(+)-(1E)-{(4R,5R,6S)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-hydroxy-4-methoxycyclohex-2-en-1-yliden}acetonitrile | 350809-51-7

• 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: (+)-(1E)-{(4R,5R,6S)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-hydroxy-4-methoxycyclohex-2-en-1-yliden}acetonitrile
• 英文别名: (2E)-2-[(4R,5R,6S)-5-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-4-methoxycyclohex-2-en-1-ylidene]acetonitrile
• CAS: 350809-51-7
• 化学式: C₁₅H₂₅NO₃Si
• 分子量: 295.454
• InChiKey: GNDHPKORXOUMCI-LOGCYIPHSA-N

物化性质

• 沸点：
  388.6±42.0 °C(predicted)
• 密度：
  1.03±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  62.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(1E)-{(4R,5R,6S)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-hydroxy-4-methoxycyclohex-2-en-1-yliden}acetonitrile 在 2,6-二叔丁基-4-甲基吡啶 、 4 A molecular sieve 、 氢氟酸 、 sodium methylate 、 silver trifluoromethanesulfonate 作用下， 以 1,4-二氧六环 、 甲醇 、 水 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 19.17h， 生成 (-)-(1Z)-[(4R,5S,6S)-6-(β-D-glucopyranosyloxy)-5-hydroxy-4-methoxycyclohex-2-en-1-yliden]acetonitrile
  参考文献：
  名称：

  Total Synthesis of (−)-Bauhinin

  摘要：

  The total synthesis of the naturally occurring cyanoglucoside (-)-bauhinin (1) was achieved starting from the optically pure oxatrinorbornenone 2 in 12 steps and 8% overall yield. The aglycone of (-)-bauhinin was easily obtained from the optically pure oxatrinorbornenone derivative 6 by a Wittig-Horner reaction followed by the opening of the oxa bridge. Glycosidation with tetra-O-isobutyryl-D-glucosyl bromide 9 as the reagent in the Koenigs-Knorr reaction afforded glucoside 10 in 58% yield, which, after photoisomerization and deprotection, gave (-)-bauhinin (1).

  DOI：

  10.1002/1522-2675(20010418)84:4<890::aid-hlca890>3.0.co;2-q
• 作为产物：
  描述：

  (-)-(1Z)-{(4R,5R,6S)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-hydroxy-4-methoxycyclohex-2-en-1-yliden}acetonitrile 以 1,4-二氧六环 为溶剂， 反应 0.17h， 以27%的产率得到(+)-(1E)-{(4R,5R,6S)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-hydroxy-4-methoxycyclohex-2-en-1-yliden}acetonitrile
  参考文献：
  名称：

  Total Synthesis of (−)-Bauhinin

  摘要：

  The total synthesis of the naturally occurring cyanoglucoside (-)-bauhinin (1) was achieved starting from the optically pure oxatrinorbornenone 2 in 12 steps and 8% overall yield. The aglycone of (-)-bauhinin was easily obtained from the optically pure oxatrinorbornenone derivative 6 by a Wittig-Horner reaction followed by the opening of the oxa bridge. Glycosidation with tetra-O-isobutyryl-D-glucosyl bromide 9 as the reagent in the Koenigs-Knorr reaction afforded glucoside 10 in 58% yield, which, after photoisomerization and deprotection, gave (-)-bauhinin (1).

  DOI：

  10.1002/1522-2675(20010418)84:4<890::aid-hlca890>3.0.co;2-q

文献信息

• Selective Formation ofβ-D-Glucosides of Hindered Alcohols
  作者：Guillaume Desmares、Delphine Lefebvre、Gilles Renevret、Claude Le Drian

  DOI：10.1002/1522-2675(20010418)84:4<880::aid-hlca880>3.0.co;2-u

  日期：2001.4.18

  Alternative conditions for the classical glycosidation method of Koenigs-Knorr allowed us to prepare selectively β-D-glucosides of several hindered alcohols in good yields in a weakly acidic to almost neutral medium. To illustrate the versatility of our conditions, we prepared the β-D-glucoside of an acid-sensitive aglycone, a key-intermediate for the total synthesis of a natural cyanoglucoside, bauhinin

  Koenigs-Knorr 经典糖苷化方法的替代条件使我们能够在弱酸性到几乎中性的介质中以高产率选择性地制备几种受阻醇的 β-D-葡萄糖苷。为了说明我们条件的多功能性，我们制备了酸敏感苷元的 β-D-葡糖苷，这是全合成天然氰基葡糖苷紫荆苷的关键中间体。