(S)-2-Propyl-pent-4-enal

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (S)-2-Propyl-pent-4-enal
• 英文别名: (2S)-2-propylpent-4-enal
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: KCZBNTGSHQURPY-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-2-Propyl-pent-4-enal 、 lithium;(2Z,5Z)-5-methoxy-4,4-dimethyl-7-[(2-methylpropan-2-yl)oxy]-7-oxohepta-2,5-dien-3-olate 以 四氢呋喃 为溶剂， 生成 (Z)-(S)-7-Hydroxy-3-methoxy-4,4,6-trimethyl-5-oxo-8-propyl-undeca-2,10-dienoic acid tert-butyl ester
  参考文献：
  名称：

  New Chemical Synthesis of the Promising Cancer Chemotherapeutic Agent 12,13-Desoxyepothilone B: Discovery of a Surprising Long-Range Effect on the Diastereoselectivity of an Aldol Condensation

  摘要：

  The epothilones are naturally occurring cytotoxic molecules that possess the remarkable ability to arrest cell division through the stabilization of microtubule assemblies. Our in vivo studies with 12,13-desoxyepothilone B (dEpoB), have established that the desoxy compound is well tolerated and virtually curative against a variety of sensitive and resistant xenograft tumors in animal models. In light of these discoveries, we sought a chemical synthesis of dEpoB that would be able to support a serious and substantial discovery research program directed toward the clinical development of this molecule. The overall strategy for this endeavor assumed the ability to synthesize dEpoB from three constructs which include an achiral beta,delta-diketo ester construct A, an (S)-2-methylpentenal moiety B, and the thiazoyl-containing vinyl iodide moiety C. We envisioned that a diastereoselective aldol condensation between an achiral C5-C6 (Z)-metalloenolate derived from construct A and an (S)-2-methylalkanal fragment, B, would generate the desired C6-C7 bond. Second, a B-alkyl Suzuki coupling between the vinyl iodide construct C and an alkyl borane would form the C11-C12 bond. Finally, a late-stage reduction of the C3 ketone to the requisite C3 alcohol with high asymmetric induction would permit us to introduce the beta,delta-diketo ester fragment A, into the synthesis as a readily accessible achiral building block. The governing concepts for our new synthesis are described herein.

  DOI：

  10.1021/ja991189l

文献信息

• Remarkable long range effects on the diastereoface selectivity in an aldol condensation
  作者：Christina R Harris、Scott D Kuduk、Aaron Balog、Ken A Savin、Samuel J Danishefsky

  DOI：10.1016/s0040-4039(99)00222-1

  日期：1999.3

  α-methyl aldehydes indicates a stabilizing through space interaction between C4C5 unsaturation and the formyl group. This interaction leads to a reaction conformation which favors a C7C8 (epothilone numbering) anti-relationship in the aldol products. Included is an extensive study that identifies steric and electronic effects of various α-methyl aldehydes in the aldol diastereoselection.

  在烯醇化物之间的醛醇反应的立体化学结果2和各种α甲基醛指示通过C的空间交互的稳定4 C 5不饱和度和甲酰基。这种相互作用导致有利于一个C的反应的构象7 C 8（埃博霉素编号）抗在醛醇缩合产品-relationship。其中包括一项广泛的研究，确定了醛醇非对映体中各种α-甲基醛的空间和电子效应。