(1S,2S,8aS)-1,2-Bis<(tert-butyldiphenylsilyl)oxy>octahydroindolizine | 160208-49-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (1S,2S,8aS)-1,2-Bis<(tert-butyldiphenylsilyl)oxy>octahydroindolizine
• 英文别名: [(1S,2S,8aS)-1-[tert-butyl(diphenyl)silyl]oxy-1,2,3,5,6,7,8,8a-octahydroindolizin-2-yl]oxy-tert-butyl-diphenylsilane
• CAS: 160208-49-1
• 化学式: C₄₀H₅₁NO₂Si₂
• 分子量: 634.021
• InChiKey: VZRYZNCCHUQVGO-QXUSSCGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.74
• 重原子数：
  45
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2S,8aS)-1,2-Bis<(tert-butyldiphenylsilyl)oxy>octahydroindolizine 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以70%的产率得到(+)-lentiginosine
  参考文献：
  名称：

  立体选择性手性硝酮环加成反应合成香豆苷和应变螺旋螺异唑烷的热重排

  摘要：

  报告了Lentiginosine（3）的总合成。该策略基于将TBDPS保护的3,4-二羟基吡咯啉N-氧化物的1,3-偶极环加成至亚甲基环丙烷，然后将所得的螺环丙烷异恶唑烷进行热重排，以得到官能化的吲哚并立定骨架。该化合物的[α] D值与报道的天然异构体相同，但符号相反，但具有相同的绝对构型。

  DOI：

  10.1016/s0040-4039(00)76008-4
• 作为产物：
  描述：

  (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-N-benzylpyrrolidine 在 palladium dihydroxide sodium tetrahydroborate 、 selenium(IV) oxide 、 3 A molecular sieve 、 氢气 、 双氧水 作用下， 以 甲醇 、 丙酮 、 xylene 、 苯 为溶剂， 20.0~35.0 ℃ 、413.69 kPa 条件下， 反应 277.67h， 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

文献信息

• Synthesis of lentiginosine by stereoselective chiral nitrone cycloaddition and thermal rearrangement of strained spiroisoxazolidine
  作者：Franca M. Cordero、Stefano Cicchi、Andrea Goti、Alberto Brandi

  DOI：10.1016/s0040-4039(00)76008-4

  日期：1994.1

  The total synthesis of Lentiginosine (3) is reported. The strategy is based on the 1,3-dipolar cycloaddition of a TBDPS protected 3,4-dihydroxypyrroline N-oxide to methylenecyclopropane followed by the thermal rearrangement of the resulting spirocyclopropaneisoxazolidine to give the functionalised indolizidine skeleton. The compound shows an [α]D value identical, but opposite in sign, with that reported

  报告了Lentiginosine（3）的总合成。该策略基于将TBDPS保护的3,4-二羟基吡咯啉N-氧化物的1,3-偶极环加成至亚甲基环丙烷，然后将所得的螺环丙烷异恶唑烷进行热重排，以得到官能化的吲哚并立定骨架。该化合物的[α] D值与报道的天然异构体相同，但符号相反，但具有相同的绝对构型。
• 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.