2-tridecylcycloprop-1-enyllithium | 649767-88-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-tridecylcycloprop-1-enyllithium
• 英文别名: 2-tridecyl-1-cyclopropenyl-lithium
• CAS: 649767-88-4
• 化学式: C₁₆H₂₉Li
• 分子量: 228.347
• InChiKey: KLVAOTDZLHIYDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  17.0
• 可旋转键数：
  12.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-tridecylcycloprop-1-enyllithium 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 (1S,7aR)-5,5-dimethyl-1-(2-tridecylcycloprop-1-enyl)dihydro[1,3]oxazolo[3,4-c][1,3]oxazol-3-one
  参考文献：
  名称：

  Synthesis of Cyclopropene Analogues of Ceramide and Their Effect on Dihydroceramide Desaturase

  摘要：

  The synthesis of several analogues of the N-[(1R,2S)-2-hydroxy-1-hydroxymethyl-2-(2-tridecyl-1-cyclopropenyl)ethyl]octanamide (GT11), the first reported inhibitor of dihydroceramide desaturase, as well as their effects on this enzyme, are described. Modifications of the parent structure include variations on the cyclopropene ring, the N-acyl chain length, the configuration of the stereocenters, and the hydroxyl group at C1. The key intermediates for the synthesis are the products resulting from the addition of suitable organolithium. compounds to either Garner's aldehyde or its enantiomer. The final products are obtained by TMSTf-induced cleavage of the protecting groups and N-acylation, both under specific conditions. An alternative method for N-Boc deprotection is also reported that allows us to obtain the cyclopropene analogue of sphingosine 12a, which can be transformed into GT11 upon acylation. The procedure consists of the conversion of the Garner aldehyde addition products into the bicyclic dihydrooxazolo[3,4,0]oxazol-3-ones 19 by transesterification in basic medium of the tert-butyl group with the hydroxyl function at C3. Mild cleavage of the N,O-isopropylidene cyclic acetal present in 19 affords the oxazolidin-2-one 20, which gives 12a upon saponification. Furthermore, compound 20 is also the key intermediate in the synthesis of the terminal deoxy, methoxy, and fluoro derivatives 9, 10, and 11, respectively. Determination of dihydroceramide desaturase activity in vitro showed that GT11 was a competitive inhibitor (K-i = 6 muM) and that its analogues with N-hexanoyl (6) and N-decanoyl (7) moieties inhibited the enzyme with similar potencies (IC50 = 13 and 31 muM, respectively). No decrease in dihydroceramide desaturase activity was observed with any of the other compounds tested.

  DOI：

  10.1021/jo030141u
• 作为产物：
  描述：

  1,1,2-三溴-2-十三烷基环丙烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 2-tridecylcycloprop-1-enyllithium
  参考文献：
  名称：

  DIHYDROCERAMIDE DESATURASE INHIBITORS.

  摘要：

  环丙烯基鞘氨醇衍生物作为脱饱和酶抑制剂，其一般式为I，其中R1可以是烷基，烯基，炔基，芳基或任何杂环基团，n可以有任何值，可以是支链或直链，可以含有不饱和碳，并且R2和R3可以具有相同或不同的值，并且可以表示带有一个或多个链上不饱和碳的芳基，杂环芳基，烷基或酰基基团，可以是支链或直链，并且可以用OH基团取代。这种新类化合物的成员已经表现出极高的脱氢鞘氨醇酰酶和鞘氨醇生物合成抑制活性，并且对于治疗与细胞内鞘氨醇增加有关的临床病症非常有用。

  公开号：

  EP1354870A1