Supporting Information Intermolecular Oxidative C−N Bond Formation under Metal-Free Conditions: Control of Chemoselectivity between Aryl sp2 and Benzylic sp3 C−H Bond Imidation Hyun Jin Kim, Jiyu Kim, Seung Hwan Cho,* and Sukbok Chang*
Department of Chemistry and Molecular–Level Interface Research Center, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea
I.
General Methods
S2
II.
Preparation of Substrates of the Coupling Products
S2
III.
Optimization Study for the Oxidative Imidation of Benzene
IV.
Experimental Procedure for the Oxidative Amination with Various Nitrogen Sources (Table 2)
V.
S3 ~ S7
Experimental Procedure for Oxidative Imidation of Arenes S7 ~ S16
with Phthalimide (Table 3) VI.
S2 ~ S3
Experimental Procedure for the Oxidative Imidation of Benzylic C-H bond (Table 4)
VII.
Scale up Experiment and Hydrazinolysis (Eq 3)
VIII.
Mechanistic Studies
S18 ~ S19 S19 ~ S25
S26 ~ S58
Appendix I 1
S16 ~ S18
13
Copies of H- and C-NMR Spectral Data Obtained in this Study
S1
I. General Methods Unless otherwise stated, all commercial reagents and solvents were used without additional purification. Analytical thin layer chromatography (TLC) was performed on precoated silica gel 60 F254 plates. Visualization on TLC was achieved by the use of UV light (254 nm). Flash column chromatography was undertaken on silica gel (400-630 mesh). 1H NMR was recorded on 300 MHz and 400 MHz. Chemical shifts were quoted in parts per million (ppm) referenced to the appropriate solvent peak or 0.0 ppm for tetramethylsilane. The following abbreviations were used to describe peak splitting patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublet. Coupling constants, J, were reported in hertz unit (Hz). 13C NMR was recorded on 100 MHz and was fully decoupled by broad band proton decoupling. Chemical shifts were reported in ppm referenced to the center line of a triplet at 77.0 ppm of chloroform-d. Infrared (IR) spectra were recorded neat in 0.5 mm path length using a sodium chloride cell. Frequencies are given in reciprocal centimeters (cm-1) and only selected absorbance is reported. Mass spectral data were obtained from the Korea Basic Science Institute (Daegu) by using EI method.
II. Preparation of Substrates of the Coupling Products Authetic reference compounds of each isomer listed in Table 3 were prepared by the recation of phthalic anhydride with the corresponding anilines according to literature procedure. 1
All
products listed in Table 3 were unambigously assigned by the point-by-point comparison with prepared authentic samples.
1
Capitosti, S. M.; Hansen, T. P.; Brown, M. L. Bioorg. Med. Chem. 2004, 12, 327.
S2
III. Optimization Study for the Oxidative Imidation of Benzene (Table S1) To a 5 mL screw-capped vial equipped with a 15 x 10 mm spinvane triangular-shaped Teflon stirbar, were added succinimide (29.7 mg, 0.3 mmol, 1 equiv), oxidant (indicated equiv) and benzene (1.5 mL). The resulting mixture was sealed with a Teflon-lined cap and stirred at the indicated temperature for 4 h in an oil bath with vigorous stirring. The reaction mixture was cooled to room temperature, filtered through a plug of silica and washed with EtOAc (30 mL). The filtrate was concentrated, and evaporated to dryness under high vacuum. The 1H-NMR yield of desired product was determined by integration using an internal standard (1,1,2,2tetrachloroethane).
Table S1. Optimization Screen of Oxidative Imidation of Benzene. O
O
conditions
H + H N
1a
O 2a
N O 3a
entry
oxidant (equiv)
temp. (oC)
conv. (%)
NMR yield (%)
1
PhI(OAc)2 (5)
80
2
