c), 130.25 (C4), 129.16 (C10), 126.84
(C3), 112.47 (C6), 112.05 (C3a), 110.79 (C9), 110.00 (C8), 109.60
(C10a), 107.34 (C2), 103.07 (C5), 50.50 (C1), 39.42 (C11), 37.58 (C19),
33.93 (C14), 33.64 (C16), 32.54 (C15), 30.89 (C18), 30.35 (C12), 27.27
(C17), 26.84 (C13) ppm.
10.44 Hz, H1), 2.39 (m, 1H, H11), 2.30 (m, 1H, H19), 1.95 (m, 1H,
H19′), 1.91 (m, 1H, H11′), 1.42 (m, 1H, H18), 1.14 (m, 1H, H12),
1.08 (m, 1H, H18′), 0.87 (m, 3H, H12′, H17, and H17′), 0.69 (m, 1H,
H13′), 0.60 (m, 1H, H13), 0.27 (m, 2H, H15′ and 16), 0.08 (m, 3H,
H14, H15, and H16′), -0.14 (1H, H14′) ppm. δC (THF-d8, 240 K)
142.59 (C5a), 140.94 (C8a), 136.58 (C10b), 135.89 (C7), 135.21
(C10c), 131.07 (C10), 128.89 (C4), 126.43 (C3), 112.85 (C10a), 112.53
(C3a), 111.75 (C6), 108.73 (C8 and C9), 106.84 (C2), 102.18 (C5),
52.39 (C1), 40.85 (C11), 37.65 (C19), 34.13 (C14), 33.73 (C16), 32.42
(C15), 30.84 (C18), 30.75 (C12), 27.01 (C17), 26.66 (C13) ppm. δLi
(THF-d8, 240 K) -0.69 ppm.
5a/2K+: δH (THF-d8, 220 K, wine-red) 6.40 (d, 1H, H4), 5.88 (s,
1H, H3), 5.84 (d, 1H, H9), 5.74 (d, 1H, H10), 5.65 (s, 1H, H8), 5.60
(d, 1H, H5), 5.54 (s, 1H, H6), 3.36 (s, 1H, H1, JC,H ) 132.05 Hz, JH,*H
) 10.15 Hz), 2.44 (m, 1H, H11), 2.33 (m, 1H, H19), 1.95 (m, 1H,
H19′/H11′), 1.89 (m, 1H, H11′/H19′), 1.43 (m, 1H, H18), 1.21 (m,
6: Synthesis. A. 1,10-Bis(3,5-bis(methoxycarbonyl)phenyl)-1,9-
decadiyne (9). A mixture of 3,5-bis(methoxycarbonyl)phenyl triflate
86c (8.18 g, 23.9 mmol), DBU (4.93 mL, 9.03 g, 59.4 mmol), 1,9-
decadiyne (2.14 mL, 1.67 g 11.4 mmol), CuI (0.45 g, 2.4 mmol), and
9
J. AM. CHEM. SOC. VOL. 126, NO. 21, 2004 6773