rac-(1R,2S,3R)-1-isopropyl-3-hydroxy-2-methylpentyl isopropylcarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: rac-(1R,2S,3R)-1-isopropyl-3-hydroxy-2-methylpentyl isopropylcarboxylate
• 英文别名: [(3S,4R,5S)-5-hydroxy-2,4-dimethylheptan-3-yl] 2-methylpropanoate
• 化学式: C₁₃H₂₆O₃
• 分子量: 230.348
• InChiKey: WDCSYGZAOLLBMT-WOPDTQHZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  rac-(1R,2S,3R)-1-isopropyl-3-hydroxy-2-methylpentyl isopropylcarboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 (3RS,4SR,5RS)-2,4-dimethylheptane-3,5-diol
  参考文献：
  名称：

  Toward Asymmetric Aldol-Tishchenko Reactions with Enolizable Aldehydes: Access to Defined Configured Stereotriads, Tetrads, and Stereopentads

  摘要：

  Asymmetric aldol-Tishchenko, reactions of enolizable aldehydes and ketones in the presence of chiral BINOLTi(OtBU)(2)/Cinchona alkaloids complexes are described. Different configurative outcomes of these reactions depend on an equilibration through a retro aldol/aldol sequence and can be influenced by the configurative architecture of substrates. The results are explained by means of transition state models and rate constants. These considerations offer a fine-tuning of diastereoselectivity in aldol-Tishchenko reactions. Extensions of this research give access to defined configured stereotriads, stereotetrads, and stereopentads.

  DOI：

  10.1021/jo9003635
• 作为产物：
  描述：

  5-hydroxy-4,6-dimethyl-3-heptanone 、 异丁醛 在 titanium(IV) tetrabutoxide 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,2R,3R)-1-isopropyl-3-hydroxy-2-methylpentyl isopropylcarboxylate 、 rac-(1R,2S,3R)-1-isopropyl-3-hydroxy-2-methylpentyl isopropylcarboxylate
  参考文献：
  名称：

  Toward Asymmetric Aldol-Tishchenko Reactions with Enolizable Aldehydes: Access to Defined Configured Stereotriads, Tetrads, and Stereopentads

  摘要：

  Asymmetric aldol-Tishchenko, reactions of enolizable aldehydes and ketones in the presence of chiral BINOLTi(OtBU)(2)/Cinchona alkaloids complexes are described. Different configurative outcomes of these reactions depend on an equilibration through a retro aldol/aldol sequence and can be influenced by the configurative architecture of substrates. The results are explained by means of transition state models and rate constants. These considerations offer a fine-tuning of diastereoselectivity in aldol-Tishchenko reactions. Extensions of this research give access to defined configured stereotriads, stereotetrads, and stereopentads.

  DOI：

  10.1021/jo9003635

文献信息

• Samarium Ion-Promoted Cross-Aldol Reactions and Tandem Aldol/Evans−Tishchenko Reactions
  作者：Ling Lu、Hung-Yu Chang、Jim-Min Fang

  DOI：10.1021/jo981675b

  日期：1999.2.1

  effective Lewis acids to catalyze tandem aldol/Evans-Tishchenko reactions. The aldol/Evans-Tishchenko reactions of methyl ketones with aldehydes occurred at 0 degrees C to give alpha,gamma-anti diol monoesters 53a-59a. When the reactions were conducted at room temperature, a certain degree of transesterification took place. The aldol/Evans-Tishchenko reactions of ethyl or benzyl ketones with aldehydes

  通过在环境温度下SmI（2）或SmI（3）以及分子筛的催化，可以实现羰基化合物的跨醇醛反应。在与供体底物如丙酮，环戊酮和环己酮的交叉醇醛缩合反应中，可以将1，3-二氯丙酮和1-氯丙酮用作受体底物。与（R）-甘油醛丙酮化物的交叉醛醇缩合反应产生光学纯的化合物25-32，其立体化学与偶极模式的椅子状螯合物过渡态一致。SmI（2）分子筛或SmI（3）分子筛也可作为有效的路易斯酸来催化串联羟醛/埃文斯-季申科反应。甲基酮与醛的aldol / Evans-Tishchenko反应在0℃下发生，得到α，γ-抗二醇单酯53a-59a。当反应在室温下进行时，发生了一定程度的酯交换反应。乙基或苄基酮与醛的aldol / Evans-Tishchenko反应生成α，β-抗-α，γ-抗二醇单酯60a-65a。然而，环状酮与苯甲醛的醛醇/埃文斯-季申科反应以不同的立体选择性发生，得到α，β-syn-α，γ-抗二醇
• Titanium-Mediated Aldol-Tishchenko Reaction: A Stereoselective Synthesis of Differentiated anti 1,3-Diol Monoesters
  作者：Rainer Mahrwald、Burkhard Costisella

  DOI：10.1055/s-1996-4339

  日期：1996.9

  anti 1,3-Diol monoesters were obtained in a high level of stereoselectivity by a one-pot aldol-Tishchenko reaction of ketones with aldehydes using substoichiometric amounts of titanium ate complexes.

  通过酮与醛在亚化学计量量的钛配合物存在下进行的一锅法羟醛缩合-Tishchenko反应，高效地获得了anti 1,3-二醇单酯产物，并展现出高度的立体选择性。
• Toward Asymmetric Aldol-Tishchenko Reactions with Enolizable Aldehydes: Access to Defined Configured Stereotriads, Tetrads, and Stereopentads
  作者：Kerstin Rohr、Robert Herre、Rainer Mahrwald

  DOI：10.1021/jo9003635

  日期：2009.5.15

  Asymmetric aldol-Tishchenko, reactions of enolizable aldehydes and ketones in the presence of chiral BINOLTi(OtBU)(2)/Cinchona alkaloids complexes are described. Different configurative outcomes of these reactions depend on an equilibration through a retro aldol/aldol sequence and can be influenced by the configurative architecture of substrates. The results are explained by means of transition state models and rate constants. These considerations offer a fine-tuning of diastereoselectivity in aldol-Tishchenko reactions. Extensions of this research give access to defined configured stereotriads, stereotetrads, and stereopentads.