Supporting Information. Rh(III)-Catalyzed C7-Thiolation and Selenation of Indolines

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1 Supporting Information Rh(III)-Catalyzed C7-Thiolation and Selenation of Indolines Wucheng Xie, Bin Li, Baiquan Wang *,,, State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin , China State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,Shanghai , China Contents Table of Contents S1 Crystallographic Studies S2 Figure S S2 Optimization of Reaction S3 NMR Spectra S4-S47 S1

2 Crystallographic Studies. Single crystals of 3ag suitable for X-ray analysis were grown from petroleum ether/ ethyl acetate at room temperature. Data collections were carried out on a Rigaku Saturn 70 diffractometer equipped with a rotating anode system at 113(2) K by using graphite-monochromated Mo Kα radiation (ω 2θ scans, λ = Å). Semiempirical absorption corrections were applied for all complexes. The structures were solved by direct methods and refined by full matrix least-squares. Calculations were performed by using the SHELXL-97 program system. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were assigned idealized positions and were included in structure factor calculations. Figure S1. The molecular structure of 3ag. Thermal ellipsoids are shown at the 30% level. Hydrogen atoms have been omitted for clarity. S2

3 Table S1. Optimization of Reaction Conditions a N N 1a N + PhSSPh 2a [Cp*RhCl 2 ] 2 Additive toluene, 12 h 110 o C N SPh N 3a N entry Ag Source solvent Additive yield (%) a AgSbF 6 AgOAc AgBF 4 toluene toluene toluene Ag 2 CO 3 Ag 2 CO 3 Ag 2 CO 3 Trace n.r AgOTf toluene Ag 2 CO AgOTf toluene K 2 CO 3 Trace 6 AgOTf toluene Cu(OAc) AgOTf toluene Zn(OAc). 2 2H 2 O Trace 8 AgOTf toluene Ag 2 O 85 a Condition: 1a (0.3 mmol), 2a (0.3 mmol), [Cp*RhCl 2 ] 2 (0.015 mmol), Ag Source (0.06 mmol, 20 mol %), Additive (0.3 mmol), solvent (1.5 ml), heating in a sealed tube, under air; isolated yield are shown. Table S2. Optimization of Reaction Conditions a S3

4 Spectral Copies of 1 H, 13 C, and 19 F NMR of Compounds Obtained in This Study S4

5 1 H NMR spectrum of compound 3aa 13 C NMR spectrum of compound 3aa S5

6 1 H NMR spectrum of compound 3ba 13 C NMR spectrum of compound 3ba S6

7 1 H NMR spectrum of compound 3ca 13 C NMR spectrum of compound 3ca S7

8 1 H NMR spectrum of compound 3da 13 C NMR spectrum of compound 3da S8

9 1 H NMR spectrum of compound 3ea 13 C NMR spectrum of compound 3ea S9

10 1 H NMR spectrum of compound 3fa 13 C NMR spectrum of compound 3fa S10

11 19 F NMR spectrum of compound 3fa 1 H NMR spectrum of compound 3ga S11

12 13 C NMR spectrum of compound 3ga 1 H NMR spectrum of compound 3ha S12

13 13 C NMR spectrum of compound 3ha 1 H NMR spectrum of compound 3ia S13

14 13 C NMR spectrum of compound 3ia 1 H NMR spectrum of compound 3ja S14

15 13 C NMR spectrum of compound 3ja 1 H NMR spectrum of compound 3ka S15

16 13 C NMR spectrum of compound 3ka 1 H NMR spectrum of compound 3la S16

17 13 C NMR spectrum of compound 3la 19 F NMR spectrum of compound 3la S17

18 1 HNMR spectrum of compound 3ma 13 C NMR spectrum of compound 3ma S18

19 1 H NMR spectrum of compound 3ab 13 C NMR spectrum of compound 3ab S19

20 1 H NMR spectrum of compound 3ac 13 C NMR spectrum of compound 3ac S20

21 19 F NMR spectrum of compound 3ac 1 H NMR spectrum of compound 3ad S21

22 13 C NMR spectrum of compound 3ad 1 H NMR spectrum of compound 3ae S22

23 13 C NMR spectrum of compound 3ae 1 H NMR spectrum of compound 3af S23

24 13 C NMR spectrum of compound 3af 1 H NMR spectrum of compound 3ag S24

25 13 C NMR spectrum of compound 3ag 1 H NMR spectrum of compound 3ah S25

26 13 C NMR spectrum of compound 3ah 1 H NMR spectrum of compound 3ai S26

27 13 C NMR spectrum of compound 3ai 1 H NMR spectrum of compound 3aj S27

28 13 C NMR spectrum of compound 3aj 1 H NMR spectrum of compound 5aa S28

29 13 C NMR spectrum of compound 5aa 1 H NMR spectrum of compound 5ba S29

30 13 C NMR spectrum of compound 5ba 1 H NMR spectrum of compound 5ca S30

31 13 C NMR spectrum of compound 5ca 1 H NMR spectrum of compound 5da S31

32 13 C NMR spectrum of compound 5da 1 H NMR spectrum of compound 5ea S32

33 13 C NMR spectrum of compound 5ea 1 H NMR spectrum of compound 5fa S33

34 13 C NMR spectrum of compound 5fa 19 F NMR spectrum of compound 5fa S34

35 1 H NMR spectrum of compound 5ga 13 C NMR spectrum of compound 5ga S35

36 1 H NMR spectrum of compound 5ha 13 C NMR spectrum of compound 5ha S36

37 1 H NMR spectrum of compound 5ia 13 C NMR spectrum of compound 5ia S37

38 1 H NMR spectrum of compound 5ja 13 C NMR spectrum of compound 5ja S38

39 1 H NMR spectrum of compound 5ab 13 C NMR spectrum of compound 5ab S39

40 1 H NMR spectrum of compound 5ac 13 C NMR spectrum of compound 5ac S40

41 1 H NMR spectrum of compound 5ad 13 C NMR spectrum of compound 5ad S41

42 1 H NMR spectrum of compound 5ae 13 C NMR spectrum of compound 5ae S42

43 1 H NMR spectrum of compound 5af 13 C NMR spectrum of compound 5af S43

44 1 H NMR spectrum of compound 6 13 C NMR spectrum of compound 6 S44

45 1 H NMR spectrum of compound 7 13 C NMR spectrum of compound 7 S45

46 1 H NMR spectrum of compound 8 13 C NMR spectrum of compound 8 S46

47 1 H NMR of 1a recovered in the deuterium exchange reaction without diphenyl disulfide. 1 H NMR of 1a recovered in the deuterium exchange reaction with diphenyl disulfide. S47