Supporting Information

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1 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 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

2 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 () [RhCp*Cl2]2 (5) AgTf2 () [RhCp*(MeC)3](SbF6)2 (5) [IrCp*Cl2]2 (5) AgTf2 () [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

3 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

4 1H), (m, 3H), (m, 3H), (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, (two carbon signals), 12 (two carbon signals), HRMS (ESI) Calcd for [CH142+H] , Found 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), (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, HRMS (ESI) Calcd for [CH12Cl22+H] , Found 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), (m, 4H), (m, 1H), (m, 3H). 13 C MR (1 MHz, CDCl3) δ 167.1, 16, 152.7, 137.5, 13, 131.9, (two overlapping signals), 13, 13.7, 128.7, 128.6, 128.5, 127.8, 124.9, 1.. HRMS (ESI) Calcd for [CH12Br22+H] , Found S4

5 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), (m, 3H), (m, 3H). 13 C MR (1 MHz, CDCl3) δ 166.9, (d, JC-F = Hz), 164.3, 16 (d, JC-F = Hz), 16, 153.8, 137.7, (d, JC-F = 3.2 Hz), (d, JC-F = 8.5Hz), 13.9, (d, JC-F = 1.4 Hz), (d, JC-F = 14.8 Hz), 118.8, (d, JC-F = 2 Hz), (d, JC-F = 21.6 Hz), (d, JC-F =.2Hz). HRMS (ESI) Calcd for [CH12F22+H] , Found Product 3ea was obtained as a white solid in 52% yield (43.5 mg). 1 H MR ( MHz, CDCl3) δ (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), (m, 3H). 13 C MR (1 MHz, CDCl3) δ 167.1, 161.3, 151.5, 1.4, 137.1, (q, JC-F = 32.9 Hz), (q, JC-F = 32.6 Hz), 131.3, 13.5, 13.2, 128.8, 128.7, 127.7, (q, JC-F = 4.3 Hz), (q, JC-F = 3.7 Hz), 12 (q, JC-F = 51.2 Hz) (q, JC-F = 3.1 Hz), 122.6, (q, JC-F = 5 Hz). HRMS (ESI) Calcd for [C22H12F62+H] , Found S5

6 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), (m, 3H), 7.43 (s, 1H), (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, HRMS (ESI) Calcd for [C22H1822+H] , Found 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), (m, 3H), (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, HRMS (ESI) Calcd for [C22H182+H] , Found Product 3ha was obtained as a white solid in 68% yield ( mg). 1 H MR ( MHz, CDCl3) δ (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), (m, 3H), 7.22 (dd, J = 4.8, 4.1 Hz, 1H). 13 C MR (1 S6

7 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, HRMS (ESI) Calcd for [C16H12S2+H] , Found 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), (m, 3H), (m, 5H), 2.52 (s, 6H). 13 C MR (1 MHz, CDCl3) δ 167.8, 159.7, 15.5, (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, HRMS (ESI) Calcd for [C22H182+H] , Found Product 3ja was obtained as a white solid in 73% yield (46.5 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.89 (d, J = 8.4 Hz, 1H), (m, 8H), (m, 1H). 13 C MR (1 MHz, CDCl3) δ (d, JC-F = 2.7 Hz), , (d, JC-F = Hz), 1.3 (d, JC-F = 1.3 Hz), (d, JC-F = Hz), (d, JC-F = 12.2 Hz), (d, JC-F = 7.4 Hz), 137.5, 13, 13.2 (d, JC-F = 8.1 Hz), 128.8, 128.6, (d, JC-F = 7.5 Hz), (d, JC-F = Hz), (d, JC-F = 2.2 Hz), (d, JC-F = 4.9 Hz), (d, JC-F = 18.2 Hz), (d, JC-F = 22.5 Hz), (d, JC-F = 21 Hz). HRMS (ESI) Calcd for [CH12F22+H] , Found S7

8 Product 3ka was obtained as a yellow solid in 78% yield (59.7 mg). 1 H MR ( MHz, CDCl3) δ (m, 3H), 8.75 (s, 1H), 8.47 (s, 1H), (m, 3H), 3 (t, J = 8.5 Hz, 2H), 7.97 (d, J = 8.5 Hz, 1H), (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, (two overlapping signals), (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] , Found Product 3la was obtained as a white solid in 61% yield (4 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 8.16 (d, J = Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), (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] , Found ma S8

9 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), (m, 3H), 7.3 (d, J = 9.8 Hz, 1H), (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, HRMS (ESI) Calcd for [C23H2+H] , Found 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), (m, 4H), (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, HRMS (ESI) Calcd for [C22H182+H] , Found Product 3oa was obtained as a white solid in 82% yield (53.9 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.75 (dd, J = 9.8, 2.5 Hz, 1H), 7.7 (dd, J = 9.1, 6.1 Hz, 1H), (m, 3H), (m, 3H), 7.19 (s, 1H), 2. (s, 1H), 2.16 (s, 1H). 13 C MR (1 MHz, CDCl3) δ 169.7, (d, JC-F = Hz), 161.2, (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), (d, JC-F = 1.9 Hz), 128.8, 128.5, 119.9, (d, JC-F = 2 Hz), S9

10 112.6 (d, JC-F =.2 Hz),.9, HRMS (ESI) Calcd for [C22H17F2+H] , Found Product 3pa was obtained as a white solid in 46% yield (21.6 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.97 (d, J = 8.4 Hz, 1H), 7.85 (s, 1H), (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, HRMS (ESI) Calcd for [C16H142+H] , Found 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), (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, (d, JC-F = 7.7 Hz), 161.1, (d, JC-F = 13.7 Hz), 137.9, 13.7, 128.6, 128.5, (d, JC-F = 1.5 Hz), 1.2, (d, JC-F = 2 Hz), (d, JC-F =. Hz),.6. HRMS (ESI) Calcd for [C15H11F2+H] , Found 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), (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

11 141.3, 13, (q, JC-F = 32.4 Hz), 13.6, 13.4 (two overlapping signals), 129.7, 128.6, 128.6, 128.3, 126.1, (q, JC-F = Hz), 119.6, HRMS (ESI) Calcd for [C22H15F32+H] , Found Product 3ra was obtained as a white solid in 48% yield (3 mg). 1 H MR ( MHz, CDCl3) δ (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), (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, (q, JC-F = 32.9 Hz), 134.2, 13, 13.2, 129.5, 128.8, 128.6, 128.5, (q, JC-F = 4.3 Hz), 122.9, (q, JC-F = 2.1 Hz), 122.1, HRMS (ESI) Calcd for [C22H15F32+H] , Found 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), (m, 3H), (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), HRMS (ESI) Calcd for [CH13Cl2+H] , Found S11

12 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), (m, 3H), 7.65 (d, J = 8.6 Hz, 2H), (m, 3H), (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, 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 (m, 2H), 8.13 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 7.3 Hz, 1H), (m, 3H), (m, 3H), (m, 1H), (m, 2H). 13 C MR (1 MHz, CDCl3) δ 168.3, (d, JC-F = Hz), 159.3, 151.9, 137.5, (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, (d, JC-F = 2 Hz). HRMS (ESI) Calcd for [CH13F2+H] , Found ae 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), (m, 3H), (m, 3H), (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, HRMS (ESI) Calcd for [CH162+H] , Found S12

13 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), (m, 3H), (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, HRMS (ESI) Calcd for [C24H222+H] , Found 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), (m, 3H), (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, HRMS (ESI) Calcd for [C21H162+H] , Found 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), (m, 3H), (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

14 133.3, 131.6, 13.2, 134, 132, 129.2, 128.6, 127.4, 127.2, 127.1, 122.8, HRMS (ESI) Calcd for [CH13Br2+H] + 363, Found Product 3ai was obtained as a white solid in 72% yield (45.6 mg). 1 H MR ( MHz, CDCl3) δ 8.71 (s, 1H), (m, 1H), 8.15 (t, J = 7.7 Hz, 2H), (m, 3H), (m, 3H), (m, 1H), (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, HRMS (ESI) Calcd for [CH13Cl2+H] , Found 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), (m, 2H), (m, 3H), 7.76 (d, J = 7.5 Hz, 1H), (m, 5H). 13 C MR (11 MHz, CDCl3) δ 168.6, 158.7, 151.8, 13, 137.4, 133.8, (two overlapping signals), 13 (q, JC-F = 32.1 Hz), 13.2, 13.1, 129.2, 128.9, 128.6, 127.5, 127.1, (q, JC-F = 3.7 Hz), (q, JC-F = 3.8 Hz), HRMS (ESI) Calcd for [C21H13F32+H] , Found S14

15 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), (m, 3H), (m, 4H), (m, 1H), 7. (t, J = 8.2 Hz, 1H). 13 C MR (1 MHz, CDCl3) δ 168.4, 16 (d, JC-F = 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, (d, JC-F = 2.7 Hz), 121.8, (d, JC-F = 21.4 Hz), (d, JC-F = 2 Hz). HRMS (ESI) Calcd for [CH13F2+H] , Found Product 3al was obtained as a white solid in 83% yield (49.2 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 8.16 (dd, J = 8.4 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), (m, 3H), (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, , , 137.7, 133.5, 131.3, 13.2, 129.9, , , 128.5, 128.4, 12, 126.9, 125.9, 121.7, HRMS (ESI) Calcd for [C21H162+H] , Found 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), (m, 3H), (m, 4H), (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, HRMS (ESI) Calcd for [C21H162+H] , Found S15

16 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), (m, 3H), (m, 3H), (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, HRMS (ESI) Calcd for [C18H122S+H] , 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), (m, 3H), (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, HRMS (ESI) Calcd for [C18H17Cl2+H] , Found H 3aaa Ph Product 3aaa was obtained as a white solid in 36% yield (28.9 mg). 1 H MR ( MHz, CDCl3) δ (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), (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, (two S16

17 overlapping signals), 127.4, 123.8, 123.2, 121.1, 12. HRMS (ESI) Calcd for [C27H193+H] , Found 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), (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, HRMS (ESI) Calcd for [C16H142+H] , Found ba Product 5ba was obtained as a white solid in 86% yield (48.8 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 8.12 (d, J = 8.7 Hz, 1H), 2 (d, J = 1.9 Hz, 1H), S17

18 (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, HRMS (ESI) Calcd for [C16H13Cl2+H] , Found ca Product 5ca was obtained as a white solid in 88% yield (57.7 mg). 1 H MR ( MHz, CDCl3) δ (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), (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, HRMS (ESI) Calcd for [C16H13Br2+H] , Found da 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), (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, HRMS (ESI) Calcd for [C17H162+H] , Found ea 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), (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

19 1.7, 154.2, 138.3, 13.3, 128.3, 128.3, 124.7, 118.4, 19.6, 16.4, 62.5, 55.5, HRMS (ESI) Calcd for [C17H1622+H] , Found fa Product 5fa was obtained as a white solid in 76% yield (39.9 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.83 (s, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.52 (dd, J = 8.5, 1.5 Hz, 1H), (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, HRMS (ESI) Calcd for [C17H162+H] , Found ga Product 5ga was obtained as a white solid in 67% yield (36.1 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.84 (d, J = 7.8 Hz, 1H), (m, 1H), (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 (d, J = 4.9 Hz), 1.5 (2C), (d, J = 2.8 Hz), 153.9, 137.6, (d, J = 9.7 Hz), 13.8, 128.5, 128.4, (d, J = 4.4 Hz), (d, J = 21.2 Hz), 63.24, HRMS (ESI) Calcd for [C16H13F2+H] , Found ha Product 5ha was obtained as a white solid in 74% yield (47.3 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.88 (d, J = Hz, 1H), (m, 3H), (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, HRMS (ESI) Calcd for [C16H12Cl22+H] , Found S19

20 ia Product 5ia was obtained as a white solid in 72% yield (36.7 mg). 1 H MR ( MHz, CDCl3) δ (m, 2H), 7.9 (d, J = 5.4 Hz, 1H), (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, HRMS (ESI) Calcd for [C14H122S+H] , Found ja 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), (m, 1H), (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] , Found ka 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), (m, 1H), (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, HRMS (ESI) Calcd for [C17H162+H] , Found S

21 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, , 127.9, 126.5, 123.6, 115.4, 62.9, HRMS (ESI) Calcd for [C16H13Cl2+H] , Found ad 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, (d, J = Hz), 159.1, 151.8, (d, J = 2.9 Hz), 133.5, 13.5 (d, J = 8.5 Hz), 127.8, 126.3, 123.6, (d, J = 21.5 Hz), 115.2, 62.9, HRMS (ESI) Calcd for [C16H13F2+H] , Found af 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

22 62.8, 34.9, 31.3, HRMS (ESI) Calcd for [CH232+H] , Found ai 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), (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, HRMS (ESI) Calcd for [C16H13Cl2+H] , Found aj 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, (q, J = 3.7 Hz), 126.7, (q, J = 3.9 Hz), (q, J = 27.6 Hz), 123.5, 115.5, 6, HRMS (ESI) Calcd for [C17H13F32+H] , Found am 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), (m, 1H), 7.82 (t, J = 7.7 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), (m, 3H), 4.69 (q, J = 7.1 S22

23 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, HRMS (ESI) Calcd for [C17H162+H] , Found an 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), (m, 1H), 7.94 (d, J = 8.4 Hz, 1H), (m, 1H), (m, 1H), 6.98 (dd, J = 8.4, 2.7 Hz, 1H), (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, HRMS (ESI) Calcd for [C18H1923+H] , Found ao 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), (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, HRMS (ESI) Calcd for [C14H122S+H] , Found ap 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

24 1H), 7.48 (t, J = 7.5 Hz, 1H), 4.64 (q, J = 7.1 Hz, 2H), 4 (s, 2H), (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, HRMS (ESI) Calcd for [C14H17Cl2+H] , Found aq 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), (m, 1H), (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, HRMS (ESI) Calcd for [C17H16Cl2+H] , Found 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), (m, 4H), 7.68 (dd, J = 7.5, 1.2 Hz, 1H), (m, 1H), (m, 3H), (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

25 13.3, 129.9, 129.8, 129.3, 128.7, , 127.4, 126.9, 122.8, 121.4, 16.2, 9, 18.5, HRMS (ESI) Calcd for [C31H342Si+H] , Found ,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%, mg). 1 H MR ( MHz, DMS-d6) δ (s, 1H), 8.19 (d, J = 7.6 Hz, 1H), 7.93 (dd, J = 8.5, 1.7 Hz, 1H), (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

26 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, HRMS (ESI) Calcd for [C16H1523+H] , Found 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 (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] , Found S26

27 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

28 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) 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 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

29 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 e.å-3 S29

30 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

31 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

32 References (1) McMahon, J. P.; Ellman, J. A. rg. Lett. 4, 6, (2) Yaday, V. K.; Babu, K. G. Eur. J. rg. Chem. 5, 452. S32

33 S33 MR Spectra

34 S Cl Cl 3ba Cl Cl 3ba

35 S Br Br 3ca Br Br 3ca

36 S

37 S CF 3 F 3 C 3ea

38 S

39 S

40 S

41 S ia 3ia

42 S

43 S ka 3ka

44 S f1 (ppm) Cl 3la Cl 3la

45 S

46 S na major, :1 3na major, :1

47 S F 3oa major, :1 F 3oa major, :1

48 S

49 S

50 S CF 3 3ra CF 3 3ra

51 S F 3 C 3ra' F 3 C 3ra'

52 S Cl 3ab Cl 3ab

53 S

54 S F 3ad F 3ad

55 S ae 3ae

56 S

57 S

58 S Br 3ah Br 3ah

59 S

60 S

61 S al 3al

62 S

63 S an S 3an S

64 S

65 S H

66 S

67 S Cl Cl

68 S Br Br

69 S H 3 C H 3 C

70 S

71 S H 3 C H 3 C

72 S F F