## 2 Materials and Methods  
### Synthesis  
#### Synthesis  
2.1.1. Synthesis of 4,5-Dichloro-9,10-dihydro-9,10-ethanoanthracene-12-carbonitrile **5 anti**, 1,8-Dichloro-9,10-dihydro-9,10-ethanoanthracene-12-carbonitrile **5 syn**, and 9,10-Dihydro-9,10-ethanoanthracene-12-carbonitrile **5 dec**  
A solution of 1,8-dichloroanthracene **1** (200 mg, 0.8 mmol) and acrylonitrile **2** (200 \(\mu\)L, 3 mmol) in (1 mL) xylene was added into a 10 mL microwave reaction tube containing a stir bar. This tube was taken into the Microwave CEM Discover SP system after sealing with a plastic septum. The reaction was stirred for 40 h (4 times, 10 h per each) at 150 \({}^{\circ}\)C temperature, with power at 250 W and pressure of 17 psi as a default setting. After removing the solvent via a rotary evaporator, the NMR of the residue was recorded. \({}^{1}\)H-NMR (CDCl\({}_{3}\), JEOL 400 MHz): \(\delta\) = 1.95-2.01 (m, 1H, CH(H-12, H-12\({}^{\prime}\), H-12\({}^{\prime\prime}\))), 2.17-2.26 (m, 1H, CH(H-12, H-12\({}^{\prime}\), H-12\({}^{\prime\prime}\))), 2.90-2.95 (m, 1H, CH(H-11, H-11\({}^{\prime}\), H-11\({}^{\prime\prime}\))), 4.39 (t, \(J\) = 3.2 Hz, 0.18H, H-9\({}^{\prime\prime}\)), 4.44 (t, \(J\) = 2.8 Hz, 0.26H, H-9\({}^{\prime}\)), 4.57 (d, \(J\) = 2.4 Hz, 0.18H, H-10\({}^{\prime\prime}\)), 4.60 (d, \(J\) = 3.2 Hz, 0.56H, H-10), 5.46 (t, \(J\) = 2.4 Hz, 0.56H, H-9), 5.71 (d, \(J\) = 2.8 Hz, 0.26H, H-10\({}^{\prime}\)), 7.07-7.42 (m, 6.36H). 1.2 Synthesis of 4,5-Dichloro-12-cyano-9,10-dihydro-9,10-ethanoanthracen-12-yl Acetate **6**anti**, 1,8-Dichloro-12-cyano-9,10-dihydro-9,10-ethanoanthracen-12-yl Acetate **6**syn**, and 12-Cyano-9,10-dihydro-9,10-ethanoanthracen-12-yl Acetate **6**dec**  
A solution of 1,8-dichloroanthracene **1** (1.2 g, 5 mmol) and 1-cyanovinyl acetate **3** (1.5 mL, 14 mmol) in (5 mL) xylene was refluxed at 150 \({}^{\circ}\)C for 48 h. After removing the solvent via a rotary evaporator, the isomers mixture was separated on thick TLC with the eluent system ethyl acetate: petroleum ether (1:10). For **6**_anti_**: \({}^{1}\)H-NMR (CDCl\({}_{3}\), JEOL 400 MHz): \(\delta\) = 1.92(m,3H), 2.65(dd, \(J\) = 2.8 Hz, 3.2, 2H), 5.12(s, 1H), 5.38(t, \(J\) = 2.8 Hz, 1H), 7.10-7.20 (m,2H), 7.24(s, 2H), 7.26(s,1H), 7.37(d, \(J\) = 7.2 Hz, 1H); \({}^{13}\)C-NMR (CDCl\({}_{3}\), JEOL 100 MHz): \(\delta\) = 20.63, 36.21, 41.93, 51.71, 72.50, 117.90, 124.44, 125.06, 127.73, 127.98, 128.11, 128.37,129.64, 129.81, 138.41, 138.53, 138.64, 139.52, 168.80 ppm. For **6**_syn_**: \({}^{1}\)H-NMR (CDCl\({}_{3}\), JEOL 400 MHz): \(\delta\) = 1.97 (s, 3H), 2.03(dd, \(J\) = 2, 3.2 Hz, 1H), 2.70(dd, \(J\) = 3.2, 2.8 Hz, 1H), 4.41(t, \(J\) = 2.8 Hz, 1H), 6.09 (s, 1H), 7.14-7.26(m, 6H) ppm; \({}^{13}\)C-NMR (CDCl\({}_{3}\), JEOL 100 MHz): \(\delta\) = 20.64, 42.96, 43.66, 44.83, 72.07, 117.76, 122.02, 122.17, 127.29, 127.66, 128.54, 128.98, 132.40, 132.52, 133.53, 133.80, 144.23, 164.43, 168.80 ppm. For **6**_dec_: \({}^{1}\)H-NMR (CDCl\({}_{3}\), JEOL 400 MHz): \(\delta\) = 1.90(s, 3H), 2.04(dd, J = 2.4, 3.2, 1H), 2.65(dd, \(J\) = 2.4, 2, 1H), 4.36(t, \(J\) = 2, 1H), 5.07(s, 1H), 7.12-7.31(m, 7H), 7.47-7.49(m, 1H) ppm; \({}^{13}\)C-NMR (CDCl\({}_{3}\), JEOL 100 MHz): \(\delta\) = 20.68, 42.91, 43.72, 44.71, 7.20, 118.44, 123.42, 123.55, 125.96, 126.48, 127.25, 127.60, 128.50, 128.96, 136.34, 136.65, 141.96, 142.84, 169.01 ppm. 1.3 Synthesis of 4,5-Dichloro-12-(phenylsulfonyl)-9,10-dihydro-9,10-ethanoanthracene **7**_anti_**, 1,8-Dichloro-12-(phenylsulfonyl)-9,10-dihydro-9,10-ethanoanthracene **-7**_syn_**, and 12-(Phenylsulfonyl)-9,10-dihydro-9,10-ethanoanthracene **-7**_dec_  
A solution of 1,8-dichloroanthracene **1** (370 mg, 1.5 mmol) and phenyl vinyl sulfone **4** (302 mg, 2.4 mmol) in (3.5 mL) xylene was added into a 10-mL microwave reaction tube containing a stir bar. This tube was taken into the Microwave CEM Discover SP system after sealing with a plastic septum. The reaction was stirred for 40 h at 150 \({}^{\circ}\)C temperature, with power at 250 W and pressure at 17 psi as a default setting.