Asymmetric Inter- and Intramolecular Cyclopropanation Reactions Catalyzed by a Reusable Macroporous-Polymer-Supported Chiral Ruthenium(II)/Phenyloxazoline Complex
Asymmetric Inter- and Intramolecular Cyclopropanation Reactions Catalyzed by a Reusable Macroporous-Polymer-Supported Chiral Ruthenium(II)/Phenyloxazoline Complex
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DOI：
10.1002/anie.201002240
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Iwasa, Seiji
中科院分区：
文献类型：
--
作者：
Abu-Elfotoh, Abdel-Moneim;Phomkeona, Kesiny;Iwasa, Seiji
总则：除另有说明外，所有反应均在氩气气氛下进行。脱水后的二氯甲烷（CH2Cl2）和二甲基甲酰胺（DMF）购自关东化学公司。乙腈和乙醚脱水购自Wako Pure Chemical Industries Ltd.。EDA购自SIGMA-ALDRICH， Co.。所有反应均采用薄层色谱（TLC）监测，玻璃板预涂有Merck KGaA 60 F254硅胶，层厚0.2 mm。所有的原料都是市售的，提纯后使用。用紫外光或I2照射观察产物。采用硅胶(Merck, Art；7734号)。1H NMR （400 MHz或300 MHz）和13C NMR （100 MHz或75 MHz）光谱记录在Varian Inova-400或Mercury-300光谱仪上。化学位移被报道为CDCl3中相对于内部四甲基硅烷（0.00 ppm）的δ值（ppm）。红外光谱用JASCO FT/IR-230光谱仪记录，以厘米（cm-1）为倒数单位。熔点在Yanaco MP-J3上测量，未校正。元素分析在Yanaco CHN CORDER MT-6上进行。用JASCO P-1030偏振仪在钠D线（1.0 ml样品池）进行旋光。对构象过量采用高效液相色谱（HPLC）分析，采用雅斯科GULLIVER （Daicel CHIRALPAK或CHIRALCEL色谱柱）或气相色谱（GC）分析，采用Shimazu GC-2014。采用加速电压为10.0 kV的日立s -4800 （FESEM）进行了场发射扫描电子显微镜（FESEM）研究，并在15 mA， 6 Pa的电流下溅射镀Pt-Pd 60 s。用自己的方法制备了Ru (II)-pheox配合物。
General: All reactions were performed under an atmosphere of argon unless otherwise noted. Dichloromethane (CH2Cl2) and dimethylformamide (DMF) dehydrated were purchased from Kanto Chemical Co., Inc.. Acetonitrile and diethyl ether dehydrated were purchased from Wako Pure Chemical Industries, Ltd.. EDA was purchased from SIGMA-ALDRICH, Co. All reactions were monitored by thin layer chromatography (TLC), glass plates pre-coated with silica gel Merck KGaA 60 F254, layer thickness 0.2 mm. All the starting materials are commercially available and were used after purification. The products were visualized by irradiation with UV light or using I2. Flash column chromatography was performed using silica gel (Merck, Art. No. 7734). 1H NMR (400 MHz or 300 MHz) and 13C NMR (100 MHz or 75 MHz) spectra were recorded on Varian Inova-400 or Mercury-300 spectrometer. Chemical shifts are reported asδvalues (ppm) relative to internal tetramethylsilane (0.00 ppm) in CDCl3. IR spectra were recorded by using JASCO FT/IR-230 spectrometer and are reported in reciprocal centimeter (cm-1). Melting points were measured on a Yanaco MP-J3 and not corrected. Elemental analyses were measured on a Yanaco CHN CORDER MT-6. Optical rotations were performed with a JASCO P-1030 polarimeter at the sodium D line (1.0 ml sample cell). Enantiomeric excesses were determined by highperformance liquid chromatography (HPLC) analyses with a JASCO GULLIVER using Daicel CHIRALPAK or CHIRALCEL columns, or determined by gas chromatography (GC) using Shimazu GC-2014. Field Emission Scanning Electron Microscope (FESEM) studies were performed using a Hitachi S-4800 (FESEM) with accelerating voltage of 10.0 kV and the fracture surfaces were sputter-coated with Pt-Pd under an electric current of 15 mA at 6 Pa for 60 s. Ru (II)-pheox complex was prepared by our own method.