Gold(I)-catalyzed synthesis of functionalized cyclopentadienes
Gold(I)-catalyzed synthesis of functionalized cyclopentadienes
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DOI：
10.1002/anie.200604006
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Toste, F. Dean
中科院分区：
文献类型：
--
作者：
Lee, Jun Hee;Toste, F. Dean
一般信息：除非另有说明，否则所有商业材料不经纯化使用。二氯甲烷购自EMD并按原样使用，除非另有说明。在使用前，在氮气正压下从钠/二苯甲酮酮基中蒸馏THF。六氟锑酸银（AgSbF 6）从Aldrich Chemical Company获得并储存在干燥箱中。根据文献方法制备氯化（三苯基膦）金（I）（Ph 3 PAuCl）和氯化（三叔丁基膦）金（I）（tert-Bu 3 PAuCl）。[1]根据Palenzuela等人[2]的方法制备乙烯基丙二烯4，并使用脱氧苯甲醛类似地制备d-4。[3]涉及对湿气和/或空气敏感的化合物的实验在氮气正压下在具有橡胶隔片的烘箱或火焰干燥的玻璃器皿中进行。通过在0.25 mm E. Merck硅胶板（60 F-254），使用UV光作为显色剂，磷钼酸/硫酸铈在乙醇和硫酸中，加热作为显色剂。根据Still等人的方法，在Merck 60硅胶（32-63 mm）上进行快速色谱。[4]用Bruker AVB-400（分别为400 MHz和100 MHz）、AVQ-400（分别为400 MHz和100 MHz）和DRX-500（分别为500 MHz和125 MHz）光谱仪记录1H和13 C NMR光谱。1H NMR谱参考残留的CHCl 3（7.26 ppm），并报告如下：化学位移，多重性（br=宽峰，s=单峰，d=双峰，t=三重峰，q=四重峰，m=多重峰）。相对于CDCl 3（77.0 ppm）测量13 C NMR光谱的化学位移。在50 ℃下获得N-Boc衍生物的1H和13 C NMR谱以使峰增宽最小化。质谱数据通过加州大学伯克利分校化学学院运行的微质量/分析设备获得。使用Perkin-Elmer旋光计测定旋光度，并报告如下：[α] D 23（浓度c= g/100 mL，溶剂）。在Shimadzu VP系列手性HPLC上使用购自Daicel Chemical Industries的CHIRALCEL OD和CHIRALCEL OJ-H柱进行HPLC分离。
General Information: Unless otherwise noted all commercial materials were used without purification. Dichloromethane were purchased from EMD and used as is unless otherwise mentioned. THF was distilled from sodium/benzophenone ketyl under a positive pressure of nitrogen prior to use. Silver hexafluoroantimonate (AgSbF6) was obtained from Aldrich Chemical Company and stored in a drybox. Chloro (triphenylphosphine) gold (I) chloride (Ph3PAuCl) and Chloro (tri-tert-butylphosphine) gold (I) chloride (tert-Bu3PAuCl) were prepared according to the literature procedures.[1] Vinylallene 4 was prepared according to the procedure of Palenzuela et al [2] and d-4 was also prepared similarly using deurobenzaldehyde.[3] Experiments involving moisture-and/or air-sensitive compounds were performed in oven-or flame-dried glassware with rubber septa under a positive pressure of nitrogen. Reactions were monitored by thin-layer chromatography (TLC) carried out on 0.25 mm E. Merck silica gel plates (60F-254) using UV light as a visualizing agent and phosphomolybdic acid/cerium sulfate in ethanol and sulfuric acid, and heat as developing agent. Flash chromatography was carried out on Merck 60 silica gel (32-63 mm) according to the procedure of Still et al.[4] 1H and 13C NMR spectra were recorded with Bruker AVB-400 (400 MHz and 100 MHz, respectively), AVQ-400 (400 MHz and 100 MHz, respectively) and DRX-500 (500 MHz and 125 MHz, respectively) spectrometers. 1H NMR spectra were referenced to residual CHCl3 (7.26 ppm) and are reported as follows: chemical shift, multiplicity (br= broad, s= singlet, d= doublet, t= triplet, q= quartet, m= multiplet). Chemical shifts of the 13C NMR spectra were measured relative to CDCl3 (77.0 ppm). 1H and 13C NMR spectra of the N-Boc derivatives were obtained at 50 C to minimize peak broadening. Mass spectral data were obtained via the Micro-Mass/Analytical Facility operated by the College of Chemistry, University of California, Berkeley. Optical rotations were determined using a Perkin-Elmer polarimeter and are reported as follows:[α] D 23 (concentration c= g/100 mL, solvent). HPLC separations were performed on a Shimadzu VP series chiral HPLC using a CHIRALCEL OD and a CHIRALCEL OJ-H column purchased from Daicel Chemical Industries.