[2+1] Cycloaddition of diazo compounds to C60
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 8, August, 2009
1729
142.95, 143.15, 143.29, 143.48, 143.65, 143.83, 144.51, 144.73,
147.26, 167.60 (COOEt).
1´ꢀBenzylꢀ1´ꢀethoxycarbonyl(C60ꢀIh)[2´,3´:1,9]cyclopropaꢀ
[5,6]fullerene (5c). IR, ν/cm–1: 520; 1180; 1210; 1430; 1630;
1730. UV, λmax/nm: 260, 329, 425. H NMR, δ: 1.34 (t, 3 H,
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1
Bisꢀadduct 3. H NMR, δ: 1.47—1.55 (m); 2.43, 2.46, 2.47,
2.48, 2.49, 2.51, 2.55, 2.56, and 2.58 (all s); 4.45—4.55 (m).
13C NMR, δ: 14.39, 15.35, 15.53, 15.66, 44.26, 44.49, 45.26,
45.55, 50.02, 62.20, 138—147, 167.54 (COOEt), 167.61
(COOEt), 167.63 (COOEt), 167.76 (COOEt). MS, m/z: 920 [M]+.
Bisꢀadduct 4. 1H NMR, δ: 1.29—1.38 (m); 3.03, 3.05, 3.12,
3.17, 3.19, 3.21 and 3.25 (all s); 4.18—4.29 (m). 13C NMR, δ:
14.12, 14.29, 25.08, 25.27, 25.34, 25.38, 25.60, 25.67, 25.93,
52.78, 52.89, 52.96, 53.23, 53.46, 53.44, 53.51, 61.39, 61.49,
128—147, 169.09 (COOEt), 169.11 (COOEt), 169.23 (COOEt),
169.34 (COOEt).
Me, J = 7.2 Hz); 4.25 (s, 2 H, CH2); 4.37 (q, 2 H, CH2, J = 7.2 Hz);
7.21 (t, H, CH, J = 7.2 Hz); 7.43 (t, 2 H, 2 CH, J = 7.2 Hz); 7.60
(d, 2 H, 2 CH, J = 7.6 Hz). 13C NMR, δ: 14.53, 35.26, 50.20,
62.45, 76.01 (sp3), 127.67 (Ph), 129.03 (Ph), 129.23 (Ph), 136.55
(Ph), 138.09, 140.27, 141.16, 141.57, 142.08, 142.21, 142.27,
142.96, 143.06, 143.14, 143.21, 143.74, 143.96, 144.38, 144.61,
144.68, 144.71, 144.88, 145.25, 145.27, 145.30, 145.35, 145.51,
146.82, 147.88, 166.31 (COOEt). MS, m/z: 896 [M]+.
1´aꢀBenzylꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ1´(2´)aꢀhomoꢀ
(C60ꢀIh)[5,6]fullerene (6c). IR, ν/cm–1: 510; 680; 720; 1180;
1
1´ꢀEthylꢀ1´ꢀethoxycarbonylꢀ(C60ꢀIh)[2´,3´:1,9]cyclopropaꢀ
1720. UV, λmax/nm: 262, 333. H NMR, δ: 1.12 (t, 3 H, Me,
[5,6]fullerene (5a). IR, ν/cm–1: 530; 1130; 1180; 1200; 1230;
J = 7.2 Hz); 3.98 (q, 2 H, CH2, J = 7.2 Hz); 5.16 (s, 2 H, CH2);
7.22 (t, H, CH, J = 7.2 Hz); 7.44 (t, 2 H, 2 CH, J = 7.2 Hz); 7.46
(d, 2 H, 2 CH, J = 7.6 Hz). 13C NMR, δ: 14.15, 44.61, 60.39,
61.56, 127.73 (Ph), 128.71 (Ph), 129.62 (Ph), 134.54, 134.82,
134.93, 135.49, 135.86 (Ph), 137.90, 138.67, 138.76, 139.41,
140.27, 141.57, 141.75, 141.97, 142.13, 142.39, 142.56, 142.93,
143.25, 143.32, 143.49, 143.72, 143.89, 144.05, 144.06, 144.88,
147.64, 167.30 (COOEt).
1´aꢀBenzylꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ1´(2´)aꢀhomoꢀ
(C60ꢀIh)[5,6]fullerene (7b). 1H NMR, δ: 1.23 (t, 3 H, Me,
J = 7.2 Hz); 3.09 (s, 2 H, CH2); 4.32 (q, 2 H, CH2, J = 7.2 Hz);
7.24 (t, H, CH, J = 7.2 Hz); 7.32 (t, 2 H, 2 CH, J = 7.2 Hz); 7.35
(d, 2 H, 2 CH, J = 7.6 Hz). 13C NMR, δ: 14.32, 36.94, 62.32,
64.89, 127.55 (Ph), 128.46 (Ph), 130.01 (Ph), 136.91 (Ph),
135.49, 136.55, 137.07, 138.04, 138.27, 138.97, 139.29, 140.46,
141.54, 142.24, 142.30, 142.50, 142.97, 143.21, 143.25, 143.49,
143.51, 143.62, 143.70, 144.20, 144.60, 144.73, 145.14, 147.59,
171.25 (COOEt).
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1730. UV, λmax/nm: 261, 327, 425. H NMR, δ: 1.53 (t, 3 H,
Me, J = 7.2 Hz); 1.58 (t, 3 H, Me, J = 7.2 Hz); 2.96 (q, 2 H,
CH2, J = 7.2 Hz); 4.54 (q, 2 H, CH2, J = 7.2 Hz). 13C NMR, δ:
11.63, 14.44, 23.18, 50.93, 62.13, 76.20 (sp3), 137.36, 137.79,
140.53, 140.79, 141.71, 141.84, 141.87, 141.92, 142.60, 142.66,
142.74, 142.87, 143.33, 143.53, 143.92, 144.23, 144.32, 144.47,
144.83, 144.85, 144.87, 144.90, 145.27, 145.81, 147.78, 166.75
(COOEt). MS, m/z: 834 [M]+.
1´aꢀEthylꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ1´(2´)aꢀhomoꢀ
(C60ꢀIh)[5,6]fullerene (6a). IR, ν/cm–1: 520; 1200; 1220; 1730.
UV, λmax/nm: 262, 333. 1H NMR, δ: 1.35 (t, 3 H, Me, J = 7.2 Hz);
1.46 (t, 3 H, Me, J = 7.2 Hz); 3.89 (q, 2 H, CH2, J = 7.2 Hz);
4.25 (q, 2 H, CH2, J = 7.2 Hz). 13C NMR, δ: 10.58, 14.34, 32.18,
59.13, 61.40, 134.23, 134.85, 135.44, 137.73, 138.42, 138.70,
139.04, 139.99, 141.28, 141.88, 142.00, 142.07, 142.21, 142.65,
142.74, 142.80, 142.88, 142.94, 143.02, 143.19, 143.68, 144.04,
144.34, 144.96, 147.38 168.84 (COOEt).
1´ꢀIsobutylꢀ1´ꢀethoxycarbonylꢀ(C60ꢀIh)[2´,3´:1,9]cycloꢀ
propa[5,6]fullerene (5b). IR, ν/cm–1: 520; 1120; 1170; 1220;
1460; 1620; 1730. UV, λmax/nm: 260, 328, 425. 1H NMR, δ: 1.36
(d, 6 H, 2 Me, J = 6.4 Hz); 1.52 (t, 3 H, Me, J = 7.2 Hz);
2.25—2.31 (m, 1 H, CH); 2.84 (d, 2 H, CH2, J = 7.2 Hz); 4.52
(q, 2 H, CH2, J = 7.2 Hz). 13C NMR, δ: 14.88, 22.94, 28.03,
37.71, 49.27, 62.39, 75.88 (sp3), 137.65, 138.09, 140.92, 141.16,
142.09, 142.20, 142.27, 142.96, 143.02, 143.10, 143.22, 143.76,
143.94, 144.35, 144.59, 144.67, 144.69, 144.85, 145.22, 145.25,
145.27, 145.35, 145.52, 146.82, 148.08, 166.96 (COOEt). MS,
m/z: 862 [M]+.
1´ꢀ(1HꢀIndolꢀ3ꢀylmethyl)ꢀ1´ꢀethoxycarbonylꢀ(C60ꢀIh)ꢀ
[2´,3´:1,9]cyclopropa[5,6]fullerene (11). IR, ν/cm–1: 500; 710;
1180; 1410; 1440; 1620; 1720. UV, λmax/nm: 260, 329, 425.
1H NMR, δ: 1.28 (t, 3 H, Me, J = 7.2 Hz); 4.31 (q, 2 H, CH2,
J = 7.2 Hz); 4.39 (s, 2 H, CH2); 7.16 (t, H, CH, J = 6.8 Hz); 7.21
(d, H, CH, J = 6.0 Hz); 7.22 (d, H, CH, J = 6.0 Hz); 7.43 (d, H,
CH, J = 8.0 Hz); 7.55 (t, H, CH, J = 8.0 Hz); 9.81 (s, 1 H, NH).
13C NMR, δ: 14.49, 25.86, 50.83, 62.55, 76.61 (sp3), 111.30,
111.41, 119.00, 120.20, 122.93, 127.65, 133.07, 137.92, 138.25,
140.96, 141.26, 141.58, 142.09, 142.18, 142.25, 142.32, 143.01,
143.06, 143.15, 143.22, 143.29, 143.75, 143.93, 144.04, 144.35,
144.66, 144.73, 144.87, 145.23, 145.27, 145.59, 146.49, 147.80,
166.75 (COOEt). MS, m/z: 935 [M]+.
1´aꢀIsobutylꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ1´(2´)aꢀhomoꢀ
(C60ꢀIh)[5,6]fullerene (6b). IR, ν/cm–1: 520; 740; 1120; 1200;
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1430; 1460; 1620. UV, λmax/nm: 263, 330. H NMR, δ: 1.23
1´aꢀ(1HꢀIndolꢀ3ꢀylmethyl)ꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ
(d, 6 H, 2 Me, J = 6.8 Hz); 1.36 (t, 3 H, Me, J = 7.2 Hz); 1.94—2.02
(m, 1 H, CH); 3.79 (d, 2 H, CH2, J = 7.2 Hz); 4.21 (q, 2 H, CH2,
J = 7.2 Hz). 13C NMR, δ: 14.59, 23.89, 27.71, 47.27, 57.81,
61.62, 134.51, 134.98, 135.14, 135.23, 137.91, 138.67, 138.75,
139.34, 140.27, 141.34, 141.76, 141.92, 142.17, 142.42, 142.61,
142.88, 143.17, 143.19, 143.46, 143.71, 143.86, 143.99, 144.03,
144.89, 147.64, 168.82 (COOEt).
1´(2´)aꢀhomo(C60ꢀIh)[5,6]fullerene (12). IR, ν/cm–1: 520; 1180;
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1210; 1430; 1630; 1730. UV, λmax/nm: 263, 330. H NMR, δ:
1.03 (t, 3 H, CH3, J = 7.2 Hz); 3.87 (q, 2 H, CH2, J = 7.2 Hz);
5.35 (s, 2 H, CH2); 7.11 (t, H, CH, J = 6.8 Hz); 7.21 (d, H, CH,
J = 6.0 Hz); 7.37 (d, H, CH, J = 6.0 Hz); 7.43 (d, H, CH,
J = 8.0 Hz); 7.55 (t, H, CH, J = 8.0 Hz); 9.76 (s, H, NH).
13C NMR, δ: 14.05, 35.04, 61.73, 62.43, 111.59, 111.22, 118.82,
120.10, 122.69, 130.60, 135.20, 135.72, 135.93, 136.20, 137.92,
138.09, 138.75. 138.96, 139.42, 140.24, 141.58, 141.80, 141.95,
142.18, 142.32, 142.50, 142.56, 143.48, 143.60, 143.71, 143.88,
144.04, 144.87, 147.62, 167.83 (COOEt).
1´aꢀIsobutylꢀ1´aꢀethoxycarbonylꢀ1´aꢀcarbaꢀ1´(2´)aꢀhomoꢀ
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(C60ꢀIh)[5,6]fullerene (7a). H NMR, δ: 1.05 (d, 6 H, 2 Me,
J = 6.4 Hz); 1.69 (t, 3 H, Me, J = 7.2 Hz); 1.75—1.81 (m, 1 H,
CH); 2.93 (d, 2 H, CH2, J = 7.2 Hz); 4.59 (q, 2 H, CH2, J = 7.2 Hz).
13C NMR, δ: 14.79, 23.89, 26.63, 46.18, 54.25, 62.13, 135.14,
135.23, 136.55, 137.21, 138.04, 140.46, 141.68, 142.17, 142.36,
142.45, 142.97, 143.17, 143.19, 143.46, 143.57, 143.71, 144.16,
144.54, 144.79, 145.23, 147.64.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00287)
and the Council on Grants of the President of the Rusꢀ