Supporting Information For. Visible Light Photocatalytic Radical-Radical Cross-Coupling. Reactions of Amines and Carbonyls: A Route to 1,2-Amino

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1 Supporting Information For Visible Light Photocatalytic Radical-Radical Cross-Coupling Reactions of Amines and Carbonyls: A Route to,2-amino Alcohols Wei Ding, Liang-Qiu Lu, Jing Liu, Dan Liu, Hai-Tao Song, and Wen-Jing Xiao* Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 52 Luoyu Road, Wuhan, Hubei , China wxiao@mail.ccnu.edu.cn Table of Contents. Details for Conditions Optimization S2 2. Luminescence Quenching S5 3. Investigation of Homo-coupling By-product S6 4. Quantum Yield Mensuration S7 5. Other Plausible Reaction Mechanisms S8 6. Copies of H NMR and 3 C NMR Spectra of Products 3 S9 S

2 . Details for Conditions Optimization Table S. Studies of the effect of photocatalysts and solvents a entry photocatalyst solvent Yield b Ir(ppy) 2(bpy)PF 6 THF 0% 2 Ir[dF(CF 3)ppy] 2(dtbbpy)PF 6 THF 0% 3 fac-ir(ppy) 3 THF 34% 4 Ru(bpy) 3(PF 6) 2 THF 0% 5 N-Me-9-Mes-Acr-ClO 4 THF 0% 6 fac-ir(ppy) 3 CH 3OH 0% 7 fac-ir(ppy) 3 CH 2Cl 2 23% 8 fac-ir(ppy) 3 CHCl 3 0% a Unless otherwise noted, reactions were performed with a (0.2 mmol,.0 equiv.), 2a (0.4 mmol, 2.0 equiv.), photocatalyst (0.004 mmol, 2 mol%), DABCO (0.4 mmol, 2.0 equiv.), LiBF4 (0.2 mmol,.0 equiv.), solvent (2.0 ml) under Ar. b Determined by H NMR using,3,5-trimethoxybenzene as an internal standards. S2

3 Table S2. Studies of the effect of bases and additives a entry base aditive Yield b 2,6-lutidine LiBF 4 0% 2 i Pr 2NEt LiBF 4 50% 3 Et 3N LiBF 4 2% 4 Cs 2CO 3 LiBF 4 0% 5 K 2HPO 4 LiBF 4 47% 6 DMAP LiCO 3 22% 7 DMAP LiBr 58% 8 DMAP LiCl 32% 9 DMAP LiClO 4 48% 0 DMAP Mg(ClO 4) 2 42% DMAP Sc(OTf) 3 5% 2 DMAP La(OTf) 3 37% 3 DMAP CF 3CO 2H 22% 4 DMAP TsOH-H 2O 43% 5 DMAP (PhO) 2OPOH 0% 6 c DMAP LiBF 4 34% 7 d DMAP LiBF 4 32% 8 e DMAP LiBF 4 49% 9 f DMAP LiBF 4 60% a Unless otherwise noted, reactions were performed with a (0.6 mmol, 3.0 equiv.), 2a (0.2 mmol,.0 equiv.), fac-ir(ppy)3 (0.004 mmol, 2 mol%), base (0.4 mmol, 2.0 S3

4 equiv.), additive (0.2 mmol,.0 equiv.), THF (2.0 ml) under Ar. b Determined by H NMR using,3,5-trimethoxybenzene as an internal standard. c a (0.2 mmol) and 2a (0.4 mmol, 2.0 equiv.) were used. d a (0.2 mmol,.0 equiv.) and 2a (0.2 mmol) were used. e a (0.4 mmol, 2.0 equiv.) and 2a (0.2 mmol) were used. f a (0.8 mmol, 4.0 equiv.) and 2a (0.2 mmol) were used. S4

5 I 2. Luminescence Quenching The luminescence quenching experiment was taken using a Cary Eclipse fluorescence spectrophotometer (Varian, USA). The experiments were carried out in 0.05 mmol/l of fac-ir(ppy)3/thf at 25 o C and the excitation wavelength was 375 nm. The concentrations of quenchers (amine a and benzophenone 2a) in THF were 0, 0.5 mmol/l, mmol/l, 5 mmol/l, 0 mmol/l, 20 mmol/l, and 30 mmol/l. 000 I Io/I Wavelength (nm) Quencher concentration (mm) Luminescence quenching of fac-ir(ppy) 3 by amine a Io/I Wavelength (nm) Quencher concentration (mm) Luminescence quenching of fac-ir(ppy) 3 by benzophenone 2a S5

6 3. Investigation of Homo-coupling By-product 3. Detection of,2-diamine By-product 3.2 Control Experiments Using Only Amine a or Ketone 2a S6

7 4. Quantum Yield Mensuration A cuvette was charged with secondary amine a (0.3 mmol, 3.0 equiv), benzophenone 2a (0. mmol,.0 equiv), DMAP (0.2 mmol, 2.0 equiv), LiBF4 (0. mmol,.0 equiv), fac-ir(ppy)3 (0.002 mmol, 2 mol%), and 2.0 ml THF (0.05 M). The sample was stirred and irradiated (λ=436 nm, slit width=0.0 nm with intensity of 3 mw cm -2 ) for 7200 s (2 h). After irradiation, the yield of product formed was determined by H NMR based on a,3,5-trimethoxybenzene standard. The quantum yield was determined as follows. ϕ = Mole number for product/mole number for absorption of photons = n3aa: the mole number of the product 3aa; t: reaction time (7200 s); NA: /mol; f: -0 -A (436 nm, A=0.563); P: P=E*S (E: illumination intensity, E=3 mw/cm 2 ; S: the area that irradiated S= cm 2 ); λ: wavelength (λ= m); h: planck constant (h= J*s); c: velocity of light (c=3 0 8 m/s). S7

8 5. Other Plausible Reaction Mechanisms 5. Radical Addition Pathway 5.2 Coordination of -Amino Radical and Ketyl Radical by Li + S8

9 6. Copies of H NMR and 3 C NMR spectra of products 3 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3aa S9

10 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ba S0

11 H NMR (400 MHz, CDCl 3) and 3 C NMR (50 MHz, CDCl 3) spectrum of product 3ca S

12 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3da S2

13 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ea S3

14 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3fa S4

15 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ga S5

16 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ha S6

17 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ia S7

18 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ja S8

19 H NMR (600 MHz, CDCl 3) and 3 C NMR (50 MHz, CDCl 3) spectrum of product 3ka S9

20 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ab S20

21 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ac S2

22 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ad S22

23 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ae S23

24 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3af S24

25 H NMR (600 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ag S25

26 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3la S26

27 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3ma S27

28 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3na S28

29 H NMR (400 MHz, CDCl 3) and 3 C NMR (00 MHz, CDCl 3) spectrum of product 3oa S29