Supporting Information Co(III)-Catalyzed Synthesis of Quinazolines via C-H Activation of -Sulfinylimines and Benzimidates Fen Wang, He Wang, Qiang Wang, Songjie Yu, Xingwei Li* Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 1113, China Email: xwli@dicp.ac.cn Table of Contents General Considerations...S2 General procedure for synthesis of -sulfinyl imines....s2 ptimization Studies......S2-S3 Procedure for the annulation of -sulfinyl imines with dioxazolones...s3 Spectral Data of Compounds 3aa-3ao and 3aaa...S4-S15 Synthesis of Quinazoline Product 5...S15 Spectral Data of Compounds 5aa-5aq...S16-S22 Derivatization of product 3aa...S22-S23 Derivatization of product 7...S23-S24 Synthesis of intermediate 8...S24-S25 Crystal structure of 3aaa...S26-S27 Mechanistic Studies...S28-S3 References...S3 MR Spectra...S31-S86 S1
General Considerations All cobalt-catalyzed reactions were carried out in a nitrogen-filled dry box. 1 H and 13 C MR spectra were recorded using CDCl3 as a solvent on a MHz spectrometer at 298 K. The chemical shift is given in dimensionless δ values and is frequency referenced relative to SiMe4 in 1 H and 13 C MR spectroscopy. High-resolution mass spectra were obtained on an Agilent Q-TF 65 spectrometer. Dichloroethane was distilled from CaH2 and was stored in a dry box. All other solvents were obtained from commercial sources and were used as received. General procedure for synthesis of -sulfinyl imine via condensation of ketones with tert-butanesulfinamide According to a reported literature, 1 to a solution of tert-butanesulfinamide (5 mmol,.625 g) and a ketone (5 mmol) in THF (15 ml) was added dropwise (Et)4Ti (1 mmol, 2.5 ml) under 2 atmosphere. Then the mixture was stirred at 65 o C for 12 hours. After this, EtAc (1 ml) was added, followed by slow addition of saturated brine (3 ml). The mixture was immediately filtered through celite and the filter cake was washed with EtAc. The solution was transferred to a separatory funnel and was washed with brine. The organic layer was dried over anhydrous a2s4. The crude product was purified by silica gel chromatography with an eluent of PE/EtAc. Table S1. ptimization Studies a Ph S 1a Ph Ph 2a Co, Ir, or Rh catalyst additive solvent, 1-1 o C 16 h H Ph entry catalyst (mol %) additive yield (%) b (mol %) 3aa 3aaa 1 [RhCp*Cl2]2 (5) AgSbF6 () 34 36 2 [RhCp*Cl2]2 (5) AgTf2 () 37 27 3 [RhCp*(MeC)3](SbF6)2 (5) - 28 38 4 [IrCp*Cl2]2 (5) AgTf2 () 25 18 5 [CoCp*Cl2]2 (5) AgTf2 () 71 6 [CoCp*(C)I2] (1) AgTf2 () 78 7 [CoCp*(C)I2] (1) AgSbF6 () 1 8 [CoCp*(C)I2] (8) AgTf2 (16) 68 S2 3aa 3aaa
9 c [CoCp*(C)I2] (1) AgTf2 () 94 1 d [CoCp*(C)I2] (1) AgTf2 () 11 e [CoCp*(C)I2] (1) AgTf2 () 34 5 a Reaction conditions: imine 1a (.2 mmol), 2a (1.2 mmol), DCE (3 ml), catalyst, additive, 16 h, 1 o C, sealed tube under nitrogen. b yield of isolated products. c 1 o C. d PhC()3 was used as the amidating reagent. e Benzophenone imine was used. Procedure for the annulation of -sulfinyl imines with dioxazolones -Sulfinyl imine (1a, 57.1 mg,.2 mmol), CoCp*(C)I2 (9.5 mg, 1 mol %), AgTf2 (15.5 mg, mol %), and dioxazolone 2a (39.1 mg, 1.2 equiv) were weighed into a pressure tube, to which was added 1,2-dichloroethane (3 ml) under 2. The reaction mixture was stirred for 16 h at 1 o C. After removal of 1,2-dichloroethane under reduced pressure, methanol (3 ml) was added, followed by addition of sodium borohydride (22.8 mg, 3 equiv). ote: The hydrolyzed benzophenone by-product and the quinazoline product accidentally have the same Rf in chromatography, so abh4 was added to convert benzophenone to the corresponding alcohol. The mixture was stirred at room temperature for 3 min. Purification was performed by flash column chromatography on silica gel using EtAc and petroleum ether to afford the desired product. Yield: 78% (56.4 mg). Spectral Data of Compounds 3aa-3ao and 3aaa 3aa Product 3aa was obtained as a white solid in 78% yield (56.4 mg). 1 H MR ( MHz, CDCl3) δ 8.7 (d, J = 7.4 Hz, 2H), 8.17 (d, J = 8.5 Hz, 1H), 8.13 (d, J = 8.4 Hz, S3
1H), 7.91-7.88 (m, 3H), 7.64-7. (m, 3H), 7.57-7.5 (m, 4H). 13 C MR (1 MHz, CDCl3) δ 168.3, 1.2, 15, 138.2, 137.6, 133.5, 13.5, 13.2, 129.9, 129.1, 128.6, 128.5 (two carbon signals), 12 (two carbon signals), 121.7. HRMS (ESI) Calcd for [CH142+H] + 283.1235, Found 283.1233. Product 3ba was obtained as a white solid in 81% yield (56.9 mg). 1 H MR ( MHz, CDCl3) δ 8.66 (dd, J = 6.6, 2.9 Hz, 2H), 8.15 (d, J = 1.9 Hz, 1H), (d, J = 8.9 Hz, 1H), 7.81 (d, J = 8.4 Hz, 2H), 7.59 (d, J= 8.4 Hz, 2H), 7.55-7.48(m, 4H). 13 C MR (1 MHz, CDCl3) δ 16, 161.1, 152.7, 1., 137.6, 136.6, 135.7, 131.4, 13, 12, 128.7, 128.6, 128.3, 128.2, 12, 119.9. HRMS (ESI) Calcd for [CH12Cl22+H] + 35456, Found 35454. Product 3ca was obtained as a white solid in 64% yield (56.3 mg). 1 H MR ( MHz, CDCl3) δ 8.64 (dd, J = 6.6, 3.2 Hz, 2H), 8.33 (d, J = 1.9 Hz, 1H), 7.9 (d, J = 8.9 Hz, 1H), 7.75-7.71 (m, 4H), 7.63-7. (m, 1H), 7.54-7.5 (m, 3H). 13 C MR (1 MHz, CDCl3) δ 167.1, 16, 152.7, 137.5, 13, 131.9, 131.6 (two overlapping signals), 13, 13.7, 128.7, 128.6, 128.5, 127.8, 124.9, 1.. HRMS (ESI) Calcd for [CH12Br22+H] + 438.9445, Found 438.9442. S4
F 3da F Product 3da was obtained as a white solid in 85% yield (54.1 mg). 1 H MR ( MHz, CDCl3) δ 8.63 (d, J = 4.5 Hz, 2H), 6 (dd, J = 8.9, 6.1 Hz, 1H), 7.84 (dd, J = 7.9, 5.6 Hz, 2H), 7.72 (dd, J = 9.6, 1.8 Hz, 1H), 7.5-7.49 (m, 3H), 7.3-7.23 (m, 3H). 13 C MR (1 MHz, CDCl3) δ 166.9, 165.5 (d, JC-F = 254.4 Hz), 164.3, 16 (d, JC-F = 249.2 Hz), 16, 153.8, 137.7, 133.5 (d, JC-F = 3.2 Hz), 132.2 (d, JC-F = 8.5Hz), 13.9, 129.5 (d, JC-F = 1.4 Hz), 128.6 (d, JC-F = 14.8 Hz), 118.8, 117.7 (d, JC-F = 2 Hz), 115.8 (d, JC-F = 21.6 Hz), 112.9 (d, JC-F =.2Hz). HRMS (ESI) Calcd for [CH12F22+H] + 319.147, Found 319.144. Product 3ea was obtained as a white solid in 52% yield (43.5 mg). 1 H MR ( MHz, CDCl3) δ 8.7-8.67 (m, 2H), 8.47 (s, 1H), 8.15 (d, J = 8.7 Hz, 1H), 7.99 (d, J = 8.1 Hz, 2H), 7.9 (d, J = 8.2 Hz, 2H), 7.73 (dd, J = 8.7, 1.5 Hz, 1H), 7.55-7.53 (m, 3H). 13 C MR (1 MHz, CDCl3) δ 167.1, 161.3, 151.5, 1.4, 137.1, 135.3 (q, JC-F = 32.9 Hz), 132.3 (q, JC-F = 32.6 Hz), 131.3, 13.5, 13.2, 128.8, 128.7, 127.7, 127.2 (q, JC-F = 4.3 Hz), 125.7 (q, JC-F = 3.7 Hz), 12 (q, JC-F = 51.2 Hz) 122.9 (q, JC-F = 3.1 Hz), 122.6, (q, JC-F = 5 Hz). HRMS (ESI) Calcd for [C22H12F62+H] + 41983, Found 41986. S5
Product 3fa was obtained as a white solid in 58% yield (39.7 mg). 1 H MR ( MHz, CDCl3) δ 8.67 (d, J = 6.8 Hz, 2H), 4 (d, J = 9.1 Hz, 1H), 7.86 (d, J = 8.3 Hz, 2H), 7.53-7.51 (m, 3H), 7.43 (s, 1H), 7.16-7.1 (m, 3H), 1 (s, 3H), 3.92 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 166.6, 163.6, 161.1, 1.7, 154.5, 138.4, 131.7, 13.32, 13.3, 128.5, 128.4, 128.3, 119.9, 11, 113.9, 16.6, 55.7, 55.4. HRMS (ESI) Calcd for [C22H1822+H] + 343.1447, Found 343.1446. Product 3ga was obtained as a white solid in 84% yield (52.1 mg). 1 H MR ( MHz, CDCl3) δ 8.71 (d, J = Hz, 2H), 3 (d, J = 8.5 Hz, 1H), 7.94 (s, 1H), 7.8 (d, J = 7.8 Hz, 2H), 7.55-7.5 (m, 3H), 7.41-7.35 (m, 3H), 2. (s, 3H), 2.5 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 167.7, 1.3, 152.2, 144.3, 1., 138.4, 13, 13.3, 13.1, 129.2, 129.1, 128.6, 128.4, 12, 126.7, 119.8, 2, 21.4. HRMS (ESI) Calcd for [C22H182+H] + 311.1548, Found 311.155. Product 3ha was obtained as a white solid in 68% yield ( mg). 1 H MR ( MHz, CDCl3) δ 8.64-8. (m, 2H), 1 (d, J = 3.8 Hz, 1H), 7.92 (d, J = 5.5 Hz, 1H), 7.58 (t, J = 4.6 Hz, 2H), 7.53-7.47 (m, 3H), 7.22 (dd, J = 4.8, 4.1 Hz, 1H). 13 C MR (1 S6
MHz, CDCl3) δ 163.3, 1.8, 153.4, 142.7, 137.8, 135.2, 13.7, 13.3, 129.3, 128.5, 128.4, 128.3, 125.1, 122.8. HRMS (ESI) Calcd for [C16H12S2+H] + 29364, Found 29364. Product 3ia was obtained as a white solid in 69% yield (21.4 mg). 1 H MR ( MHz, CDCl3) δ 8.69 (d, J = 6.4 Hz, 2H), 6 (d, J = 8.3 Hz, 1H), 7.87 (s, 1H), 7.7-7.64 (m, 3H), 7.54-7. (m, 5H), 2.52 (s, 6H). 13 C MR (1 MHz, CDCl3) δ 167.8, 159.7, 15.5, 138.3 (two overlapping signals), 137.8, 13, 135.7, 13.6, 13.5, 13.2, 128.8, 128.5, 128.4, 128.3, 127.2, 125.7, 121.7, 21.9, 21.6. HRMS (ESI) Calcd for [C22H182+H] + 311.1548, Found 311.1546. Product 3ja was obtained as a white solid in 73% yield (46.5 mg). 1 H MR ( MHz, CDCl3) δ 8.72-8.7 (m, 2H), 7.89 (d, J = 8.4 Hz, 1H), 7.64-7.49 (m, 8H), 7.33-7.28 (m, 1H). 13 C MR (1 MHz, CDCl3) δ 166.76 (d, JC-F = 2.7 Hz), 166.73, 162.8 (d, JC-F = 245.8 Hz), 1.3 (d, JC-F = 1.3 Hz), 157.8 (d, JC-F = 257.5 Hz), 142.6 (d, JC-F = 12.2 Hz), 139.4 (d, JC-F = 7.4 Hz), 137.5, 13, 13.2 (d, JC-F = 8.1 Hz), 128.8, 128.6, 126.6 (d, JC-F = 7.5 Hz), 125.9 (d, JC-F = Hz), 122.8 (d, JC-F = 2.2 Hz), 122.3 (d, JC-F = 4.9 Hz), 117.6 (d, JC-F = 18.2 Hz), 117.14 (d, JC-F = 22.5 Hz), 117.13 (d, JC-F = 21 Hz). HRMS (ESI) Calcd for [CH12F22+H] + 319.147, Found 319.146. S7
Product 3ka was obtained as a yellow solid in 78% yield (59.7 mg). 1 H MR ( MHz, CDCl3) δ 8.81-8.78 (m, 3H), 8.75 (s, 1H), 8.47 (s, 1H), 8.14-9 (m, 3H), 3 (t, J = 8.5 Hz, 2H), 7.97 (d, J = 8.5 Hz, 1H), 7.67-7.49 (m, 7H). 13 C MR (1 MHz, CDCl3) δ 17.1, 159.1, 146.7, 138.3, 135.3, 134.1, 13, 132.1, 13.6, 13.4, 129.3, 128.8 (two overlapping signals), 128.6 (two overlapping signals), 128.4, 128.2, 128.1, 127.9, 127.8, 127.4, 127.3, 126.8, 126.7, 126.3, 1.3. HRMS (ESI) Calcd for [C28H182+H] + 383.1548, Found 383.1548. Product 3la was obtained as a white solid in 61% yield (4 mg). 1 H MR ( MHz, CDCl3) δ 8.67-8.65 (m, 2H), 8.16 (d, J = Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.54-7.51 (m, 3H), 7.43 (dd, J = 8.8, Hz, 1H), 7.31 (m, 2H), 7. (s, 1H), 2.41 (s, 3H), 2.17 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 17, 161.2, 152.1, 139.9, 137.8, 136.3, 135.3, 133.2, 13.8, 13.7, 13.1, 13, 128.8, 128.6, 128.5,12 (two overlapping signals), 12,.9,19.4. HRMS (ESI) Calcd for [C22H17Cl2+H] + 345.1159, Found 345.1161. 3ma S8
Product 3ma was obtained as a white solid in 66% yield (42.8 mg). 1 H MR ( MHz, CDCl3) δ 8.64 (d, J = 7.4 Hz, 2H), 7.93 (s, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.52-7.47 (m, 3H), 7.3 (d, J = 9.8 Hz, 1H), 7.24-7.21(m, 3H), 2.58 (s, 3H), 2.39 (s, 3H), 2.16 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 169.4, 1.4, 151.6, 144.6, 138.4, 136.9, 135.1, 133.2, 13.5, 13.3, 13, 129.8, 129.2, 128.6, 128.4, 127.9, 126.8, 1.8, 22.1,.9, 19.4. HRMS (ESI) Calcd for [C23H2+H] + 325.175, Found 325.175. Product 3na was obtained as a white solid in 43% yield (29.3 mg). 1 H MR ( MHz, CDCl3) δ 8.63 (d, J = Hz, 2H), 7.57-7.55 (m, 4H), 7.45-7.35 (m, 5H), 7.1 (d, J = 9.1 Hz, 1H), 1 (s, 3H), 2.2 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 168.5, 163.9, 1.9, 153.9, 138.4, 137.1, 136.4, 13.7, 13.4, 129.6, 129.1, 128.6, 128.5, 128.4, 125.6, 1.2, 11, 16.5, 55.8, 19.9. HRMS (ESI) Calcd for [C22H182+H] + 327.1497, Found 327.1499. Product 3oa was obtained as a white solid in 82% yield (53.9 mg). 1 H MR ( MHz, CDCl3) δ 8.66-8.64 (m, 2H), 7.75 (dd, J = 9.8, 2.5 Hz, 1H), 7.7 (dd, J = 9.1, 6.1 Hz, 1H), 7.52-7.49 (m, 3H), 7.29-7.21 (m, 3H), 7.19 (s, 1H), 2. (s, 1H), 2.16 (s, 1H). 13 C MR (1 MHz, CDCl3) δ 169.7, 165.6 (d, JC-F = 254.1 Hz), 161.2, 153.2 (d, JC-F = 13.2 Hz), 137.9, 136.5, 135.2, 1331, 13.7 (d, JC-F = 8.5 Hz), 13 (d, JC-F = 1.4 Hz), 129.9 (d, JC-F = 1.9 Hz), 128.8, 128.5, 119.9, 117.3 (d, JC-F = 2 Hz), S9
112.6 (d, JC-F =.2 Hz),.9, 19.4. HRMS (ESI) Calcd for [C22H17F2+H] + 329.1454, Found 329.1456. Product 3pa was obtained as a white solid in 46% yield (21.6 mg). 1 H MR ( MHz, CDCl3) δ 8.61-8. (m, 2H), 7.97 (d, J = 8.4 Hz, 1H), 7.85 (s, 1H), 7.54-7.48 (m, 3H), 7. (d, J = 8.4 Hz, 1H), 2.98 (s, 3H), 2.58 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 167.7, 1.3, 15.7, 144.4, 138.4, 13.2, 12, 128.5, 128.4, 128.1, 124.7, 121.1, 2, 21.9. HRMS (ESI) Calcd for [C16H142+H] + 235.1235, Found 235.1235. Product 3qa was obtained as a white solid in 48% yield (22.9 mg). 1 H MR ( MHz, CDCl3) δ 8.54 (dd, J = 7.6, Hz, 2H), 2 (dd, J = 9.1, Hz, 1H), 7.61 (dd, J = 9.8, 2.5 Hz, 1H), 7.49-7.44 (m, 3H), 7.26 (td, J = 8.7, 2.5 Hz, 1H), 2.92 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 167.9, 165.5 (d, JC-F = 7.7 Hz), 161.1, 152 2 (d, JC-F = 13.7 Hz), 137.9, 13.7, 128.6, 128.5, 127.6 (d, JC-F = 1.5 Hz), 1.2, 117.1 (d, JC-F = 2 Hz), 112.8 (d, JC-F =. Hz),.6. HRMS (ESI) Calcd for [C15H11F2+H] + 23985, Found 23984. Product 3ra was obtained as a white solid in 39% yield (28.4 mg). 1 H MR ( MHz, CDCl3) δ 8.66 (dd, J = 7.8, 1.8 Hz, 2H),7.99 (d, J = 8.1 Hz, 2H), 7.97(s, 1H), 7.92 (d, J = 8.5 Hz, 1H), 7.86 (d, J = 8.2 Hz, 2H), 7.56-7.49 (m, 3H), 7. (dd, J = 8.6, 1.5 Hz, 1H), 2.62 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 166.3, 1.3, 152.3, 144.9, S1
141.3, 13, 131.7 (q, JC-F = 32.4 Hz), 13.6, 13.4 (two overlapping signals), 129.7, 128.6, 128.6, 128.3, 126.1, 125.5 (q, JC-F = Hz), 119.6, 22.1. HRMS (ESI) Calcd for [C22H15F32+H] + 365.1266, Found 365.1265. Product 3ra was obtained as a white solid in 48% yield (3 mg). 1 H MR ( MHz, CDCl3) δ 8.72-8.7 (m, 2H), 8.45 (s, 1H), 8.28 (d, J = 8.7 Hz, 1H), 7.8 (d, J = 8.1 Hz, 2H), 7.7 (dd, J = 8.7, 1.5 Hz, 1H), 7.56-7.53 (m, 3H), 7.43 (d, J = 7.9 Hz, 2H), 2.51 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 168.6, 161.3, 151.5, 1.8, 137.6, 134.9 (q, JC-F = 32.9 Hz), 134.2, 13, 13.2, 129.5, 128.8, 128.6, 128.5, 126.9 (q, JC-F = 4.3 Hz), 122.9, 122.3 (q, JC-F = 2.1 Hz), 122.1, 21.5. HRMS (ESI) Calcd for [C22H15F32+H] + 365.1266, Found 365.1269. Product 3ab was obtained as a white solid in 83% yield (52.6 mg). 1 H MR ( MHz, CDCl3) δ 8.65 (d, J = 8.6 Hz, 2H), 8.14 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 7.92-7.9 (m, 3H), 7.61-7.59 (m, 3H), 7.56 (t, J = 7.9 Hz, 1H), 7.49 (d, J = 8.6 Hz, 2H). 13 C MR (1 MHz, CDCl3) δ 168.4, 159.2, 151.9, 137.5, 136.7, 133.7, 13.1, 13, 129.9, 129.1, 128.7, 128.6, 127.2, 12 (two overlapping signals), 121.7. HRMS (ESI) Calcd for [CH13Cl2+H] + 31846, Found 31844. S11
Product 3ac was obtained as a white solid in 85% yield (61.4 mg). 1 H MR ( MHz, CDCl3) δ 8.58 (d, J = 8.6 Hz, 2H), 8.14 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 7.9 Hz, 1H), 7.92-7.86 (m, 3H), 7.65 (d, J = 8.6 Hz, 2H), 7.61-7. (m, 3H), 7.58-7.54 (m, 1H). 13 C MR (1 MHz, CDCl3) δ 168.4, 159.3, 151.9, 137.5, 137.1, 133.7, 131.7, 13.2, 13.1, 13, 129.1, 128.6, 127.2, 127.1, 125.3, 121.7. HRMS (ESI) Calcd for [CH13Br2+H] + 363, Found 363. Product 3ad was obtained as a white solid in 75% yield (45.1 mg). 1 H MR ( MHz, CDCl3) δ 8.73-8.69 (m, 2H), 8.13 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 7.3 Hz, 1H), 7.9-7.87 (m, 3H), 7.61-7.59 (m, 3H), 7.56-7.52 (m, 1H), 7.22-7.18 (m, 2H). 13 C MR (1 MHz, CDCl3) δ 168.3, 164.6 (d, JC-F = 248.5 Hz), 159.3, 151.9, 137.5, 134.3 (d, JC-F = 2.8 Hz), 133.6, 13.7 (d, JC-F = 8.6 Hz), 13.1, 13, 12, 128.5, 127.1, 12, 121.5, 115.4 (d, JC-F = 2 Hz). HRMS (ESI) Calcd for [CH13F2+H] + 31.1141, Found 31.1142. 3ae Product 3ae was obtained as a white solid in 68% yield (42.5 mg). 1 H MR ( MHz, CDCl3) δ 8.67 (d, J = 8.9 Hz, 2H), 8.1 (t, J = 7.9 Hz, 2H), 7.9-7.83 (m, 3H), 7.61-7.59 (m, 3H), 7.52-7.48 (m, 1H), 5 (d, J = 8.9 Hz, 2H), 3.9 (s, 3H). 13 C MR (1 MHz, CDCl3): δ 168.1, 161.7, 16, 15, 137.7, 133.4, 13.9, 13.3, 13.1, 129.8, 128.9, 128.5, 12, 126.5, 121.4, 113.8, 55.3. HRMS (ESI) Calcd for [CH162+H] + 313.1341, Found 313.1341 S12
Product 3af was obtained as a white solid in 93% yield (63 mg). 1 H MR ( MHz, CDCl3) δ 8.61 (d, J = 8.4 Hz, 2H), 8.15 (d, J = 8.4Hz, 1H), 8.12 (d, J = Hz, 1H),7.9-7.86 (m, 3H), 7.61-7.51 (m, 6H), 1. (s, 9H). 13 C MR (1 MHz, CDCl3): δ 168.2, 1.4, 153.7, 15, 137.7, 135.5, 133.4, 13.2, 129.8, 129.1, 128.5, 128.4, 12, 126.7, 125.5, 121.6, 34.8, 31.3. HRMS (ESI) Calcd for [C24H222+H] + 339.1861, Found 339.1862. Product 3ag was obtained as a white solid in 83% yield (49.2 mg). 1 H MR ( MHz, CDCl3) δ 8.61 (d, J = 8.1 Hz, 2H), 8.15 (d, J = 8.4Hz, 1H), 8.13 (d, J = Hz, 1H), 7.91-7.85 (m, 3H), 7.61-7.59 (m, 3H), 7.52 (t, J = 7.5 Hz, 1H), 7.35 (d, J = Hz, 2H), 2.46 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 168.2, 1.3, 15, 1.7, 137.7, 135.5, 133.4, 13.2, 129.8, 129.3, 12, 128.6, 128.5, 126.9, 126.7, 121.6, 21.5. HRMS (ESI) Calcd for [C21H162+H] + 297.1392, Found 297.1394. Product 3ah was obtained as a white solid in 75% yield (54.2 mg). 1 H MR ( MHz, CDCl3) δ 8.86 (t, J = 1.5 Hz, 1H), 8.64 (d, J = 7.8 Hz, 1H), 8.15 (t, J = 7.6 Hz, 2H), 7.93-7.87 (m, 3H), 7.63-7.59 (m, 4H), 7.57 (t, J = 8.2 Hz, 1H), 7. (t, J = 7.9 Hz, 1H). 13 C MR (1 MHz, CDCl3) δ 168.5, 158.7, 151.8, 1.3, 137.4, 133.7, S13
133.3, 131.6, 13.2, 134, 132, 129.2, 128.6, 127.4, 127.2, 127.1, 122.8, 121.8. HRMS (ESI) Calcd for [CH13Br2+H] + 363, Found 36338. Product 3ai was obtained as a white solid in 72% yield (45.6 mg). 1 H MR ( MHz, CDCl3) δ 8.71 (s, 1H), 8.61-8.58 (m, 1H), 8.15 (t, J = 7.7 Hz, 2H), 7.93-7.87 (m, 3H), 7.62-7. (m, 3H), 7.59-7.55 (m, 1H), 7.49-7.44 (m, 2H). 13 C MR (1 MHz, CDCl3) δ 168.5, 158.9, 151.8, 1., 137.4, 134.6, 133.7, 13.4, 13.2, 13, 129.7, 129.2, 128.7, 128.6, 127.4, 12, 126.7, 121.8. HRMS (ESI) Calcd for [CH13Cl2+H] + 31846, Found 31845. Product 3aj was obtained as a white solid in 83% yield (58.1 mg). 1 H MR ( MHz, CDCl3) δ 1 (s, 1H), 8.91 (d, J = 7.7 Hz, 1H), 8.19-8.14 (m, 2H), 7.93-7.9 (m, 3H), 7.76 (d, J = 7.5 Hz, 1H), 7.67-7.56 (m, 5H). 13 C MR (11 MHz, CDCl3) δ 168.6, 158.7, 151.8, 13, 137.4, 133.8, 131.8 (two overlapping signals), 13 (q, JC-F = 32.1 Hz), 13.2, 13.1, 129.2, 128.9, 128.6, 127.5, 127.1, 126.9 (q, JC-F = 3.7 Hz), 125.5 (q, JC-F = 3.8 Hz), 121.9. HRMS (ESI) Calcd for [C21H13F32+H] + 351.119, Found 351.118. S14
Product 3ak was obtained as a white solid in 69% yield (41.4 mg). 1 H MR ( MHz, CDCl3) δ 8.51 (d, J = 7.8 Hz, 1H), 8.42 (d, J = 1.4 Hz, 1H), 8.15 (t, J = 7.9 Hz, 2H), 7.92-7.88 (m, 3H), 7.61-7.52 (m, 4H), 7.44-7.52 (m, 1H), 7. (t, J = 8.2 Hz, 1H). 13 C MR (1 MHz, CDCl3) δ 168.4, 16 (d, JC-F = 243.1 Hz), 15, 1.6 (d, JC-F = 7.7 Hz), 137.5, 133.7, 13.2, 131, 13, 129.9, 129.2, 128.5, 127.3, 12, 124.2 (d, JC-F = 2.7 Hz), 121.8, 117.3 (d, JC-F = 21.4 Hz), 115.4 (d, JC-F = 2 Hz). HRMS (ESI) Calcd for [CH13F2+H] + 31.1141, Found 31.1143. Product 3al was obtained as a white solid in 83% yield (49.2 mg). 1 H MR ( MHz, CDCl3) δ 8.52-8.5 (m, 2H), 8.16 (dd, J = 8.4 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 7.9-7.87 (m, 3H), 7.-7.56 (m, 3H), 7.54 (t, J = 7.5 Hz, 1H), 7.43 (t, J = 7.4 Hz, 1H), 7.33 (d, J = 7.1 Hz, 1H), 2.5 (s, 1H). 13 C MR (1 MHz, CDCl3) δ 168.3, 1.4, 15, 138.13, 138.11, 137.7, 133.5, 131.3, 13.2, 129.9, 129.15, 129.12, 128.5, 128.4, 12, 126.9, 125.9, 121.7, 21.5. HRMS (ESI) Calcd for [C21H162+H] + 297.1392, Found 297.1395. Product 3am was obtained as a white solid in 69% yield (.9 mg). 1 H MR ( MHz, CDCl3) δ 8.18 (d, J = 8.3 Hz, 2H), (d, J = 6.4 Hz, 1H), 7.93-7.86 (m, 3H), 7.61-7.58 (m, 4H), 7.36-7.35 (m, 3H), 2.69 (s, 1H). 13 C MR (1 MHz, CDCl3) δ 16, 163.3, 151.6, 138.8, 137.5, 137.4, 133.5, 131.2, 13.7, 13.1, 129.8, 129.2, 129.1, 128.5, 127.2, 126.9, 125.9, 12, 21.2. HRMS (ESI) Calcd for [C21H162+H] + 297.1392, Found 297.139. S15
Product 3an was obtained as a white solid in 66% yield (3.1 mg). 1 H MR ( MHz, CDCl3) δ 8.21 (dd, J = 3.7, 1.2 Hz, 1H), 8 (d, J = 8.5, 1H), 8 (d, J = 8.5, 1H), 7.87-7.83 (m, 3H), 7.63-7.58 (m, 3H), 7.52-7.48 (m, 2H), 7.19 (dd, J =, 3.7 Hz, 1H). 13 C MR (1 MHz, CDCl3) δ 168.4, 157.2, 151.8, 144.2, 137.2, 133.7, 13.2, 13, 129.8, 129.3, 128.7, 128.5, 128.2, 127.1, 126.7, 121.5. HRMS (ESI) Calcd for [C18H122S+H] + 28799, Found 288. Product 3ao was obtained as a white solid in 27% yield (.1 mg). 1 H MR ( MHz, CDCl3) δ 8.11(d, J = 8.4Hz, 1H), 8 (d, J = 8.4Hz, 1H), 7.88-7.82 (m, 3H), 7.57-7.53 (m, 4H), 4.15 (s, 2H), 1.63 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 16, 167.7, 151.4, 137.7, 133.2, 13.2, 129.8, 12, 128.4, 126.9, 126.8, 121.1, 55.1, 44.8, 25.5. HRMS (ESI) Calcd for [C18H17Cl2+H] + 297.1159, Found 297.1159. H 3aaa Ph Product 3aaa was obtained as a white solid in 36% yield (28.9 mg). 1 H MR ( MHz, CDCl3) δ 13.78 (br, 1H), 8.97 (d, J = 8.2, 1H), 8.88 (d, J = 7.4 Hz, 1H), 8.15 (d, J = 8.4 Hz, 1H), 8 (d, J = 8.4 Hz, 1H), 3 (d, J = 7.5 Hz, 2H), 7.93 (t, J = 7.6 Hz, 1H), 7.86 (d, J = 6.1 Hz, 2H), 7.68-7.49 (m, 6H), 7.39 (t, J = 7.6 Hz, 2H), 7.28 (d, J = 7.6 Hz, 1H). 13 C MR (1 MHz, CDCl 3) δ 168.4, 166.3, 1.8, 15.5, 1.2, 137.1, 136.2, 134.3, 13, 131.5, 131.5, 13.4, 13.2, 128.8, 128.5, 12, 127.7 (two S16
overlapping signals), 127.4, 123.8, 123.2, 121.1, 12. HRMS (ESI) Calcd for [C27H193+H] + 2.16, Found 2.15. Synthesis of Quinazoline Product 5. Arylimidate 2 (29.8 mg,. mmol), 3-phenyl-1,4,2-dioxazol-5-one (39.1 mg,.24 mmol), CoCp*(C)I2 (9.5 mg, 1 mol %), AgSbF6 (13.7 mg, 4 mmol), and DCE ( ml) were charged into a pressure tube. The reaction mixture was stirred under nitrogen at 1 ºC for h. After the solvent was removed under reduced pressure, the residue was purified by silica gel chromatography using PE/EA to afford the desired product. Spectral Data of Compounds 5aa-5aq 5aa Product 5aa was obtained as a white solid in 9% yield (4 mg). 1 H MR ( MHz, CDCl3) δ 8.49 (d, J = 7.6 Hz, 2H), 5 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.68 (t, J = 7.7 Hz, 1H), 7.42-7.36 (m, 4H), 4.66 (q, J = 7.1 Hz, 2H), 1.46 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.7, 1.1, 151.9, 138.3, 133.4, 13.4, 128.5, 128.4, 127.9, 126.3, 123.5, 115.4, 62.8, 14.5. HRMS (ESI) Calcd for [C16H142+H] + 251.1179, Found 251.1171. 5ba Product 5ba was obtained as a white solid in 86% yield (48.8 mg). 1 H MR ( MHz, CDCl3) δ 8.64-8. (m, 2H), 8.12 (d, J = 8.7 Hz, 1H), 2 (d, J = 1.9 Hz, 1H), S17
7.59-7.56 (m, 3H), 7.48 (dd, J = 8.7, 1.9 Hz, 1H), 4.8 (q, J = 7.1 Hz, 2H), 1.63 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.5, 161.1, 152.6, 139.4, 137.8, 13.7, 128.5, 128.4, 12, 12, 124.9, 113.6, 6, 14.3. HRMS (ESI) Calcd for [C16H13Cl2+H] + 28789, Found 28786. 5ca Product 5ca was obtained as a white solid in 88% yield (57.7 mg). 1 H MR ( MHz, CDCl3) δ 8.54-8.51 (m, 2H), 8.11 (d, J = 1.3 Hz, 1H), 7.94 (dd, J = 8.7,.7 Hz, 1H), 7.53 (d, J = 8.7 Hz, 1H), 7.5-7.46 (m, 3H), 4.7 (q, J = 7.1 Hz, 2H), 1.53 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.6, 16, 152.7, 137.8, 13.8, 13.4, 129.7, 128.6, 128.4, 12, 12, 11, 63.1, 14.4. HRMS (ESI) Calcd for [C16H13Br2+H] + 32284, Found 32289. 5da Product 5da was obtained as a white solid in 84% yield (44.4 mg). 1 H MR ( MHz, CDCl3) δ 8.66 (dd, J = 7.9, 1.8 Hz, 2H), 8.12 (d, J = 8.3 Hz, 1H), 7.85 (s, 1H), 7.61-7.54 (m, 3H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 4.83 (q, J = 7.1 Hz, 2H), 2.62 (s, 3H), 1.64 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.5, 1.1, 152.1, 14, 138.4, 13.3, 128.4, 128.3, 128.2, 127.1, 123.1, 113.2, 62.6, 2, 14.4. HRMS (ESI) Calcd for [C17H162+H] + 265.1335, Found 265.1336. 5ea Product 5ea was obtained as a white solid in 93% yield (51.9 mg). 1 H MR ( MHz, CDCl3) δ 8.64 (dd, J = 7.8, 1.8 Hz, 2H), 8.1 (d, J = Hz, 1H), 7.61-7.54 (m, 3H), 7.37 (d, J = 2.4 Hz, 1H), 7.17 (dd, J =, 2.5 Hz, 1H), 4.81 (q, J = 7.1 Hz, 2H), 2 (s, 3H), 1.62 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.3, 163.7, S18
1.7, 154.2, 138.3, 13.3, 128.3, 128.3, 124.7, 118.4, 19.6, 16.4, 62.5, 55.5, 14.4. HRMS (ESI) Calcd for [C17H1622+H] + 281.1285, Found 281.1289. 5fa Product 5fa was obtained as a white solid in 76% yield (39.9 mg). 1 H MR ( MHz, CDCl3) δ 8.48-8.46 (m, 2H), 7.83 (s, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.52 (dd, J = 8.5, 1.5 Hz, 1H), 7.43-7.35 (m, 3H), 4.66 (q, J = 7.1 Hz, 2H), 2.42 (s, 3H), 1.47 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.3, 159.3, 15.3, 138.4, 136.4, 135.4, 13.2, 128.4, 128.3, 127.7, 122.4, 115.2, 62.7, 21.6, 14.5. HRMS (ESI) Calcd for [C17H162+H] + 265.1335, Found 265.1339. 5ga Product 5ga was obtained as a white solid in 67% yield (36.1 mg). 1 H MR ( MHz, CDCl3) δ 8.66-8.62 (m, 2H), 7.84 (d, J = 7.8 Hz, 1H), 7.78-7.74 (m, 1H), 7.-7.57 (m, 3H), 7. (ddd, J = 1.4, 7.8,.9 Hz, 1H), 4.86 (q, J = 7.1 Hz, 2H), 1.66 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 165.7 (d, J = 4.9 Hz), 1.5 (2C), 158.6 (d, J = 2.8 Hz), 153.9, 137.6, 133.2 (d, J = 9.7 Hz), 13.8, 128.5, 128.4, 123.9 (d, J = 4.4 Hz), 111.9 (d, J = 21.2 Hz), 63.24, 14.29. HRMS (ESI) Calcd for [C16H13F2+H] + 269.185, Found 269.188. 5ha Product 5ha was obtained as a white solid in 74% yield (47.3 mg). 1 H MR ( MHz, CDCl3) δ 8.57-8.55 (m, 2H), 7.88 (d, J = Hz, 1H), 7.53-7.57 (m, 3H), 7.52-7.51 (m, 1H), 4.77 (q, J = 7.1, 2H), 1.64 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 165.9, 1.8, 154.3, 138.2, 13, 131.9, 13, 12, 128.5, 128.4, 126.4, 112.1, 63.7, 14.2. HRMS (ESI) Calcd for [C16H12Cl22+H] + 31399, Found S19
31397. 5ia Product 5ia was obtained as a white solid in 72% yield (36.7 mg). 1 H MR ( MHz, CDCl3) δ 8.61-8.58 (m, 2H), 7.9 (d, J = 5.4 Hz, 1H), 7.61-7.53 (m, 4H), 4.85 (q, J = 7.1 Hz, 2H), 1.62 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 16, 16, 161.1, 13, 133.7, 13.2, 128.4, 128.2, 124.8, 115.8, 62.7, 14.5. HRMS (ESI) Calcd for [C14H122S+H] + 25743, Found 25744. 5ja Product 5ja was obtained as a white solid in 62% yield (29.1 mg). 1 H MR ( MHz, CDCl3) δ 8.69 (dd, J = 7.8, 1.8 Hz, 2H), 8.23 (dd, J = 8.1,.8 Hz, 1H), 8 (d, J = 8.4 Hz, 1H), 7.91-7.84 (m, 1H), 7.62-7.55 (m, 4H), 4.36 (s, 3H). 13 C MR (1 MHz, CDCl3) δ 16, 16, 151.7, 138.1, 133.4, 13.5, 128.5, 128.4, 127.9, 126.4, 123.4, 115.2, 5. HRMS (ESI) Calcd for [C15H122+H] + 237.122, Found 237.126. 5ka Product 5ka was obtained as a Colorless oil in 42% yield (22.2 mg). 1 H MR ( MHz, CDCl3) δ 8.65 (dd, J = 7.7, 1.8 Hz, 2H), 8.24 (dd, J = 8.1, 1.1 Hz, 1H), 5 (d, J = 8.3 Hz, 1H), 7.9-7.85 (m, 1H), 7.61-7.54 (m, 4H), 5.89 (sept, J = 6.2 Hz, 1H), 1.62 (d, J = 6.2 Hz, 6H). 13 C MR (1 MHz, CDCl3) δ 166.3, 1.1, 151.9, 138.4, 133.3, 13.3, 128.4, 128.4, 127.9, 126.1, 123.6, 115.7, 69.9, 21.9. HRMS (ESI) Calcd for [C17H162+H] + 265.1335, Found 265.1337. S
5ab Product 5ab was obtained as a white solid in 78% yield (44.5 mg). 1 H MR ( MHz, CDCl3) δ 8.51 (d, J = 8.5 Hz, 2H), 8.15 (d, J = 8.1 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.79 (t, J = 7.7 Hz, 1H), 7.49 (t, J = 7.7 Hz, 1H), 7.45 (d, J = 8.5 Hz, 2H), 4.74 (q, J = 7.1 Hz, 2H), 1.56 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.7, 15, 151.7, 136.8, 136.6, 133.5, 129.8, 128.57, 127.9, 126.5, 123.6, 115.4, 62.9, 14.4. HRMS (ESI) Calcd for [C16H13Cl2+H] + 28789, Found 28786. 5ad Product 5ad was obtained as a white solid in 66% yield (35.2 mg). 1 H MR ( MHz, CDCl3) δ 8.57 (dd, J = 8.5, 5.9 Hz, 2H), 8.15 (d, J = 8.1 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.79 (t, J = 7.7 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.16 (t, J = 8.7 Hz, 2H), 4.74 (q, J = 7.1 Hz, 2H), 1.56 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.7, 164.6 (d, J = 248.4 Hz), 159.1, 151.8, 134.4 (d, J = 2.9 Hz), 133.5, 13.5 (d, J = 8.5 Hz), 127.8, 126.3, 123.6, 115.3 (d, J = 21.5 Hz), 115.2, 62.9, 14.4. HRMS (ESI) Calcd for [C16H13F2+H] + 269.185, Found 269.189. 5af Product 5af was obtained as a white solid in % yield (36.7 mg). 1 H MR ( MHz, CDCl3) δ 8.49 (d, J = 8.3 Hz, 2H), 8.14 (d, J = 8.1 Hz, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.53 (d, J = 8.3 Hz, 2H), 7.46 (t, J = 7.6 Hz, 1H), 4.75 (q, J = 7.1 Hz, 2H), 1.55 (t, J = 7.1 Hz, 3H), 1.38 (s, 9H). 13 C MR (1 MHz, CDCl3) δ 166.6, 1.2, 153.7, 15, 135.6, 133.3, 128.3, 127.9, 126.1, 125.4, 123.5, 115.3, S21
62.8, 34.9, 31.3, 14.5. HRMS (ESI) Calcd for [CH232+H] + 37.185, Found 37.182. 5ai Product 5ai was obtained as a white solid in 67% yield (37.9 mg). 1 H MR ( MHz, CDCl3) δ 8.55 (s, 1H), 8.45 (d, J = Hz, 1H), 8.14 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 7.79 (t, J = 7.7 Hz, 1H), 7.5 (t, J = 7.6 Hz, 1H), 7.45-7.39 (m, 2H), 4.74 (q, J = 7.1 Hz, 2H), 1.56 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.8, 158.7, 151.7, 1.1, 134.5, 133.5, 13.3, 129.6, 128.5, 12, 126.6, 126.5, 123.6, 115.5, 6, 14.4. HRMS (ESI) Calcd for [C16H13Cl2+H] + 28789, Found 28789. 5aj Product 5aj was obtained as a white solid in 81% yield (51.4 mg). 1 H MR ( MHz, CDCl3) δ 8.93 (s, 1H), 8.83 (d, J = 7.8 Hz, 1H), 8.23 (dd, J = 8.2,.8 Hz, 1H), 5 (d, J = 8.4 Hz, 1H), 7.89 (ddd, J = 8.4,, 1.5 Hz, 1H), 7.8 (d, J = 7.7 Hz, 1H), 7.67 (t, J = 7.8 Hz, 1H), 7.59 (ddd, J = 8.1, 7.1, 1.1 Hz, 1H), 4.83 (q, J = 7.1 Hz, 2H), 1.65 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.8, 158.4, 151.6, 13, 133.5, 131.5, 13.8 (q, J = 32.1 Hz), 128.8, 127.9, 126.8 (q, J = 3.7 Hz), 126.7, 125.2 (q, J = 3.9 Hz), 124.3 (q, J = 27.6 Hz), 123.5, 115.5, 6, 14.3. HRMS (ESI) Calcd for [C17H13F32+H] + 319.153, Found 319.157. 5am Product 5am was obtained as a white solid in 53% yield (27.9 mg). 1 H MR ( MHz, CDCl3) δ 8. (d, J = 8.2 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.94-7.92 (m, 1H), 7.82 (t, J = 7.7 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.36-7.31 (m, 3H), 4.69 (q, J = 7.1 S22
Hz, 2H), 2.64 (s, 3H), 1.53 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.3, 163.2, 151.6, 138.9, 137.4, 133.4, 131.3, 13.5, 129.2, 127.9, 126.5, 125.9, 123.5, 114.8, 6, 21.5, 14.5. HRMS (ESI) Calcd for [C17H162+H] + 265.1335, Found 265.1337. 5an Product 5an was obtained as a white solid in 64% yield (39.7 mg). 1 H MR ( MHz, CDCl3) δ 8.21 (dt, J = 8.5, 1.6 Hz, 1H), 8.17 (s, 1H), 8.16-8.13 (m, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.8-7.76 (m, 1H), 7.49-7.44 (m, 1H), 6.98 (dd, J = 8.4, 2.7 Hz, 1H), 4.79-4.72 (m, 2H), 5 (d, J =.9 Hz, 3H), 3.96 (d, J = 2.3 Hz, 3H), 1.57 (td, J = 7.1, 2.5 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.5, 159.7, 151.9, 151.2, 148.8, 133.3, 131.1, 127.6, 125.9, 123.5, 121.8, 115.1, 11, 11.6, 62.6, 55.9, 14.4. HRMS (ESI) Calcd for [C18H1923+H] + 311.139, Found 311.1391. 5ao Product 5ao was obtained as a white solid in 82% yield (42.2 mg). 1 H MR ( MHz, CDCl3) δ 8.1 (d, J = 8.1 Hz, 1H), 7 (d, J = 3.6 Hz, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.76 (t, J = 7.7 Hz, 1H), 7.47-7.42 (m, 2H), 7.15 (t, J = 4.3 Hz, 1H), 4.71 (q, J = 7.1 Hz, 2H), 1.54 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.4, 156.8, 151.7, 144.2, 133.5, 129.4, 128.8, 12, 127.4, 125.9, 123.5, 115.2, 6, 14.3. HRMS (ESI) Calcd for [C14H122S+H] + 25743, Found 25745. 5ap Product 5ap was obtained as a Colorless oil in 67% yield (35.3 mg). 1 H MR ( MHz, CDCl3) δ 8.12 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.76 (t, J = 7.7 Hz, S23
1H), 7.48 (t, J = 7.5 Hz, 1H), 4.64 (q, J = 7.1 Hz, 2H), 4 (s, 2H), 1.53-1.48 (m, 9H). 13 C MR (1 MHz, CDCl3) δ 168.8, 166.4, 151.3, 133.1, 127.8, 126.2, 123.3, 114.9, 62.7, 5, 44.7, 25.2, 14.4. HRMS (ESI) Calcd for [C14H17Cl2+H] + 265.112, Found 265.117. 5aq Product 5aq was obtained as a white solid in % yield (31.8 mg). 1 H MR ( MHz, CDCl3) δ 8.1 (dd, J = 8.2,.8 Hz, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.78-7.74 (m, 1H), 7.48-7.44 (m, 3H), 7.28 (t, J = 7.5 Hz, 2H), 7. (t, J = 7.3 Hz, 1H), 4.58 (q, J = 7.1 Hz, 2H), 4.25 (s, 2H), 1.44 (t, J = 7.1 Hz, 3H). 13 C MR (1 MHz, CDCl3) δ 166.6, 165.2, 151.4, 138.7, 133.2, 129.3, 128.2, 127.2, 126.3, 126.1, 123.4, 114.9, 62.8, 46.3, 14.2. HRMS (ESI) Calcd for [C17H16Cl2+H] + 265.1335, Found 265.1337. Derivatization of Product 3aa 2,4-Diphenylquinazoline (.2 mmol, 56.4 mg), EBX-TIPS (12.7 mg, 1.2 equiv), [Cp*RhCl2]2 (6.2 mg, 5 mol%), and Zn(Tf)2 (14.5 mg, mol%) were weighed into a pressure tube, to which 1,2-dichloroethane (3 ml) was added under 2 conditions. The reaction mixture was stirred for 16 h. After removal of 1,2-dichloroethane under reduced pressure, purification was performed by flash column chromatography on silica gel using EtAc and petroleum ether to afford the desired product 6 in 45% yield (41.6 mg). 1 H MR ( MHz, CDCl3) δ 8.18 (d, J = 9.1 Hz, 2H), 7.93-7.88 (m, 4H), 7.68 (dd, J = 7.5, 1.2 Hz, 1H), 7.63-58 (m, 1H), 7.57-7.55 (m, 3H), 7.46-7. (m, 2H),.89 (s, 21H). 13 C MR (1 MHz, CDCl3) δ 168.2, 162.3, 151.6, 142.1, 137.4, 134.3, 133.4, S24
13.3, 129.9, 129.8, 129.3, 128.7, 128.5 128.3, 127.4, 126.9, 122.8, 121.4, 16.2, 9, 18.5, 11.2. HRMS (ESI) Calcd for [C31H342Si+H] + 463.257, Found 463.2571. 2,4-Diphenylquinazoline (.1mmol, 28.2 mg), potassium trifluoromethylborate (36.6 mg, 3 equiv), AgF (35.5 mg, 2.8 equiv), [Cp*RhCl2]2 (2.5 mg, 4 mol %), and AgSbF6 (5.5 mg, 16 mol %) were charged into a pressure tube, to which 1,2-dichloroethane (3 ml) was added under 2. The reaction mixture was stirred for 16 h. After removal of 1,2-dichloroethane under reduced pressure, purification was performed by flash column chromatography on silica gel using EtAc and petroleum ether to afford the desired product 3am in 51% yield (15.1 mg). Derivatization of Product 5an To a solution of product 5an (155 mg,.5 mmol) in dioxane (2.5 ml) was added aqueous HCl (12 M, 2.5 ml), and the mixture was heated at 1 C overnight. After the solution was neutralized with saturation ahc3, the solution was extracted three times with dichloromethane (5 ml). The organic layer was washed with brine (1 ml) and dried over MgS4. The solvent was removed under reduced pressure to afford the crude product. The product was recrystallized from ethanol to yield a white solid 7 (91%, 128.3 mg). 1 H MR ( MHz, DMS-d6) δ 12.48 (s, 1H), 8.19 (d, J = 7.6 Hz, 1H), 7.93 (dd, J = 8.5, 1.7 Hz, 1H), 7.88-7.85 (m, 2H), 7.77 (d, J = 8.1 Hz, 1H), 7.54 (t, J = 7.4 Hz, 1H), 7.17 (d, J = 8.5 Hz, 1H), 3.94 (s, 3H), 3.9 (s, 3H). 13 C MR (1 MHz, S25
DMS-d6) δ 162.8, 152.2, 15, 149.3, 14, 13, 127.7, 126.5, 126.2, 125.2, 121.6, 121.1, 111.8, 111.1, 56.1. HRMS (ESI) Calcd for [C16H1523+H] + 283.177, Found 283.178. Synthesis of Intermediate 8 To a solution of tert-butanesulfinamide (1.7 mmol,.515 g) and -(2-benzoylphenyl)benzamide (1.7 mmol,.6 g) in THF (1mL) was added dropwise (Et)4Ti (3.4 mmol,.72 ml) under 2 atmosphere. Then the mixture was stirred at 65 o C for overnight. EtAc (5 ml) was then added, followed by slow addition of saturated brine (2 ml). The mixture was immediately filtered through celite and the filter cake was washed with EtAc. The solution was transferred to a separatory funnel and was washed with brine. The organic layer was dried over anhydrous a2s4. The crude product was purified by silica gel chromatography with an eluent of PE/EtAc to give 8 in 54% yield (371 mg). Product 8 was isolated as a mixture of stereoisomers in.36:1 ratio. 1 H MR ( MHz, C6D6): selected signals δ 13.22 (br s, 1H, minor), 9.9 (s, 1H, major), 9.64 (d, J = 7.2 Hz, 1H, minor), 8. (d, J = 7.2 Hz, 1H, minor), 8.24 (d, J = 7.8 Hz, 2H, minor), 6 (d, J = 7.9 Hz, 1H, major), 7.78 (d, J = 7.2 Hz, 1H, major), 7.37 (m, 1H, minor), 7.76 (d, J = 7.8 Hz, 1H, major), 6.54 (m, 1H, minor), 1.19 (s, 9H, major),.87 (s, 9H, minor). HRMS (ESI) Calcd for [C24H2422S+H] + 5.1637, Found 5.1639. S26
1 12.5 1 9.5 8.5 7.5 6.5 5.5 4.5 3.5 2.5 1.5.5 Compound 8 (.1 mmol,.4 mg) was dissolved in DCE (2 ml) and was heated at 1 o C for 16 h under 2. The crude product was purified by flash column chromatography on silica gel using EtAc and petroleum ether to afford 3aa in 86% yield (24.2 mg). S27
Crystal Structure of 3aaa Table 1. Crystal data and structure refinement for 3aaa. Identification code mo_dm15682_m Empirical formula C27H193 Formula weight 1.45 Temperature 296(2) K Wavelength.7173 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 4.83(7) Å = 9 b = 342(5) Å = 9.81(4) c = 13.79(2) Å = 9 Volume 1.6(5) Å3 Z 4 Density (calculated) 1.332 Mg/m3 Absorption coefficient 83 mm-1 F() 8 Crystal size.21 x.12 x 8 mm3 Theta range for data collection 1.36 to. Index ranges -5<=h<=5, -34<=k<=37, -17<=l<=16 Reflections collected 14437 Independent reflections 391 [R(int) = 446] Completeness to theta = 1 % Absorption correction Semi-empirical from equivalents Max. and min. transmission.9934 and.9828 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 391 / 72 / 38 Goodness-of-fit on F2.896 S28
Final R indices [I>2sigma(I)] R1 = 55, wr2 =.1328 R indices (all data) R1 = 967, wr2 =.1685 Largest diff. peak and hole.156 and -.166 e.å-3 S29
Mechanistic Studies (a) H/D exchange experiment -Sulfinyl imine (.2 mmol, 57.1 mg), CoCp*(C)I2 (9.5 mg, 1 mol %), AgTf2 (15.5 mg, mol %), and aceticacid-d4 (64 mg, 5 equiv) were weighed into a pressure tube, to which 1,2-dichloroethane (3 ml) was added under 2. The reaction mixture was stirred at 1 o C for 16 h. After removal of 1,2-dichloroethane under reduced pressure, the crud product was determined by GC-MS. (b) Intramolecular KIE experiments 1a-d5 (.2 mmol, 58.1mg), CoCp*(C)I2 (9.5 mg, 1 mol %), AgTf2 (15.5 mg, mol %), and dioxazolones (32.6 mg, 1 equiv) were weighed into a 25 ml pressure tube, to which 1,2-dichloroethane (3 ml) was added under 2. The reaction mixture was stirred at 1 o C for 3 min. After removal of 1,2-dichloroethane under reduced pressure, MeH was added (3 ml). Sodium borohydride (22.8 mg, 3 equiv) was then added, and then the mixture was stirred at room temperature for 3 min. Purification was performed by flash column chromatography on silica gel using EtAc and petroleum ether to afford the product mixture. KIE (kh/kd = 1.3) was determined on the basis of 1 H MR analysis. S3
1.15 1.72 1.68 3.64 8.73 8.7263 8.71 7.8898 7.8696 7.8666 7.6235 7.6137 7.611 7.22 7.597 7.5643 7.5477 7.5293 7.596 7.2596 1.6699 1.6656 1 f1 (ppm) (c) Intermolecular KIE Experiments An equimolar mixture of -sulfinyl imine (.2 mmol, 57.1 mg), 1a-d1 (.2 mmol, 59.1 mg), CoCp*(C)I2 (9.5 mg, 1 mol %), AgTf2 (15.5 mg, mol %), and dioxazolones (32.6 mg, 1 equiv) were weighed into a 25 ml pressure tube, to which 1,2-dichloroethane (3 ml) was added under 2. The reaction mixture was stirred at 1 o C for 3 min. After removal of 1,2-dichloroethane under reduced pressure, MeH (3 ml) was added. Sodium borohydride (22.8 mg, 3 equiv) was then added and the mixture was stirred at room temperature for 3min. Purification was performed by flash column chromatography on silica gel using EtAc and petroleum ether to afford the desired products. KIE value (kh/kd =1.3) was determined on the basis of 1 H MR analysis. S31
1.14 1.57 1.43 3.7 8.7345 8.734 8.7142 8.7112 8.1817 8.15 8.1461 8.1253 7.9182 7.978 7.8995 7.8943 7.8871 7.8693 7.8664 7.6255 7.6157 7.6119 7. 7.5989 7.57 7.5666 7.555 7.53 7.5121 7.24 References (1) McMahon, J. P.; Ellman, J. A. rg. Lett. 4, 6, 1645. (2) Yaday, V. K.; Babu, K. G. Eur. J. rg. Chem. 5, 452. S32
S33 MR Spectra 1 1 9 5 8 7.5147 7.53 7.5525 7.5688 7.5 7.6159 7.8716 7.8929 7.8974 7.985 7.9161 8.12 8.1469 8.1698 8.191 8.7168 8.7363 1 3 5 7 8 9 11 13 15 17 19 76.6822 76.9998 77.3175 121.6697 126.9945 128.5127 128.6437 129.136 129.918 13.1651 13.4799 133.5293 137.6483 138.1819 151.9621 1.2288 168.3124
S34 1 4.11 2.21 6 3 1 7.4792 7.48 7.515 7.565 7.53 7.5253 7.53 7.5369 7.5468 7.575 7.5959 7.85 7.8214 7.9885 17 8.1478 8.1525 8.6452 8.65 8.6592 8.6691 1 3 5 7 8 9 11 13 15 17 19 76.6828 73 77.3177 119.867 127.958 128.1812 128.275 128.5911 128.7331 128.9657 13.9584 131.4123 136. 137.5765 139.9474 152.7218 161.16 11 Cl Cl 3ba Cl Cl 3ba
S35 1 3.19 1.24 4.22 6 8 7.21 7.545 7.5135 7.5192 7.5275 7.537 7.5398 7.12 7. 7.6234 7.6282 7.6341 7.7296 7.7441 7.8853 7.975 8.3256 8.333 8.6284 8.6338 8.6422 8.6529 1 3 5 7 8 9 11 13 15 17 19 76.6822 76.9998 77.3175 119.9898 124.9289 127.8121 128.589 128.5649 128.6926 13.729 13.9567 131.62 131.8941 13232 137.4774 152.7479 1.9677 167.1298 Br Br 3ca Br Br 3ca
S36 1 3.24 3.11 3 8 5 7.2271 7.2426 7.2635 7.2843 7.2985 7.4914 7.51 7.7137 7.7333 7.7378 7.8199 7.83 7.8396 7.8536 442 595 666 818 8.6269 8.638 1 3 5 7 8 9 11 13 15 17 19 76.6824 76.9998 77.3175 112.7621 112.9636 115.6611 115.8773 128.5581 129.37 129.8356 13737 153.799 153.9282 16727 162.7756 164.2664 165.2678 166.817 166.8867
S37 1 3.13 3 2.19 8 3 3 7.24 7.538 7.5385 7.5471 7.7174 7.7213 7.7393 7.7431 7.8867 7.972 7.9819 21 8.1473 8.169 8.4719 8.6652 8.6718 8.6765 8.687 8.6859 8.6895 1 3 5 7 8 9 11 13 15 17 19 76.6826 72 77.3178 122.8537 122.8844 125.7 125.7376 127.35 127.2461 127.741 128.6851 128.7772 13.4748 131.2835 137.117 151.582 161.341 167.14 CF 3 F 3 C 3ea
S38 1 2.81 2.8 3.11 7 3.11 2.11 4 3.91 86 918 7.1125 7.1367 7.161 7.2 7.4277 7.585 7.5271 7.8488 7.8694 283 511 8.6586 8.6757 1 3 5 7 8 9 11 13 15 17 19 55.423 55.7264 76.6818 76.9996 77.3175 16.6439 113.938 119.9284 128.36 138.4264 154.4668 1.7315 16773 163.5735 166.5762
S39 1 9 3.16 8 3.23 4 2 2.5 2.59 7.2597 7.3451 7.3661 7.3943 7.4136 7.4976 7.5189 7.5379 7.5536 7.7934 7.8129 7.9359 8.6973 8.7148 1 3 5 7 8 9 11 13 15 17 19 21.4217 81 76.6849 73 77.3187 119.8415 126.6972 12422 128.4114 128.5775 12679 129.171 13.174 13.2752 13199 138.4183 139.9791 144.2574 152.2459 1.2558 167.6831
S 1 1.38 3.49 5 2 3 1 7.22 7.2973 7.383 7.3188 7.5246 7.5419 7.51 7.6824 7.6947 7.7987 418 547 8.1178 8.1269 8.6649 8.6827 1 3 5 7 8 9 11 13 15 17 19 76.6824 7 77.3177 122.8224 125.1165 128.359 128.4633 128.4847 129.3352 13.3183 13.6768 135.2396 137.7738 142.774 153.4172 1.7673 163.291
S41 1 6.48 5.32 3.22.98 2.11 2.54 7.2598 7.3 7.4173 7.4757 7.4931 7.5146 7.5354 7.6423 7.6596 7.735 7.7271 7.871 8.687 8.6967 1 3 5 7 8 9 11 13 15 17 19 21.5518 21.847 76.6827 76.9998 77.3173 121.6788 125.6715 127.215 128.261 128.4473 128.537 128.7788 13.4626 15.4569 159.5635 167.7675 3ia 3ia
S42 1 4 2 1.97 7.24 7.335 7.357 7.398 7.3121 7.4856 7.4984 7.5 7.5185 7.5253 7.5298 7.5385 7.5437 7.57 7.5661 7.568 7.5715 7.5798 7.5874 7.5932 7.5964 7.5999 7.36 7.614 7.6124 7.6272 7.6333 7.6429 7.6458 7.6488 7.665 7.8838 7.948 8.744 8.792 8.7175 8.7214 8.729 1 3 5 7 8 9 11 13 15 17 19 76.6821 76.9997 77.3171 11316 117.529 122.3198 125.8766 126.6516 13.1557 137.58 139.421 139.4946 156.5327 159.175 1.32 1.3336 161.5434 115 166.7297 166.7545 166.781
S43.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 7.43 4 2.14 3.11 4 3.11 7.23 7.5125 7.5315 7.5484 7.5576 7.5765 7.5933 7.6137 7.621 7.6256 7.639 7.6376 7.6444 7.651 7.6542 7.9587 7.9799 9 295 513 8.162 8.11 8.1153 8.1223 8.4684 8.7485 8.78 8.828 8.862 1 3 5 7 8 9 11 13 15 17 19 76.6828 73 77.318 1.27 126.7291 128.1269 13.5774 146.6569 15972 17516 3ka 3ka
S44.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 f1 (ppm) 3.17 3.21 5 1.9 8 3.15 4 9 2.1713 2.4131 7.44 7.24 7.2795 7.283 7.2911 7.4173 7.4224 7.4394 7.4445 7.51 7.5171 7.5252 7.5298 7.5397 7.62 7.6481 8.1536 8.1586 8.6471 8.6521 8.67 8.6715 1 3 5 7 8 9 11 13 15 17 19 19.4357.93 76.683 71 77.3189 12382 127.96 128.8225 13.724 135.2654 15533 161.41 169.951 Cl 3la Cl 3la
S45 1 4 5 5 2.96 1.31 3.1 6 2 2.1552 2.3886 2.578 7.54 7.2239 7.2352 7.2445 7.29 7.2843 7.388 7.4677 7.4846 7.537 7.5188 7.5524 7.5735 7.9251 8.6356 8.6541 1 3 5 7 8 9 11 13 15 17 19 19.45.9368 22.113 76.6821 76.9999 77.3175 1.7832 126.7962 127.865 128.43 128.6469 129.1777 129.816 137 13.374 13.5255 133.1826 13696 136.9148 138.3879 144.5992 151.6491 1.378 169.4185
S46 1 5 3 5.27 8 2.2374 155 96 7.1134 7.22 7.3545 7.3867 7.17 7.41 7.44 7.51 7.51 8.6258 8.6433 1 3 5 7 8 9 11 13 15 17 19 19.9488 55.7724 76.6822 76.9996 77.3171 16.549 116 1. 125.5678 136.3961 138.4142 153.9261 1.8945 163.991 168.5193 3na major, :1 3na major, :1
S47 1 2.96 2.95 1 3.25 6 4.97 2.1563 2.3957 7.1931 7.215 7.2168 7.2332 7.2386 7.2543 7.23 7.2728 7.2925 7.4942 7.4988 7.5121 8.6363 8.69 8.65 8.6527 8.64 8 1 1 1 1 18 19.4194.9239 76.6823 76.9999 77.3175 112.4721 112.6738 117.2268 117.4768 128.5193 129.9835 13.75 153.145 153.2427 161.22 164.3664 166.973 169.7158 F 3oa major, :1 F 3oa major, :1
S48 1 3.1 5 2 3.15 4 4 1.6725 2.5832 2.9787 7.22 7.3885 7.95 7.489 7.4883 7.4977 7.544 7.5235 7.5397 7.5445 7.6999 7.859 8.595 8.72 8.618 8 1 1 1 1 18 21.8952 2542 76.683 74 77.3181 121.1434 124.673 128.1449 128.4529 128.48 13.2259 138.48 144.3556 15.6548 1.26 167.6673
S49 1 3.12 3 7.98 1.97 2.9193 7.1999 7.2339 7.22 7.25 7.2621 7.2773 7.2836 7.44 7.4539 7.9988 8.5316 8.5358 8.5499 8.5556 1 3 5 7 8 9 11 13 15 17 19 2558 76.6823 76.9998 77.3174 112.7231 112.9235 116.9715 117.2216 1.2132 127.5414 137.8614 152.1898 152.3266 161.1163 164.213 166.7456 167.8863
S5 1 6 2 3.11 2 1 2 1.95 2.6184 7.22 7.388 7.3916 7.93 7.413 7.4886 7.5 7.5171 7.5354 7.5492 7.8519 7.9997 8.6518 8.6557 8.677 8.6758 1 3 5 7 8 9 11 13 15 17 19 22.1145 119.6275 125.47 128.5555 13159 144.9175 152.3141 1.3421 166.35 CF 3 3ra CF 3 3ra
S51 1 2 6 3.12 7 4 4 3 2.5163 7.21 7.4245 7.4441 7.5323 7.537 7.5454 7.551 7.58 7.691 7.6939 7.795 8.2729 8.2947 8.45 8.6961 8.79 8.794 8.7127 8.75 1 3 5 7 8 9 11 13 15 17 19 5.97 21.491 76.6826 71 77.3176 122.1414 122.353 126.9449 128.487 128.7968 13.1956 1.7891 151.476 161.2813 168.5844 F 3 C 3ra' F 3 C 3ra'
S52 1.9 3.96 2.95.9 7.3311 7.5563 7.5765 7.6229 7.6421 7.6623 7.6799 7.6871 7.9473 7.9568 7.9763 7.9956 8.1966 8.2173 8.252 8.271 8.7281 8.7486 1 3 5 7 8 9 11 13 15 17 19 76.6818 76.9995 77.3169 121.6932 1248 127.1873 128.5568 128.6939 129.17 129.9815 13.19 151.8925 159.193 168.33 Cl 3ab Cl 3ab
S53 1 1.19 2.81 8 2 1.59 7.2596 7.5636 7.6132 8.1488 8.5718 8.5932 1 3 5 7 8 9 11 13 15 17 19 76.6831 74 77.3181 121.7241 125.265 12546 127.2175 128.5587 129.112 139 13.1427 151.88 159.2625 168.84
S54 1 1.98 3 2.86 4 2 1.675 7.1798 7.17 7.2234 7.52 7.5443 7.5645 7.5958 7.71 7.868 7.8835 7.9 8.111 8.1293 8.6927 8.6978 8.769 8.7149 8.7238 8.729 1 3 5 7 8 9 11 13 15 17 19 76.6821 76.9998 77.3174 115.2951 115.595 121.5398 12153 122 13.1223 13.7641 151.975 159.2589 163.3662 165.8511 168.3489 F 3ad F 3ad
S55 1 2.81 2 6 2 8 6 1.6884 3.8983 339 7.22 7.518 7.5222 7.5924 7. 7.8358 7.8567 7.8735 8.139 8.6567 8.6789 8 1 1 1 1 18 55.3368 76.6822 76.9998 77.3173 113.8112 121.3611 126.97 128.918 13.136 13.8879 15225 15 168.1194 3ae 3ae
S56 1 9.24 7 4 1 1.3965 7.2599 7.511 7.5299 7.558 7.5722 7.5922 7.597 7.53 7.857 7.8753 7.881 7.8862 7.8949 8.37 8.6247 1 3 5 7 8 9 11 13 15 17 19 31.2622 34.832 76.6823 7 77.3174 121.5573 125.4778 126.7258 126.9616 128.4258 128.4719 12995 13.1677 15197 153.7458 1.3595 168.1592
S57 1 2.86 1 8 2.99 4 6 2.4567 7.21 7.3372 7.3572 7.539 7.5224 7.5415 7.5938 7.5982 7.66 7.8519 7.874 7.891 8.3 8.6232 1 3 5 7 8 9 11 13 15 17 19 21.534 76.6823 76.9999 77.3174 121.5572 126.725 126.9452 128.4665 128.5916 12353 129.2541 13.1484 151.9766 1.2773 168.156
S58 1 7 1.23 3.98 3.17 2.1 4 1.5991 7.2598 7.378 7.3977 7.4173 7.5547 7.5744 7.5948 7. 7.614 7.6182 7.63 7.8717 8.1477 8.6316 8.6512 8.8575 8.8614 8.8652 1 3 5 7 8 9 11 13 15 17 19 76.6825 7 77.3176 121.8276 122.8288 12519 127.1912 127.3775 128.5714 129.1713 13.1644 151.8366 158.7291 168.4782 Br 3ah Br 3ah
S59.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 1.5 5.19 5 8 4 1 1.6593 7.22 7.54 7.6268 7.753 7.972 8.919 8.9212 17 1 3 5 7 8 9 11 13 15 17 19 76.6834 73 77.3181 121.8758 125.522 126.952 12551 128.9363 13.1721 131.1161 133.7591 151.8499 158.6912 168.5519
S 1 1 3 3 1 1.99 1.6421 7.1777 7.198 7.2187 7.23 7.4646 7.4834 7.517 7.5184 7.554 7.5696 7.65 7.8819 7.8989 7.9195 8.131 8.153 8.172 8.59 8.4319 8.4961 8.5155 1 3 5 7 8 9 11 13 15 17 19 76.6829 72 77.3172 115.3188 117.1962 121.8193 124.25 127.318 129.1924 129.955 13.1593 137.4711 151.8738 158.9876 162 164.457 168.3993
S61 1 2.91.95 2 1.11 2.94 1 1.94 1.634 2.53 7.23 7.3175 7.3354 7.4142 7.433 7.4514 7.5258 7.5445 7.5631 7.22 7.8689 7.8912 8.513 8.57 1 3 5 7 8 9 11 13 15 17 19 21.538 76.6822 73 77.3165 121.6663 125.954 126.8965 126.9876 128.4416 128.569 129.1251 13.1769 151.9761 1.91 168.2754 3al 3al
S62 1 2.97 5 1 3 2.6877 7.25 7.3499 7.3588 7.5767 7.5899 7.6154 7.8618 7.8688 7.8743 7.8945 7.9151 7.9333 7.9965 125 8.1653 8.18 1 3 5 7 8 9 11 13 15 17 19 21.2317 76.6815 76.9999 77.3168 1.9755 125.9278 126.9257 127.2336 128.586 12783 129.1796 13993 151.6434 163.3471 167.977
S63 1 5 8 3. 3.21 2.1 7.177 7.1863 7.1895 7.1987 7.21 7.4824 7.4857 7.526 7.557 7.5151 7.5182 7.56 7.5234 7.5757 7.5853 7.5921 7.5965 7.17 7.86 7.8333 7.8362 7.8545 7.8584 7.84 7.8663 7.8696 7.8753 7.8785 677 74 89 917 8.14 8.44 8.216 8.2136 1 3 5 7 8 9 11 13 15 17 19 76.6819 76.9995 77.3172 121.4892 126.6815 127.1138 128.1934 128.4963 128.6793 13.1534 144.1615 151.8178 168.34 3an S 3an S
S64 1 5.97 1 2.99 1.95 1.599 1.6288 4.1544 7.24 7.5256 7.5452 7.5711 7.8167 7.8288 7.8359 7.87 7.8788 671 884 8.133 8.1244 1 3 5 7 8 9 11 13 15 17 19 25.4862 44.8289 55.1219 76.6833 75 77.3177 12945 126.74 128.4467 129.811 133.12 151.3649 167.763 16256
S65 1.5 1 13.5 1.15 1 6.14 1.99 6 2 1 1.91 7.2577 7.2689 7.2879 7.3733 7.3924 7.4113 7.546 7.5229 7.5454 7.5676 7.589 7.75 7.6257 7.641 7.8512 7.8664 7.968 7.9262 7.9449 9 396 665 876 8.135 8.15 8.8783 8.8968 8.9564 8.977 13.7847 H 76.68 76.9996 77.3173 1.981 123.1984 127.3277 148 128.721 13.2958 131.499 134.25 15.4532 1.7412 166.2378 168.3527
S66.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 1.99 1.98.99 1.96 1.4415 1.4592 1.4769 4.6327 4.654 4.6681 4.6857 7.3593 7.378 7.3941 7.41 7.4229 7.665 7.8657 8.4789 8.4979-1 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.4518 62.8427 115.394 123.5335 127.91 128.4789 138.2988 151.8915 16879 166.6988
S67.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 1 2.96.98.97 1.97 1.92 1.627 1.6447 4.7778 4.7955 4.8132 4.839 7.4669 7.4717 7.4886 7.4934 7.5594 7.5684 175 8.162 8.45 8.6128 8.6186 8.6279 8.6372 Cl -1 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.313 62.9998 113.6345 124.929 12319 128.4911 137.7638 139.27 152.5513 16647 166.4614 Cl
S68.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 2.91 1.11.98.94 1.94 1.5114 1.5292 1.5469 4.6754 4.6931 4.718 4.7285 7.4636 7.4729 7.4797 7.4895 7.4968 7.5146 7.5363 7.931 7.9536 8.51 8.5179 8.527 Br -1 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.3899 63.115 113.9932 124.9533 128.4315 13.7859 137.7995 152.7222 16313 166.6233 Br
S69.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 2.98 2 1 3.99 1.99 1.66 1.6384 1.6561 2.6226 4.851 4.8228 4.85 4.8583 7.3765 7.3972 7.5377 7.5571 7.5712 7.59 7.42 7.8473 8.158 8.1265 8.6497 8.6535 8.6687 8.6737 H 3 C 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 19 14.3 2199 62.5967 113.1669 123.1345 128.2138 128.3556 138.3631 1435 152.18 16764 166.566 H 3 C
S7.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 2.97 1.99 1 2.95 1 1.98 1.5998 1.6175 1.6352 5 4.7796 4.7973 4.8151 4.8328 7.159 7.157 7.1733 7.1795 7.3714 7.3775 7.5353 7.5678 927 8.1152 8.6312 8.6352 8.6499 8.6552 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.84 55.535 62.519 16.44 19.6257 118.4493 124.7393 128.3481 138.382 154.1622 1.698 163.6837 166.2765
S71.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 2.96 2.96.98.97.95 1.94 1.4498 1.4675 1.4853 2.4178 4.6286 4.6463 4.66 4.6817 7.3517 7.3695 7.3876 7.66 7.42 7.5289 7.76 7.8251 8.4633 8.4795 8.4825 H 3 C -1 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.4787 21.6448 62.7144 115.1891 122.445 127.671 135.3642 136.3689 15.27 159.2975 166.261 H 3 C
S72.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 1.98 2.99.99.97 1.98 1.6385 1.6562 1.6739 4.838 4.8557 4.8734 4.8911 7.1776 7.1797 7.1972 7.1995 7.36 7.5657 7.589 7.7433 7.833 8.6193 8.6281 8.6337 8.6426 8.647 8.6527 F 1 3 5 7 8 9 1 11 1 13 1 15 1 17 18 14.2884 63.24 111.7851 111.9969 123.8386 123.8825 128.397 13.75 137.6228 153.9133 157.277 159.8849 1.591 165.77 165.771 F