A FORMAL TOTAL SYNTHESIS OF KOPSININE
A FORMAL TOTAL SYNTHESIS OF KOPSININE
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DOI：
10.1021/jo00255a044
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发表时间：
1988-09-30
影响因子：
3.6
通讯作者：
PESTCHANKER, MJ
中科院分区：
文献类型：
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作者：
WENKERT, E;PESTCHANKER, MJ
熔点记录在Reichert微热台设备上，未校正。甲醇溶液的紫外光谱和二氯甲烷溶液的红外光谱分别用IBM 9400和Perkin-Elmer 1330分光光度计测定。在Varían EM-390和Nicolet q -300光谱仪上获得了氘氯仿溶液（内标：Me4Si）的核磁共振光谱，在后一种仪器上获得了氘氯仿溶液的13C核磁共振光谱，工作频率为75.5 MHz，傅里叶变换模式。从Me4Si向下，碳的变化以百万分之一为单位；< 5 (Me4Si)= 5 (CDC13)+ 76.9 ppm。所有粗产物用二氯甲烷提取，用盐水洗涤，用无水Na2S04干燥，蒸发。所有色谱分离均在中压Lichoprep Si 60 (40-63 Mm) Lobar柱上进行，使用Fluid Metering， Inc.的泵。20-Deethyl-17-dehydro-2/3-hydro-5-oxovincadifformine(5)。将300 mg （0.88 mmol）的羟基酯4a、1100 mL （1.2 mmol）的甲磺酰氯和1ml的三乙胺加入10 mL的二氯乙烷中，在0℃下搅拌1 h，然后倒入饱和碳酸氢钠溶液中。提取、干燥和蒸发成粗、中质
Melting points were recorded on a Reichert microhotstage apparatus and are uncorrected. Ultraviolet spectra of methanol solutions and infrared spectra of methylene chloride solutions were measured on IBM 9400 and Perkin-Elmer 1330 spectrophotometers, respectively. NMR spectra of deuteriochloroform solutions (internal standard: Me4Si) were obtained on Varían EM-390 and Nicolet QE-300 spectrometers and 13C NMR spectra of deuteriochloroform solutions on the latter instrument, operating at 75.5 MHz in the Fourier transform mode. The carbon shifts are in parts per million downfield from Me4Si;< 5 (Me4Si)= 5 (CDC13)+ 76.9 ppm. All crude products were extracted with methylene chloride, and the extracts were washed with brine, dried over anhydrous Na2S04, and evaporated. All chromatographic sepa-rations were carried out on medium-pressure, Lichoprep Si 60 (40-63 Mm) Lobar columns with the use of a Fluid Metering, Inc., pump.20-Deethyl-17-dehydro-2/3-hydro-5-oxovincadifformine (5a). A solution of 300 mg (0.88 mmol) of hydroxy ester 4a, 1100 mL (1.2 mmol) of methanesulfonyl chloride, and 1 mL of triethylamine in 10 mL of ethylene dichloride was stirred at 0 C for 1 h and then poured into saturatedsodium bicarbonate so-lution. Extraction, drying, and evaporationled to crude, meta-