PDF《Supporting Information》

1 H NMR (400 MHz, CDCl3) δ 8.56 (d, J = 3.2 Hz, 1H), 8.52 (br, 1H), 7.81 (d, J = 8.8 Hz, 2H), 7.72 (td, J = 7.6, 1.6 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.20 (ddd, J = 7.2, 4.8, 0.8 Hz, 1H), 6.71 C 6.69 (m, 2H), 3.02 (s, 6H), 1.87 (s, 6H);

13 C NMR (100 MHz, CDCl3) δ 166.47, 165.32, 152.40, 147.73, 137.16, 128.50, 123.14, 121.85, 119.67, 111.24, 56.57, 40.30, 27.90. HRMS (EI-TOF) calcd for C17H21N3O (M+ ): 283.1685, found: 283.1687. N-(2-(pyridin-2-yl)propan-2-yl)furan-2-carboxamide 1q The title compound 1q was prepared according to the general procedure (Method B).

1 H NMR (400 MHz, CDCl3) δ 8.67 (br, 1H), 8.59 (d, J = 4.4 Hz, 1H), 7.74 (t, J = 8.0 Hz, 1H), 7.46 (t, J = 8.0 Hz, 2H), 7.22 (dd, J = 6.4, 5.2 Hz, 1H), 7.08 (d, J = 3.2 Hz, 1H), 6.49 C 6.48 (m, 1H), 1.86 (s, 6H);

13 C NMR (100 MHz, CDCl3) δ 164.46, 157.79, 149.31, 147.93, 143.70, 137.25, 122.05, 119.54, 113.53, 112.02, 56.83, 27.80. HRMS (EI-TOF) calcd for C13H14N2O2 (M+ ): 230.1055, found: 230.1058. N-(2-(pyridin-2-yl)propan-2-yl)furan-3-carboxamide 1r The title compound 1q was prepared according to the general procedure (Method B).

1 H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 4.0 Hz, 1H), 8.46 (br, 1H), 7.97 (s, 1H), 7.77 C 7.73 (m, 1H), 7.45 (d, J = 9.6 Hz, 2H), 7.23 (dd, J = 7.2, 5.2 Hz, 1H), 6.73 (s, S5 1H), 1.85 (s, 6H);

13 C NMR (100 MHz, CDCl3) δ 164.58, 161.88, 147.67, 144.60, 143.61, 137.41, 124.32, 122.11, 119.67, 108.73, 56.65, 27.73. HRMS (EI-TOF) calcd for C13H14N2O2 (M+ ): 230.1055, found: 230.1051. 2.2 Optimization of Reaction Conditionsa N H O

140 °C,

12 h N H PIP O 1a 3a PIP SPh Me Me [Ni] (10 mol%), L (20 mol%) additive (2.0 eqiv), DMSO H + PhSSPh 2a entry [Ni] ligand additive (equiv) solvent yield

1 Ni(OTf)2 PPh3 Na2CO3 (2.0) toluene 8%

2 Ni(OTf)2 PPh3 Na2CO3 (2.0) t-AmylOH trace

3 Ni(OTf)2 PPh3 Na2CO3 (2.0) 1,4-dioxane trace

4 Ni(OTf)2 PPh3 Na2CO3 (2.0) DMF 15%

5 Ni(OTf)2 PPh3 Na2CO3 (2.0) DMSO 45%

6 NiBr2 PPh3 Na2CO3 (2.0) DMSO 27%

7 Ni(acac)2 PPh3 Na2CO3 (2.0) DMSO 46%

8 NiCl2 PPh3 Na2CO3 (2.0) DMSO 50%

9 NiCl2・6H2O PPh3 Na2CO3 (2.0) DMSO 59%

10 NiCl2・6H2O TMEDA Na2CO3 (2.0) DMSO 50%

11 NiCl2・6H2O dppp Na2CO3 (2.0) DMSO 46%

12 NiCl2・6H2O dppb Na2CO3 (2.0) DMSO 72%

13 NiCl2・6H2O dppe Na2CO3 (2.0) DMSO 60%

14 NiCl2・6H2O PCy3 Na2CO3 (2.0) DMSO 49%

15 NiCl2・6H2O BINOL Na2CO3 (2.0) DMSO 78%

16 NiCl2・6H2O BINOL K2CO3 (2.0) DMSO 76%

17 NiCl2・6H2O BINOL NaHCO3 (2.0) DMSO 66%

18 NiCl2・6H2O BINOL KHCO3 (2.0) DMSO 55%

19 NiCl2・6H2O BINOL K3PO4 (2.0) DMSO 75% S6

20 NiCl2・6H2O BINOL NaTFA (2.0) DMSO 67%

21 NiCl2・6H2O BINOL KTFA (2.0) DMSO 88%

22 ― ― KTFA (2.0) DMSO trace

23 NiCl2・6H2O ― KTFA (2.0) DMSO 49% 24b NiCl2・6H2O BINOL KTFA (2.0) DMSO 88% (84%)c

25 Cu(OAc)2 BINOL KTFA (2.0) DMSO trace a1 H NMR yield using CH2Br2 as the internal standard. b

8 h. c Isolated yield in parenthesis. 2.3 Screening of Other Directing Groups 2.4 General Procedure for the Thiolation To a

50 mL Schlenk tube was added substrate (0.15 mmol), ArSSAr (0.3 mmol), NiCl2・6H2O (3.6 mg, 0.015 mmol), BINOL (8.6 mg, 0.03 mmol), KTFA (45.6 mg, 0.

3 mmol), and DMSO (1 mL). The vial was evacuated and filled with N2 (1 atm), and stirred at

140 °C for

8 h. The mixture was then cooled to room temperature, diluted with water, extracted with ethyl acetate (3*20 mL). The combined phase was then washed with brine, if necessary it can be washed with NaOH solution to remove the ligand BINOL and dried with anhydrous magnesium sulfate. After concentration, the S7 resulting residue was purified by preparative TLC using hexane/EtOAc as the eluent to afford the prcoduct. 6-Methyl-2-(phenylthio)-N-(2-(Pyridin-2-yl)propan-2-yl)benzamide 3a