10.1002/cctc.201700436
ChemCatChem
were 20.52 mg (0.199 mmol) per gram of catalyst. 13C CP/MAS NMR
(161.9 MHz): 147.4−120.8 (C of Ph and Ar groups), 95.7 (C of Cp
ring), 71.3−64.0 (C of –NCHPh), 62.1−56.1 (C of –N+CH2– in CTAB
molecule and C of –N+CH2– in DABCO moiety), 53.3, 44.7 (C of
N(CH2)3– in DABCO moiety), 36.3−20.8 (C of –CH2Ph, C of –CH2− in
CTAB molecule and in DABCO moiety), 20.0−14.5 (C of CH3− in
CTAB molecule and C of –CH2Si), 9.0 (C of –CH3 in Cp(CH3)5) ppm.
19F MAS NMR (169.3 MHz): −166.0 (“bulk” BF4− species), −156~ −142
ppm (F in BF4− hydrogen bonded to the surface silanol group), −144.8
2894−2906; d) C. Li, H. D. Zhang, D. M. Jiang, Q. H. Yang, Chem.
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−
(“bulk” BF4− species), −123.6 (free BF4− species), −102.4 (“bulk” BF4
species), and −81.0 (“bulk” BF4− species) ppm. 29Si MAS NMR (79.4
MHz): T2 (δ = −60.1 ppm), T3 (δ = −73.4 ppm), Q2 (δ = −95.6 ppm), Q3
(δ = −105.1 ppm), Q4 (δ = −114.3 ppm).
General procedure for the ATH/epoxidation enantio-relay
reaction of 2-haloketone
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A typical procedure was as follows: Catalyst 3 (10.05 mg, 2.0 μmol of
Rh, based on ICP analysis), HCO2Na (137.0 mg, 2.0 mmol), 2-
haloketone (0.20 mmol), and 3.0 mL H2O, reaction temperature
(25 °C), reaction time (16-20 h). During this period, the reaction was
monitored constantly by TLC. After completion of the reaction, the
catalyst was separated by centrifugation (10,000 rpm) for the
recycling experiment. The aqueous solution was extracted with ethyl
ether (3 × 3.0 mL). The combined ethyl ether extracts were washed
with brine twice and then dehydrated with Na2SO4. After evaporation
of ethyl ether, the residue was purified by silica gel flash column
chromatography to afford the desired products. The ee values were
determined by a HPLC analysis using a UV-Vis detector and Daicel
chiralcel columns (Φ 0.46 × 25 cm).
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General procedure for one-pot synthesis of chiral β-amino
alcohols
A typical procedure was as follows. Catalyst 3 (10.05 mg, 2.0 μmol of
Rh, based on ICP analysis), HCO2Na (137.0 mg, 2.0 mmol), 2-
bromoketone (0.20 mmol), amine (0.24 mmol), and 3.0 mL of the
mixed solvents (iPrOH/H2O = 2:1), reaction temperature (25 °C),
reaction time (3-5 h). During this period, the reaction was monitored
constantly by TLC. After completion of the reaction, the catalyst was
separated by centrifugation (10,000 rpm) for the recycling experiment.
The aqueous solution was extracted with ethyl ether (3 × 3.0 mL). The
combined ethyl ether extracts were washed with brine twice and then
dehydrated with Na2SO4. After evaporation of ethyl ether, the residue
was purified by silica gel flash column chromatography to afford the
desired products. The ee values were determined by a HPLC analysis
using a UV-Vis detector and Daicel chiralcel columns (Φ 0.46 × 25
cm).
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Acknowledgements ((optional))
We are grateful to China National Natural Science Foundation
(21672149), Ministry of Education of China (PCSIRT-IRT-16R49),
Shanghai Sciences and Technologies Development Fund
(13ZR1458700), the Shanghai Municipal Education Commission
(14YZ074) for financial support.
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Keywords: Asymmetric catalysis • Heterogeneous catalyst •
Immobilization • Silica • Supported catalysts
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