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 300071, China State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,Shanghai 200032, China bqwang@nankai.edu.cn Contents Table of Contents-------------------------------------------------------------------------------------S1 Crystallographic Studies-----------------------------------------------------------------------------S2 Figure S1-----------------------------------------------------------------------------------------------S2 Optimization of Reaction -----------------------------------------------------------------------------S3 NMR Spectra--------------------------------------------------------------------------------------S4-S47 S1
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 = 0.71073 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
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 1 2 3 AgSbF 6 AgOAc AgBF 4 toluene toluene toluene Ag 2 CO 3 Ag 2 CO 3 Ag 2 CO 3 Trace n.r. 22 4 AgOTf toluene Ag 2 CO 3 89 5 AgOTf toluene K 2 CO 3 Trace 6 AgOTf toluene Cu(OAc) 2 43 7 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
Spectral Copies of 1 H, 13 C, and 19 F NMR of Compounds Obtained in This Study S4
1 H NMR spectrum of compound 3aa 13 C NMR spectrum of compound 3aa S5
1 H NMR spectrum of compound 3ba 13 C NMR spectrum of compound 3ba S6
1 H NMR spectrum of compound 3ca 13 C NMR spectrum of compound 3ca S7
1 H NMR spectrum of compound 3da 13 C NMR spectrum of compound 3da S8
1 H NMR spectrum of compound 3ea 13 C NMR spectrum of compound 3ea S9
1 H NMR spectrum of compound 3fa 13 C NMR spectrum of compound 3fa S10
19 F NMR spectrum of compound 3fa 1 H NMR spectrum of compound 3ga S11
13 C NMR spectrum of compound 3ga 1 H NMR spectrum of compound 3ha S12
13 C NMR spectrum of compound 3ha 1 H NMR spectrum of compound 3ia S13
13 C NMR spectrum of compound 3ia 1 H NMR spectrum of compound 3ja S14
13 C NMR spectrum of compound 3ja 1 H NMR spectrum of compound 3ka S15
13 C NMR spectrum of compound 3ka 1 H NMR spectrum of compound 3la S16
13 C NMR spectrum of compound 3la 19 F NMR spectrum of compound 3la S17
1 HNMR spectrum of compound 3ma 13 C NMR spectrum of compound 3ma S18
1 H NMR spectrum of compound 3ab 13 C NMR spectrum of compound 3ab S19
1 H NMR spectrum of compound 3ac 13 C NMR spectrum of compound 3ac S20
19 F NMR spectrum of compound 3ac 1 H NMR spectrum of compound 3ad S21
13 C NMR spectrum of compound 3ad 1 H NMR spectrum of compound 3ae S22
13 C NMR spectrum of compound 3ae 1 H NMR spectrum of compound 3af S23
13 C NMR spectrum of compound 3af 1 H NMR spectrum of compound 3ag S24
13 C NMR spectrum of compound 3ag 1 H NMR spectrum of compound 3ah S25
13 C NMR spectrum of compound 3ah 1 H NMR spectrum of compound 3ai S26
13 C NMR spectrum of compound 3ai 1 H NMR spectrum of compound 3aj S27
13 C NMR spectrum of compound 3aj 1 H NMR spectrum of compound 5aa S28
13 C NMR spectrum of compound 5aa 1 H NMR spectrum of compound 5ba S29
13 C NMR spectrum of compound 5ba 1 H NMR spectrum of compound 5ca S30
13 C NMR spectrum of compound 5ca 1 H NMR spectrum of compound 5da S31
13 C NMR spectrum of compound 5da 1 H NMR spectrum of compound 5ea S32
13 C NMR spectrum of compound 5ea 1 H NMR spectrum of compound 5fa S33
13 C NMR spectrum of compound 5fa 19 F NMR spectrum of compound 5fa S34
1 H NMR spectrum of compound 5ga 13 C NMR spectrum of compound 5ga S35
1 H NMR spectrum of compound 5ha 13 C NMR spectrum of compound 5ha S36
1 H NMR spectrum of compound 5ia 13 C NMR spectrum of compound 5ia S37
1 H NMR spectrum of compound 5ja 13 C NMR spectrum of compound 5ja S38
1 H NMR spectrum of compound 5ab 13 C NMR spectrum of compound 5ab S39
1 H NMR spectrum of compound 5ac 13 C NMR spectrum of compound 5ac S40
1 H NMR spectrum of compound 5ad 13 C NMR spectrum of compound 5ad S41
1 H NMR spectrum of compound 5ae 13 C NMR spectrum of compound 5ae S42
1 H NMR spectrum of compound 5af 13 C NMR spectrum of compound 5af S43
1 H NMR spectrum of compound 6 13 C NMR spectrum of compound 6 S44
1 H NMR spectrum of compound 7 13 C NMR spectrum of compound 7 S45
1 H NMR spectrum of compound 8 13 C NMR spectrum of compound 8 S46
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