(+/-)-epi-muscarine iodide | 14400-75-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-epi-muscarine iodide
• 英文别名: (+/-)-(4t-hydroxy-5t-methyl-(2rH)-tetrahydro-furfuryl)-trimethyl-ammonium; iodide；(+/-)-(4t-Hydroxy-5t-methyl-(2rH)-tetrahydro-furfuryl)-trimethyl-ammonium; Jodid；[(2S,4S,5S)-4-hydroxy-5-methyloxolan-2-yl]methyl-trimethylazanium;iodide
• CAS: 14400-75-0
• 化学式: C₉H₂₀NO₂*I
• 分子量: 301.168
• InChiKey: PMFYONXEPDMBPE-YWUTZLAHSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.77
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  5-methyl-4-oxo-tetrahydro-furan-2-carboxylic acid methyl ester 在 dipotassium hydrogenphosphate 、 lithium aluminium tetrahydride 、 3α,20β-hydroxysteroid dehydrogenase 、 硫酸 、 三乙胺 、 三氟乙酸 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 29.5h， 生成 (+/-)-epi-muscarine iodide
  参考文献：
  名称：

  Chemoenzymic synthesis of the eight stereoisomeric muscarines

  摘要：

  Efficient syntheses of the eight stereoisomers of muscarine have been accomplished by dehydrogenase-catalyzed reduction of iodo ketones (+/-)-3a and (+/-)-3b. 3-alpha,20-beta-Hydroxysteroid dehydrogenase from Streptomyces hydrogenans exhibited high enantiomeric and diastereotopic selectivity for (+/-)-3a, yielding an equimolar mixture of iodo alcohol (-)-4 (2S,4S,5S) (96% ee) and iodo ketone (+)-3a (2R,5R) (96% ee) which was reduced by sodium borohydride to a mixture of (+)-4 and (+)-5. 3-beta,17-beta-Hydroxysteroid dehydrogenase from Pseudomonas testosteroni reduced (+/-)-3b with high diastereotopic selectivity to give an equimolar mixture of iodo alcohols (+)-6 (2R,4S,5S) (> 99% ee) and (-)-7 (2S,4S,5R) (81% ee). Synthesis of the remaining iodo alcohols [(-)-5, (-)-6, and (+)-7] was achieved by applying the Mitsunobu procedure to (-)-4, (-)-7, and (+)-6. The enantiomeric excess of intermediates 4-7 was determined by HPLC analysis of the (R)-(+)-MTPA esters. The chiral iodo alcohols 4-7 were then transformed into the final derivatives by conventional chemical manipulations.

  DOI：

  10.1021/jo00001a015

文献信息

• A Divergent Synthesis of (+)-Muscarine and (+)-epi-Muscarine from d-Glucose
  作者：Velimir Popsavin、Ostoja Berić、Mirjana Popsavin、Ljubica Radić、János Csanádi、Vera Ćirin-Novta

  DOI：10.1016/s0040-4020(00)00482-8

  日期：2000.8

  A novel stereospecific synthesis of (+)-muscarine and (+)-epi-muscarine has been achieved by utilizing d-glucose as a chiral precursor. The key steps of the synthesis involved stereospecific cyclization of 3,5-di-O-sulfonyl-d-glucofuranose derivatives into the corresponding 2,5-anhydrides, and stereospecific hydrogenation of 2,5-anhydro-l-threo-hex-2-enose ethylene acetal derivatives, thus providing

  通过利用d-葡萄糖作为手性前体，实现了（+）-毒蕈碱和（+）-表-毒蕈碱的立体定向合成。合成的关键步骤包括将3,5-二-O-磺酰基-d-呋喃呋喃糖衍生物进行立体定向环化成相应的2,5-酸酐，以及2,5-脱水-1-苏-hex-2的立体定向氢化。-烯化乙缩醛衍生物，从而提供了以完全立体有择的方式制备两个目标分子的不同中间体的途径。
• A concise synthesis of (+)-muscarine
  作者：T. H. Chan、C. J. Li

  DOI：10.1139/v92-346

  日期：1992.11.1

  (+)-Muscarine was synthesized from S-(−)-ethyl lactate in five steps with the application of a zinc-mediated allylation reaction in aqueous media. Reversal of chelation-control stereoselectivity wa...

  (+)-毒蕈碱是在水介质中应用锌介导的烯丙基化反应，从乳酸 S-(-)-乙酯分五步合成的。螯合控制立体选择性的逆转...
• Eugster et al., Helvetica Chimica Acta, 1958, vol. 41, p. 205,211
  作者：Eugster et al.

  DOI：——

  日期：——
• Chemoenzymic synthesis of the eight stereoisomeric muscarines
  作者：Marco De Amici、Carlo De Micheli、Giorgio Molteni、Davide Pitre、Giacomo Carrea、Sergio Riva、Sandro Spezia、Lucia Zetta

  DOI：10.1021/jo00001a015

  日期：1991.1

  Efficient syntheses of the eight stereoisomers of muscarine have been accomplished by dehydrogenase-catalyzed reduction of iodo ketones (+/-)-3a and (+/-)-3b. 3-alpha,20-beta-Hydroxysteroid dehydrogenase from Streptomyces hydrogenans exhibited high enantiomeric and diastereotopic selectivity for (+/-)-3a, yielding an equimolar mixture of iodo alcohol (-)-4 (2S,4S,5S) (96% ee) and iodo ketone (+)-3a (2R,5R) (96% ee) which was reduced by sodium borohydride to a mixture of (+)-4 and (+)-5. 3-beta,17-beta-Hydroxysteroid dehydrogenase from Pseudomonas testosteroni reduced (+/-)-3b with high diastereotopic selectivity to give an equimolar mixture of iodo alcohols (+)-6 (2R,4S,5S) (> 99% ee) and (-)-7 (2S,4S,5R) (81% ee). Synthesis of the remaining iodo alcohols [(-)-5, (-)-6, and (+)-7] was achieved by applying the Mitsunobu procedure to (-)-4, (-)-7, and (+)-6. The enantiomeric excess of intermediates 4-7 was determined by HPLC analysis of the (R)-(+)-MTPA esters. The chiral iodo alcohols 4-7 were then transformed into the final derivatives by conventional chemical manipulations.