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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