General Information
Reactions (chlorination, bromination, oxidation) were conducted in Pressure-resistant tubes. Reagents and solvents were obtained from commercial suppliers which do not require purification.1H NMR and 13C NMR spectra were measured on a Bruker spectrometer (at 400 and 101 MHz, respectively), and chemical shift were reported as values relative to internal TMS (δ 0.00 for 1H NMR), chloroform (δ 7.26 for 1 H NMR), chloroform (δ 77.00 for13C NMR). High-resolution mass spectrometry (HR MS) was recorded on a waters UPLC G2-XS Qt of instrument. GC-MS spectra were performed on Perkin Elmer Clarus 680 Gas Chromatograph and Clarus 600 T Mass Spectrometer (EI Source). In a general experiment, tubes were set between two 18 W blue lights and kept 2 cm away from the light source, with a fan for cooling the reaction.
General Procedure forChlorination
The DIB (2.08 mmol, 3.5 equiv, 670 mg) and NaCl (1.79 mmol, 3 equiv, 104 mg) were added in a Pressure-resistant tube. Then cyclohexane (65 µL, 1.0 equiv), H2O (0.5 mL), DCM (2.5 mL), were added with pipetter. The tube was sealed with a stopper and positioned between two 18 W blue light (kept above 2 cm away from the light source) and stirred at room temperature (with a fan to cool the reaction down) for 5 h. After the reaction was completed, 50 µL of internal standard (CH2Br2) was added, then 50 µL of mixture was extracted and diluted with CDCl3 to analysis by 1H NMR spectroscopy after vigorous stirring.
General Procedurefor Bromination
The DIB (2.08 mmol, 3.5 equiv, 670 mg) and KBr (0.77 mmol, 1.3 equiv, 93 mg) were added in a Pressure-resistant tube. Then cyclohexane (65 µL, 1.0 equiv), H2O (0.5 mL), DCM (2.5 mL), were added with pipetter. The tube was sealed with a stopper and positioned between two 18 W blue light (kept above 2 cm away from the light source) and stirred at room temperature (with a fan to cool the reaction down) for 5 h. After the reaction was completed, 50 µL of internal standard (CH2Br2) was added, then 50 µL of mixture was extracted and diluted with CDCl3 to analysis by 1H NMR spectroscopy after vigorous stirring.
General Procedurefor Oxidation
The DIB (0.155 mmol, 1.0 equiv, 50 mg) was added in a Pressure-resistant tube. Then cyclohexane (0.67 mL, 40 equiv), H2O (0.5 mL), DCM (2.5 mL), were added with pipetter. The tube was sealed with a stopper and positioned between two 18 W blue light (kept above 2 cm away from the light source) and stirred at room temperature (with a fan to cool the reaction) for 14 h. After the reaction was completed, 50 µL internal standard (CH2Br2) was added, then 50 µL of the mixture was extracted and diluted with CDCl3 to analysis by 1H NMR spectroscopy.
(3s,5s,7s)-adamantan-1-ol (7c1). The adamantane (0.74 mmol, 1.0 equiv, 100 mg) and DIB (0.96 mmol, 1.3 equiv., 308 mg) were added in a Pressure-resistant tube. Then H2O (0.5 mL) and DCM (2.5 mL) were added with pipetter. The tube was sealed with a rubber stopper and a needle to equalize the air pressure. Finally, the tubes were positioned between two 18 W blue light (kept above 2 cm away from the light source) and stirred at room temperature (with a fan to cool the reaction down) for 5 h. The target product was purified by flash column chromatography on silica eluting with ethyl acetate:petroleum ether [1:10 (v/v)]. Yield of 51%, White solid, Rf= 0.51 ethyl acetate:petroleum ether [1:4 (v/v)].1H NMR (400 MHz, CDCl3) δ 2.14 (t,J = 3.2 Hz, 3H), 1.71 (d, J = 2.9 Hz, 6H), 1.67 – 1.58 (m, 6H). 13C NMR (101 MHz, CDCl3)δ 68.3, 45.4, 36.1, 30.7. 1H NMR and13C NMR data correspond to the reported values.[6b]
1-oxaspiro[4.4]nonan-2-one (8c1). The target product was synthesized following general procedure for oxidation using methylcyclohexane as the substrate. The target product was purified by flash column chromatography on silica eluting with ethyl acetate:petroleum ether [1:15-1:5 (v/v)]. Yield of 62%; Colorless liquid. Rf = 0.35 ethyl acetate:petroleum ether [1:4 (v/v)]. 1H NMR (400 MHz, CDCl3) δ 1.60 – 1.39 (m, 9H), 1.31 – 1.23 (m, 1H), 1.19 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 70.0, 39.4, 29.5, 25.6, 22.7.1H NMR and 13C NMR data correspond to the reported values.[16]
(chloromethyl)benzene (12a) . The target product was synthesized following procedure for chlorination using toluene as the substrate. The target product was purified by flash column chromatography on silica eluting with ethyl acetate:petroleum ether [0:1 (v/v)]. Yield of 41%; colorless liquid. Rf = 0.50 ethyl acetate:petroleum ether [0:1 (v/v)]. 1H NMR (400 MHz, CDCl3) δ 7.49 – 7.30 (m, 5H), 4.62 (s, 2H).13C NMR (101 MHz, CDCl3) δ137.5, 128.8, 128.7, 128.5, 46.4.
(bromomethyl)benzene (12b). The target product was synthesized following general procedure for bromination using toluene as the substrate. The target product was purified by flash column chromatography on silica eluting with ethyl acetate:petroleum ether [0:1 (v/v)]. Yield of 59%; Light yellow liquid. Rf = 0.51 ethyl acetate:petroleum ether [0:1 (v/v)]. 1H NMR (400 MHz, CDCl3)δ 7.47 – 7.30 (m, 5H), 4.53 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 137.9, 129.1, 128.9, 128.5, 33.8.
benzoic acid (12c3). The target product was synthesized following general procedure for oxidation using toluene as the substrate. The target product was purified by flash column chromatography on silica eluting with ethyl acetate:petroleum ether [1:2 (v/v)]. Yield of 85%; Light yellow solid, m.p. 121–123.oC. Rf = 0.23 ethyl acetate:petroleum ether [1:1 (v/v)]. 1H NMR (400 MHz, CDCl3) δ 11.54 (s, 1H), 8.18 – 8.09 (m, 2H), 7.66 – 7.58 (m, 1H), 7.49 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, CDCl3) δ172.6, 133.9, 130.3, 129.3, 128.5.
Supporting Information
The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.2023xxxxx.
Acknowledgement
This work was supported the Natural Science Foundation of Higher Education Institutions in Anhui Province (2022AH030133, 2022AH051340), National Natural Science Foundation of China (22231003, 22271008), Shenzhen Science and Technology Program (Grant No. KQTD20190929174023858), Shenzhen Science and Technology Innovation Committee (GXWD20201231165807007-20200812100115001), Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions (2023SHIBS0004), Horizontal Cooperation Project of Fuyang Municipal Government (SXHZ202201), Key Projects of the Support Program for Outstanding Young Talents in Anhui Province Colleges and Universities (gxyqZD2020030), Yifan Pharmaceutical Co., Ltd (HX2019033), and Innovative drug design & development collaborative team (TDYY2021009).
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