MULTIPLE CODES AND ALTERNATIVE PERFORMANCES IN KING LEAR, I.i. 23–265

Reactivity of Seven-Membered-Ring trans-Alkenes with Electrophiles

“…Alkene 21 was formed in 4 d in 94% based on1 H NMR spectroscopic analysis of the area of a peak of the standard (δ 6.71) and the area of one of the alkene CH 2 peaks (δ 4.82). The spectral data are consistent with the data reported above for alkene 21 2. 6 ) δ 7.54-7.52 (m, 2H), 7.34-7.32 (m, 2H), 7.22-7.18 (m, 4H), 7.13-7.10 (m, 1H), 7.05-7.02 (m, 1H), 5.21 (t, J = 3.6, 1H), 4.89 (d, J = 9.9, 1H), 2.56-2.46 (m, 2H), 2.35 (dd, J = 18.4, 8.6, 1H), 2.30-2.27 (m, 1H), 2.10 (m, 1H), 2.02 (dd, J = 9.7, 4.7, 1H), 1.96-1.91 (m, 1H), 1.88-1.81 (m, 1H), 1.59-1.51 (m, 1H), 1.31-1.27 (m, 1H), 1.21-1.19 (m, 1H), 1.14 (s, 9H), 1.02 (m, 1H and s, 9H), 0.70 (dd, J = 14.2, 12.5, 1H); 13 C NMR (100 MHz, C 6 D 6 ) δ 178.4 (C), 174.6 (C), 145.4 (C), 144.9 (C), 133.5 (C), 129.4 (CH), 128.9 (CH), 128.5 (CH), 128.2 (CH), 127.2 (CH), 127.0 (CH), 124.8 (CH), 81.4 (CH), 50.4 (CH), 47.6 (CH), 47.0 (CH), 36.1 (CH 2 ), 29.2 (CH 3 ), 28.3 (CH 3 ), 25.5 (CH 2 ), 25.3 (CH 2 ), 21.8 (C), 21.6 (C), 18.0 (CH 2 ), 17.8 (CH 2 ); IR (ATR) 1772, 1700, 1598, 1095, 824 cm -1 ; HRMS (ESI) m / z calcd for C 35 H 43 NNaO 3 Si (M + Na) + 552.2904, found 552.2901.…”

“…Graph S1. [trans-cycloheptene 12] 0 = 0.076 M; [3,5-dichloro-1,4-benzoquinone 22] 0 = 0.12 M; k = 1.31 x 10 -4 M -1 s -1 y = 1.38E-04x -3.45E-01 R² = 9.76E-01 y = 1.27E-04x -5.10E-01 R² = 9.75E-01 y = 1.28E-04x -1.66E+00 R² = Compounds4, 11, 14, 17-19, 24, 25, 29, and 31 were assigned by analogy to nOe data and previously reported structures [1][2]. …”

“…The spectral data are consistent with the data reported previously for alkene 21. 2 Enone 24. Enone 24 was prepared using the representative procedure for conjugate additions using diene S2 (0.017 g, 0.11 mmol), cyclohexene silacyclopropane 2 (0.029 g, 0.13 mmol), AgOCOCF 3 (0.038 mL, 0.030 M in C 6 D 6 , 1 mol %), benzaldehyde (0.012 mL, 0.11 mmol), and 3,5-dichloro-1,4-benzoquinone 22 (0.019 g, 0.11 mmol) in C 6 D 6 (0.70 mL).…”

“…All solvents and reagents were degassed before use. Compounds S1-S3, 1, 1-2 2, 3 3, 9, 12, 15, 16, 20, 21, 26, and 27 [1][2] were synthesized by known methods. Unless otherwise noted all reagents were commercially available.…”

“…The spectroscopic data are consistent with the data reported previously for alkene S3. 2 The reaction mixture was concentrated in vacuo. Flash chromatography (5:95 EtOAc:hexanes) resulted in decomposition of enone 25.…”