(2S,3R,4S)-1-(benzyloxy)-3-(4-methoxybenzyloxy)-2,4-dimethyl-5-heptyne | 869781-62-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R,4S)-1-(benzyloxy)-3-(4-methoxybenzyloxy)-2,4-dimethyl-5-heptyne
• 英文别名: 1-[[(2S,3R,4S)-2,4-dimethyl-1-phenylmethoxyhept-5-yn-3-yl]oxymethyl]-4-methoxybenzene
• CAS: 869781-62-4
• 化学式: C₂₄H₃₀O₃
• 分子量: 366.5
• InChiKey: LKHSXYPCRMIXBN-MZLICYQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R,4S)-1-(benzyloxy)-3-(4-methoxybenzyloxy)-2,4-dimethyl-5-heptyne 、 Lithium; (2S,3R,4S)-1-benzyloxy-2,4-dimethyl-hept-5-yn-3-olate 在 titanium(IV) isopropylate 、 Cyclopentylmagnesium chloride 作用下， 以 乙醚 、 甲苯 、 正己烷 为溶剂， 以59%的产率得到(2S,3R,4S,5E,7E,9S,10R,11S)-1,12-bis(benzyloxy)-10-(4-methoxybenzyloxy)-2,4,6,7,9,11-hexamethyldodeca-5,7-dien-3-ol
  参考文献：
  名称：

  An Alkoxide-Directed Carbometalation of Internal Alkynes

  摘要：

  A mild and efficient alkoxide-directed carbometalation is described. Regioselective carbon-carbon bond formation occurs in all cases at the site distal to the tethered alkoxide. This reaction provides a convenient means to prepare differentially functionalized tetrasubstituted 1,3-dienes in a regio- and stereoselective manner.

  DOI：

  10.1021/ja057352w
• 作为产物：
  描述：

  (2S,3R,4S)-1-(benzyloxy)-2,4-dimethyl-5-heptyn-3-ol 、 4-甲氧基氯苄 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 以96%的产率得到(2S,3R,4S)-1-(benzyloxy)-3-(4-methoxybenzyloxy)-2,4-dimethyl-5-heptyne
  参考文献：
  名称：

  Group 4 Metals in Polyketide Synthesis:  A Convergent Strategy for the Synthesis of Polypropionate-derived (E,E)-Trisubstituted 1,3-Dienes

  摘要：

  A convergent Group 4 metal-mediated coupling process is described for the synthesis of polypropionate-derived (EE)-1,3-dienes. Both the stereochemistry of the internal alkyne and the presence/absence of a tethered alkoxide on this pi-component were found to play critical roles in dictating the regiochemical course of these reactions.

  DOI：

  10.1021/ol052241n

文献信息

• Stereoselective Synthesis of Trisubstituted (<i>E</i>,<i>E</i>)-1,3-Dienes by the Site-Selective Reductive Cross-Coupling of Internal Alkynes with Terminal Alkynes: A Fragment Coupling Reaction for Natural Product Synthesis
  作者：Lark J. Perez、Heidi L. Shimp、Glenn C. Micalizio

  DOI：10.1021/jo901451c

  日期：2009.10.2

  olefinic coupling partners (vinyl halide or vinyl organometallic); it proceeds by a single convergent C−C bond-forming event (avoiding multistep methods based on carbonyl olefination) and is tolerant of a diverse array of functional groups including free hydroxyls. Through a systematic study of titanium-mediated reductive cross-coupling reactions of internal alkynes with terminal alkynes, a fragment

  描述了炔烃之间高度选择性的收敛偶联反应，用于合成立体定义的三取代（E，E）-1,3-二烯-通常在生物活性聚酮化合物衍生的天然产物的骨架中嵌入的结构基序。尽管存在许多合成该立体定义的官能团的多步骤方法，但是由于不需要立体定义的烯烃偶联伴侣（乙烯基卤化物或乙烯基有机金属），当前的方法代表了重大进步。它通过单个会聚的C-C键形成事件来进行（避免基于羰基烯化的多步方法），并且能够耐受包括游离羟基在内的多种官能团。通过对钛介导的内部炔烃与末端炔烃的还原性交叉偶联反应的系统研究，已经出现了在天然产物合成中非常有用的片段偶联反应。这里，在预先形成的钛环丙烯的官能化中使用近端羟基控制区域选择导致了高选择性双分子偶联过程的建立，其中CC键的形成与两个立体定义的烯烃的建立相一致。与已知的有关金属介导的偶联反应的文献相比，当前的工作定义了一项有力的进步，无需使用TMS-炔烃或共轭炔烃即可实现位点选择性双分子C-
• Group 4 Metals in Polyketide Synthesis:  A Convergent Strategy for the Synthesis of Polypropionate-derived (<i>E</i>,<i>E</i>)-Trisubstituted 1,3-Dienes
  作者：Heidi L. Shimp、Glenn C. Micalizio

  DOI：10.1021/ol052241n

  日期：2005.10.1

  A convergent Group 4 metal-mediated coupling process is described for the synthesis of polypropionate-derived (EE)-1,3-dienes. Both the stereochemistry of the internal alkyne and the presence/absence of a tethered alkoxide on this pi-component were found to play critical roles in dictating the regiochemical course of these reactions.
• An Alkoxide-Directed Carbometalation of Internal Alkynes
  作者：Jamie Ryan、Glenn C. Micalizio

  DOI：10.1021/ja057352w

  日期：2006.3.1

  A mild and efficient alkoxide-directed carbometalation is described. Regioselective carbon-carbon bond formation occurs in all cases at the site distal to the tethered alkoxide. This reaction provides a convenient means to prepare differentially functionalized tetrasubstituted 1,3-dienes in a regio- and stereoselective manner.