(3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>pyrrolidine | 169619-35-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>pyrrolidine
• 英文别名: tert-butyl-[(3S,4S)-4-[tert-butyl(diphenyl)silyl]oxypyrrolidin-3-yl]oxy-diphenylsilane
• CAS: 169619-35-6
• 化学式: C₃₆H₄₅NO₂Si₂
• 分子量: 579.93
• InChiKey: IVTQKFCYTHJSQS-HEVIKAOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>pyrrolidine 在 sodium tetrahydroborate 、 selenium(IV) oxide 、 3 A molecular sieve 、 双氧水 作用下， 以 甲醇 、 丙酮 、 xylene 、 苯 为溶剂， 反应 205.67h， 生成 (1S,2S,8aS)-1,2-Bis<(tert-butyldiphenylsilyl)oxy>octahydroindolizine
  参考文献：
  名称：

  Assignment of the Absolute Configuration of Natural Lentiginosine by Synthesis and Enzymic Assays of Optically Pure (+) and (-)-Enantiomers

  摘要：

  The structure and absolute configuration of natural lentiginosine isolated from plant sources was determined to be (1S,2S,8aS)-1,2-dihydroxyindolizidine ((+)-4) on the basis of the synthesis of both enantiomers (+)-4 and (-)-4 and their inhibition of amyloglucosidases. Alkaloid (+)-4 was derived from (L)-(+)-tartaric acid via a highly stereo- and regioselective 1,3-dipolar cycloaddition of (3S,4S)-3 ,4-bis[(tert-butyldiphenylsilyl)oxy]-1-pyrroline N-oxide to methylenecyclopropane, followed by thermal rearrangement of the adduct into (1S,2S,8aS)-1,2-[(tert-butyldiphenylsily)oxy]octahydroindolizin-7-one. The enantiomer (-)-4 was derived in the same way from (D)-(-)-tartaric acid. Both (+)-4 and (-)-4 displayed inhibition specificity for amyloglucosidases, being inactive toward 17 other glycosidases. With amyloglucosidase from Aspergillus niger, synthetic (+)-4 displayed inhibition (K-i = 2 mu M) 5 times stronger than that reported for natural lentiginosine, 35 times that measured for (-)-4, and twice that of castanospermine. Alkaloid (+)-4 is thus the most potent and specific competitive inhibitor of amyloglucosidases among azasugars and their analogues.

  DOI：

  10.1021/jo00126a033
• 作为产物：
  描述：

  (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-N-benzylpyrrolidine 在 palladium dihydroxide 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、413.68 kPa 条件下， 反应 72.0h， 以71%的产率得到(3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>pyrrolidine
  参考文献：
  名称：

  Assignment of the Absolute Configuration of Natural Lentiginosine by Synthesis and Enzymic Assays of Optically Pure (+) and (-)-Enantiomers

  摘要：

  The structure and absolute configuration of natural lentiginosine isolated from plant sources was determined to be (1S,2S,8aS)-1,2-dihydroxyindolizidine ((+)-4) on the basis of the synthesis of both enantiomers (+)-4 and (-)-4 and their inhibition of amyloglucosidases. Alkaloid (+)-4 was derived from (L)-(+)-tartaric acid via a highly stereo- and regioselective 1,3-dipolar cycloaddition of (3S,4S)-3 ,4-bis[(tert-butyldiphenylsilyl)oxy]-1-pyrroline N-oxide to methylenecyclopropane, followed by thermal rearrangement of the adduct into (1S,2S,8aS)-1,2-[(tert-butyldiphenylsily)oxy]octahydroindolizin-7-one. The enantiomer (-)-4 was derived in the same way from (D)-(-)-tartaric acid. Both (+)-4 and (-)-4 displayed inhibition specificity for amyloglucosidases, being inactive toward 17 other glycosidases. With amyloglucosidase from Aspergillus niger, synthetic (+)-4 displayed inhibition (K-i = 2 mu M) 5 times stronger than that reported for natural lentiginosine, 35 times that measured for (-)-4, and twice that of castanospermine. Alkaloid (+)-4 is thus the most potent and specific competitive inhibitor of amyloglucosidases among azasugars and their analogues.

  DOI：

  10.1021/jo00126a033

文献信息

• Assignment of the Absolute Configuration of Natural Lentiginosine by Synthesis and Enzymic Assays of Optically Pure (+) and (-)-Enantiomers
  作者：Alberto Brandi、Stefano Cicchi、Franca M. Cordero、Roberta Frignoli、Andrea Goti、Sylviane Picasso、Pierre Vogel

  DOI：10.1021/jo00126a033

  日期：1995.10

  The structure and absolute configuration of natural lentiginosine isolated from plant sources was determined to be (1S,2S,8aS)-1,2-dihydroxyindolizidine ((+)-4) on the basis of the synthesis of both enantiomers (+)-4 and (-)-4 and their inhibition of amyloglucosidases. Alkaloid (+)-4 was derived from (L)-(+)-tartaric acid via a highly stereo- and regioselective 1,3-dipolar cycloaddition of (3S,4S)-3 ,4-bis[(tert-butyldiphenylsilyl)oxy]-1-pyrroline N-oxide to methylenecyclopropane, followed by thermal rearrangement of the adduct into (1S,2S,8aS)-1,2-[(tert-butyldiphenylsily)oxy]octahydroindolizin-7-one. The enantiomer (-)-4 was derived in the same way from (D)-(-)-tartaric acid. Both (+)-4 and (-)-4 displayed inhibition specificity for amyloglucosidases, being inactive toward 17 other glycosidases. With amyloglucosidase from Aspergillus niger, synthetic (+)-4 displayed inhibition (K-i = 2 mu M) 5 times stronger than that reported for natural lentiginosine, 35 times that measured for (-)-4, and twice that of castanospermine. Alkaloid (+)-4 is thus the most potent and specific competitive inhibitor of amyloglucosidases among azasugars and their analogues.