PDF《unactivated alkenes?》

S1? ? Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes? Ning-Yuan Yang,? Zhong-Liang Li,? Liu Ye, Bin Tan and Xin-Yuan Liu* Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055, China.

email: liuxy3@sustc.edu.cn Table of Contents General information…S2 Supplementary Table S1…S3 Supplementary Scheme S1…S3 Experimental procedure.S4 Mechanistic study.S26 NMR Spectrum.S31 S2? ? General information All reactions were carried out under argon using Schlenk techniques. Reagents were purchased at the commercial quality and used without further purification. Analytical thin layer chromatography (TLC) was performed on precoated silica gel

60 GF254 plates. Flash column chromatography was performed using Tsingdao silica gel (60, particle size 0.040-0.063 mm). Visualization on TLC was achieved by use of UV light (254 nm) or iodine. NMR spectra were recorded on a Bruker DPX

400 spectrometer at

400 MHz for

1 H NMR,

100 MHz for

13 C NMR and

376 MHz for

19 F NMR in CDCl3 with tetramethylsilane (TMS) as internal standard. The chemical shifts are expressed in ppm and coupling constants are given in Hz. Data for

1 H NMR are recorded as follows: chemical shift (ppm), multiplicity (s, singlet;

d, doublet;

t, triplet;

q, quarter;

m, multiplet), coupling constant (Hz), integration. Data for

13 C NMR are reported in terms of chemical shift (δ, ppm).

19 F NMR spectra were recorded on a Bruker DPX

400 MHz spectrometer (CFCl3 as an external reference (0 ppm)).?Mass spectrometric data were obtained using Bruker Apex IV RTMS. S3? ? Table S1 Screening of reaction conditions for oxytrifluoromethylation.a Entry Base (X equiv) Solvent T (°C) Yield(%) of 4a (3a)b

1 DIPEA (0.2) EtOAc

80 70 (7)

2 DIPEA (0.2) EtOH

80 58 (17)

3 DIPEA (0.2) CH3CN

80 66 (21)

4 DIPEA (0.2) DCE

80 85 (10)

5 DIPEA (0.2) DCE

80 83 (11)c

5 DIPEA (0.2) DCE

80 71 (10)d

6 DIPEA (0.15) DCE

80 75 (11)d a Unless otherwise noted, the reaction was conducted with 1a (0.1 mmol), Togni'

s ester 2a (0.2 mmol), and base (0.02 mmol) in 1.0 mL solvent for

10 h. b Determined by

19 F NMR spectroscopy using PhCF3 as an internal standard. c 2a (0.3 mmol) was used. d 2b (0.2 mmol) was used. Supplementary Scheme S1: Control experiments and KIE study ? S4? ? ? Experimental procedure for synthesis of substrates Compound 1p was synthesized following literature.1 General Procedure for the Synthesis of 1a-1l, 1s, 1t, and 1u-1y Methyltriphenylphosphonium bromide (17.20g,

48 mmol) was dissolved in THF (60 mL) in a dried round bottom flask equipped with an ice water bath. Then KOt-Bu (5.39g,

48 mmol), the yellow suspension was stirred at

0 °C for

45 min. To this suspension was added a solution of the corresponding ketone (40 mmol) in THF (0.7 mmol/mL) dropwisely and the resulting mixture was stirred for

16 h at room temperature. The mixture was concentrated under reduced pressure and filtered. The solid was washed with petroleum ether (3 *

15 mL) and the combined organic layer was concentrated and purified by flash column chromatography (petroleum ether/EtOAc 20:1) to give the corresponding propene S1. The propene S1 (1.0 equiv) was dissolved in THF (3.0 mmol/mL) in a dried round bottom flask, followed by addition of N-Bromosuccinimide (1.05 equiv) and TsOH (0.1 equiv). The reaction solution was heated to

100 °C and stirred for

4 h, then cooled down to room temperature. Quenched with water (100 mL), extracted with EtOAc (3 *