5,5-diethoxy-1-pentene | 14499-63-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-diethoxy-1-pentene
• 英文别名: 5,5-diethoxy-pent-1-ene；4-Pentenal diethyl acetal；5,5-diethoxypent-1-ene
• CAS: 14499-63-9
• 化学式: C₉H₁₈O₂
• 分子量: 158.241
• InChiKey: FDNMVYJIEXSECU-UHFFFAOYSA-N

物化性质

• 沸点：
  162-165 °C(Press: 750 Torr)
• 密度：
  0.854±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-diethoxy-1-pentene 在 吡啶 、 三异丙氧基氯化钛 、 4-二甲氨基吡啶 、 环戊基溴化镁 作用下， 以 乙醚 为溶剂， 生成 Acetic acid 2-(3,3-diethoxy-propyl)-1-[((E)-2-propenyl)-heptyl]-cyclopropyl ester
  参考文献：
  名称：

  在RCM中使用环丙醇作为构象限制。

  摘要：

  [反应：见正文]羧酸酯的库林科维奇环丙烷化的顺序应用和所得顺式-二烯基连接的环丙醇的RCM可以为官能化的中型碳环提供便利的途径。随后值得一提的是对环丙醇官能度（例如单碳环扩环）的详细说明，以提供合成上有用的α，β-烯酮。

  DOI：

  10.1021/ol0605631
• 作为产物：
  描述：

  乙醇 、 4-戊烯醛 在 三氟化硼乙醚 作用下， 反应 0.17h， 以96%的产率得到5,5-diethoxy-1-pentene
  参考文献：
  名称：

  Intensely Cytotoxic Anthracycline Prodrugs:  Glucuronides

  摘要：

  We previously reported the synthesis of a series of doxorubicin analogue prodrugs that give rise to intensely cytotoxic metabolites in the presence of carboxylate esterases. We now report studies on structurally related beta-glucuronide prodrugs that are converted to similar potent metabolites in the presence of beta-glucuronidases. These prodrugs were prepared by reductive condensation of daunomycin or doxorubicin with methyl 1-O-[(1'RS)-1'-ethoxy-4'-oxobutyl]-2,3,4-tri-O-acetyl-beta-D-glucopyranosyluronate in the presence of sodium cyanoborohydride followed by base-mediated cleavage of the glucuronate protective groups. The doxorubicin derivatives were isolated in very low yield, most likely because of the inherent base lability of the parent aglycone. By contrast, fairly good yields of the more base-stable daunomycin analogues were obtained. The target daunomycin glucuronide, N-[(4''RS)-4''-ethoxy -4''-(sodium 1'''-O-beta-D-glucopyranuronate)butyl]daunorubicin (6a), bad a half-life of 30 h when incubated at a concentration of 12 mu M in aqueous 0.05 M phosphate buffer, pH 7.4, at 37 degrees C. Under identical conditions in the presence of 197 units/mu mol of Escherichia coli beta-glucuronidase, 6a was hydrolyzed with a half-life of 1.7 h. The single metabolite observed was chromatographically identical with that formed from the hydrolysis of N-(4,4-diacetoxybut-1-yl)daunomycin by carboxylate esterases. 6a was approximately 10000-fold more toxic to human A375 melanoma cells in the presence of E. coli beta-glucuronidase than in the absence of the enzyme. These findings indicate the therapeutic potential of anthracycline glucuronide prodrugs as independent entities or for use in conjunction with enzyme tissue-targeting strategies such as antibody-directed enzyme prodrug therapy (ADEPT) or gene-directed enzyme prodrug therapy (GDEPT).

  DOI：

  10.1021/jm970066d

文献信息

• <i>In Situ</i> Generation of a Regio- and Diastereoselective Hydroaminoalkylation Catalyst Using Commercially Available Starting Materials
  作者：Peter M. Edwards、Laurel L. Schafer

  DOI：10.1021/acs.orglett.7b02149

  日期：2017.11.3

  intermolecular hydroaminoalkylation of alkenes with secondary amines is reported. The method utilizes commercially available ligands and tantalum starting materials, and does not require the isolation of air and water sensitive organometallic complexes. The in situ prepared catalyst is active toward a variety of secondary amine substrates, including those with ethyl substituents which yield α- and β-alkylated

  据报道设计了一种易于使用的催化剂体系，用于用仲胺对烯烃进行区域和非对映选择性分子间氢氨基烷基化。该方法利用可商购的配体和钽起始原料，并且不需要分离对空气和水敏感的有机金属配合物。在原位制备的催化剂是向着各种仲胺底物，包括那些用乙酸乙酯取代基得到α-和β烷基化胺作为单一非对映体的活性。该催化转化可用于制备含有促进环闭合以实现二烷基和三烷基化的N-杂环的非对映选择性合成的官能度的胺。
• <i>Trans</i>-2,5-Disubstituted Tetrahydrofurans via Addition of Carbon Nucleophiles to the Strained Bicyclic Acetal 2,7-Dioxabicyclo[2.2.1]heptane
  作者：Gregory K. Friestad、Hye Jin Lee

  DOI：10.1021/ol901613k

  日期：2009.9.3

  Addition of allyltributylstannane to 2,7-dioxabicyclo[2.2.1]heptane in the presence of TiCl4 produces 5-allyl-2-(hydroxymethyl)tetrahydrofuran with a trans/cis ratio of 93:7. The trans-selectivity is also observed in additions of various other carbon nucleophiles.

  在TiCl 4存在下，将烯丙基三丁基锡烷添加到2,7-二氧杂双环[2.2.1]庚烷中，生成反式/顺式比例为93：7的5-烯丙基-2-（羟甲基）四氢呋喃。的反式-选择性是在各种其它碳亲核试剂的添加也观察到。
• Compounds and methods for the selective treatment of cancer and bacterial infections
  申请人：Pro-Neuron, Inc.

  公开号：US06218519B1

  公开（公告）日：2001-04-17

  The present invention relates to compounds containing an anthracyclinone group such as doxorubicin, daunorubicin or a derivative thereof. The compounds of the invention also contain ester, glycoside or glucuronide structures which are hydrolyzed by the corresponding esterase, glycosidase or glucuronidase. These compounds possess potent cytotoxic activity which is developed after the hydrolysis of the ester or glycoside group of the compound and are effective in the inhibition of tumor cells and bacterial growth after activation.

  本发明涉及含有蒽环酮基团的化合物，例如多柔比星、多诺鲁比星或其衍生物。本发明的化合物还包含酯、糖苷或葡萄糖醛酸结构，这些结构通过相应的酯酶、糖苷酶或葡萄糖醛酸酶水解。这些化合物在酯或糖苷基团水解后具有强效的细胞毒性活性，并在激活后对肿瘤细胞和细菌生长具有抑制作用。
• Studies Towards the Total Synthesis of Populusone: Stereoselective Construction of Functionalized 2-Oxa-bicyclo[2.2.2]octenes
  作者：Hans-Günther Schmalz、Lars Hemmersbach

  DOI：10.1055/a-1983-1694

  日期：2023.2

  by exploiting a diastereoselective Mukaiyama aldol addition followed by a triflic anhydride-induced oxa-Michael addition to construct the sensitive 2-oxa-bicyclo[2.2.2]octene unit as an enol triflate, which is directly used in a subsequent Suzuki cross-coupling. While attempts to close the strained 10-membered ring by means of Ru-catalyzed ring-closing metathesis were not successful, the developed

  通过利用非对映选择性 Mukaiyama 羟醛加成，然后三氟甲磺酸酐诱导的 oxa-Michael 加成，构建敏感的 2-oxa-双环 [2.2. 2]辛烯单元作为烯醇三氟甲磺酸酯，直接用于后续的 Suzuki 交叉偶联。虽然尝试通过 Ru 催化的闭环复分解来关闭应变 10 元环的尝试并不成功，但开发的合成方案开辟了快速合成高级中间体的途径，这可能允许在未来。
• Kovalev,B.G. et al., Journal of Organic Chemistry USSR (English Translation), 1967, vol. 3, # 2, p. 275 - 277
  作者：Kovalev,B.G. et al.

  DOI：——

  日期：——