(3R) methyl 3-hydroxy-3-cyclohexylpropanoate | 142037-74-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (3R) methyl 3-hydroxy-3-cyclohexylpropanoate
• 英文别名: (R)-methyl 3-cyclohexyl-3-hydroxypropanoate；(R)-methyl 3-cyclohexyl-3-hydroxypropionate；methyl (R)-3-hydroxy-3-cyclohexylpropanoate；methyl (3R)-3-cyclohexyl-3-hydroxypropanoate
• CAS: 142037-74-9
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: PAKFURKPPSCHAX-SECBINFHSA-N

物化性质

• 沸点：
  295.8±13.0 °C(Predicted)
• 密度：
  1.057±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (3R) methyl 3-hydroxy-3-cyclohexylpropanoate 在 氢氧化钾 作用下， 生成 (3R)-3-cyclohexyl-3-hydroxypropanoic acid
  参考文献：
  名称：

  Burk, Mark J.; Harper, T. Gregory P.; Kalberg, Christopher S., Journal of the American Chemical Society, 1995, vol. 117, # 15, p. 4423 - 4424

  摘要：

  DOI：
• 作为产物：
  描述：

  3-环己基-3-氧代丙酸甲酯 在 1,2-bis[(R,R)-2,5-diisopropylphospholano]ethane-RuBr₂ 、 氢气 作用下， 以 甲醇 、 水 为溶剂， 35.0 ℃ 、413.68 kPa 条件下， 反应 20.0h， 生成 (3R) methyl 3-hydroxy-3-cyclohexylpropanoate
  参考文献：
  名称：

  Burk, Mark J.; Harper, T. Gregory P.; Kalberg, Christopher S., Journal of the American Chemical Society, 1995, vol. 117, # 15, p. 4423 - 4424

  摘要：

  DOI：

文献信息

• Lewis Base Activation of Lewis Acids:  Catalytic, Enantioselective Addition of Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Gregory L. Beutner、Thomas Wynn、Martin D. Eastgate

  DOI：10.1021/ja047339w

  日期：2005.3.1

  The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent

  路易斯酸的路易斯碱活化的概念已被简化用于催化甲硅烷基乙烯酮缩醛和甲硅烷基二烯醇醚与醛的羟醛反应。弱酸性物质四氯化硅 (SiCl4) 可以通过结合强路易斯碱性手性磷酰胺而被激活，导致手性路易斯酸的原位形成。该物质已被证明是将乙酸酯、丙酸酯和异丁酸酯衍生的甲硅烷基乙烯酮缩醛与共轭和非共轭醛进行羟醛加成反应的有效催化剂。此外，还证明了甲硅烷基二烯醇醚的乙烯基羟醛反应。高水平的区域-，抗非对映-，
• Efficient Enantioselective Synthesis of Methyl Esters of α-Unsubstituted β-Hydroxy Acids via Asymmetric Aldol-Type Addition of Chiral Boron Enolates of (Methylthio)acetic Acid to Aldehydes
  作者：Francesco Fringuelli、Oriana Piermatti、Ferdinando Pizzo

  DOI：10.1055/s-1996-4365

  日期：1996.10

  The aldol-type addition of chiral boron enolates of (methylthio)-acetic acid to various aldehydes gives α-(methylthio)-β-hydroxy acids stereoselectively and with good yields. The desulfenylation of methyl esters of the condensation adducts allows methyl esters of α-unsubstituted β-hydroxy acids to be obtained with high ee. Derivatives of (+)-2- and (+)-3-carene were used as chiral inducers. The enantioselectivity and diastereoselectivity of the aldol-type addition are efficaciously controlled by the SMe group in the α-position of the enolate and by the type of chiral ligand used.

  (甲硫基)乙酸的手性硼烯醇盐与各种醛进行aldol型加成反应，可以立体选择性地并以良好产率得到α-(甲硫基)-β-羟基酸。通过脱硫作用，可以将缩合加合物的甲酯转化为高对映体纯度的α-未取代-β-羟基酸的甲酯。使用(+)-2-蒎烯和(+)-3-蒎烯的衍生物作为手性诱导剂。aldol型加成的对映选择性和非对映选择性有效地受到烯醇盐α-位上的SMe基团和所用手性配体类型的控制。
• Over 98% Optical Yield Achieved by a Heterogeneous Catalysis. Substrate Design and Analysis of Enantio-Differentiating Factors of Tartaric Acid-Modified Raney Nickel Hydrogenation
  作者：Takashi Sugimura、Satoshi Nakagawa、Akira Tai

  DOI：10.1246/bcsj.75.355

  日期：2002.2

  Tartaric acid-modified Raney nickel (TA-MRNi) is a chiral heterogeneous catalyst for the hydrogenation of prochiral ketones. An optical yield (OY) of 86% with methyl acetoacetate (1) as a substrate was improved to 94–96% by employing β-keto esters having a proper bulkiness at the γ -position. The γ -bulkiness effect contributes to a high intrinsic enantio-differentiating ability (factor-i) of the TA-MRNi catalysis. Through the study, we found the best substrate, γ -cyclopropyl-β-keto ester, the hydrogenation of which resulted in 98.6% OY. This further improvement in the OY was ascribed to a smaller contribution of non-enantio-differentiating hydrogenation (N-site catalysis) due to the substrate-specific activation of the enantio-differentiating hydrogenation by the chiral modifier. The OY of the hydrogenation of 1 was analyzed by comparing with well-behaved β-keto esters, and the contribution of the factor-i and the N-site to the OY value was evaluated to deduce the origin of the enantiodifferentiation.

  酒石酸改性的Raney镍(TA-MRNi)是一种手性非均相催化剂，用于前手性酮的氢化反应。以乙酰乙酸甲酯(1)为底物，光学收率(OY)为86%，当采用在γ位置具有适当体积的β-酮酯时，OY提高至94-96%。γ体积效应有助于TA-MRNi催化剂具有高固有的手性区分能力(因子-i)。通过研究，我们发现最佳底物，即γ-环丙基-β-酮酯，其氢化反应的光学收率达到了98.6%。这一光学收率的进一步提升归因于底物特定的手性修饰剂激活手性区分氢化反应，从而减少了非手性区分氢化(N-位点催化)的贡献。通过与表现良好的β-酮酯进行比较，分析了1氢化反应的OY，并评估了因子-i和N-位点对OY值的贡献，从而推导出手性区分的起源。
• Catalytic, Enantioselective Aldol Additions with Methyl and Ethyl Acetate O-Silyl Enolates: A Chiral Tridentate Chelate as a Ligand for Titanium(IV)
  作者：Erick M. Carreira、Robert A. Singer、Wheeseong Lee

  DOI：10.1021/ja00098a065

  日期：1994.9

  Asymmetric catalysis of the Mukaiyama aldol reaction has been reported with complexes derived from Al, B, Sn(II), and Ti(IV). The levels of asymmetric induction for the addition of propionate-, isobutyrate-, and acetate-derived silyl thioketene acetals to aldehydes parallel those obtained with chiral-auxiliary-based methodologies. However, silyl ketene acetals derived from O-alkyl acetates uniformly

  据报道，Mukaiyama 醛醇反应的不对称催化作用是使用衍生自 Al、B​​、Sn(II) 和 Ti(IV) 的配合物。将丙酸、异丁酸和乙酸衍生的甲硅烷基硫酮烯缩醛添加到醛中的不对称诱导水平与使用基于手性助剂的方法获得的水平相似。然而，衍生自 O-烷基乙酸酯的甲硅烷基乙烯酮缩醛均匀地提供了具有较低水平不对称诱导的醛缩醇。我们启动了一项旨在设计和合成手性 Ti (IV) 配合物的研究，该配合物可催化 O-三甲基甲硅烷基、O-甲基和 O-乙基乙烯酮缩醛与醛的对映选择性 Mukaiyama 醛醇。我们在此报告了一种催化剂，该催化剂由衍生自 3、Ti(O'^iPr)_4 和 3,5-二叔丁基水杨酸的三齿配体组成。
• Asymmetric synthesis of secondary alcohols from primary alcohols via intramolecular carbenoid C–H insertion catalyzed by rhodium(<scp>ii</scp>) 3-phenylcholestane-2-carboxylate
  作者：Cheol Hee Hwang、You Hoon Chong、Sue Yeon Song、Hyo Shin Kwak、Eun Lee

  DOI：10.1039/b316984g

  日期：——

  Chiral secondary alcohols may be prepared from primary alcohols via asymmetric C-H insertion reactions of alpha'-alkoxy-alpha-diazoketones catalyzed by rhodium(II)(2R,3R)-3-phenylcholestane-2-carboxylate.

  可以通过伯醇（II）（2R，3R）-3-苯基胆甾烷-2-羧酸酯催化的α'-烷氧基-α-二氮酮的不对称CH插入反应，由伯醇制备手性仲醇。