(R)-methyl 3-hydroxyhexanoate | 109053-86-3

• 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: (R)-methyl 3-hydroxyhexanoate
• 英文别名: methyl (3R)-3-hydroxyhexanoate
• CAS: 109053-86-3
• 化学式: C₇H₁₄O₃
• 分子量: 146.186
• InChiKey: ACCRBMDJCPPJDX-ZCFIWIBFSA-N

物化性质

• 沸点：
  80-82 °C(Press: 8 Torr)
• 密度：
  0.999 g/cm3(Temp: 23 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  (R)-methyl 3-hydroxyhexanoate 在 lithium aluminium tetrahydride 作用下， 生成 (R)-(-)-hexane-1,3-diol
  参考文献：
  名称：

  Hosokawa, Takahiro; Shinohara, Toru; Ooka, Yoshiharu, Chemistry Letters, 1989, p. 2001 - 2004

  摘要：

  DOI：
• 作为产物：
  描述：

  3-acetoxy-pentanedioic acid monomethyl ester 在 盐酸 、 甲醇 、 sodium 作用下， 生成 (R)-methyl 3-hydroxyhexanoate
  参考文献：
  名称：

  两相介质中1,2-二氢异喹啉在1,2-二氢异喹啉上的芳基亚硝酸盐的偶极1,3-环加成反应

  摘要：

  1,2-二氢异喹啉衍生物上芳基腈的1,3-偶极环加成反应生成新的3-芳基，3a-8,9,9a-四氢[5,4- c ]-异恶唑异喹啉加合物。基于1 H和13 C NMR数据讨论了环加成反应的区域选择性。

  DOI：

  10.1002/jhet.5570370639

文献信息

• Chiral Surfactant-Type Catalyst: Enantioselective Reduction of Long-Chain Aliphatic Ketoesters in Water
  作者：Zechao Lin、Jiahong Li、Qingfei Huang、Qiuya Huang、Qiwei Wang、Lei Tang、Deying Gong、Jun Yang、Jin Zhu、Jingen Deng

  DOI：10.1021/acs.joc.5b00241

  日期：2015.5.1

  ligands were designed and synthesized. The rhodium complexes with the ligands were applied to the asymmetric transfer hydrogenation of broad range of long-chained aliphatic ketoesters in neat water. Quantitative conversion and excellent enantioselectivity (up to 99% ee) was observed for α-, β-, γ-, δ- and ε-ketoesters as well as for α- and β-acyloxyketone using chiral surfactant-type catalyst 2. The CH/π

  设计并合成了一系列两亲性配体。具有配体的铑配合物被用于纯水中宽范围的长链脂族酮酸酯的不对称转移氢化。使用手性表面活性剂型催化剂2观察到α-，β-，γ-，δ-和ε-酮酸酯以及α-和β-酰氧基酮的定量转化率和出色的对映选择性（高达99％ee）。在金属硅油核中，催化剂与底物之间的长脂肪链之间的CH /π相互作用和长脂肪链的强疏水相互作用在催化过渡态中起着关键作用。胶束中金属催化位点与核心的疏水微环境之间的协同作用有助于实现高立体选择性。
• Development of Chiral Spiro P-N-S Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of β-Alkyl-β-Ketoesters
  作者：Deng-Hui Bao、Hui-Ling Wu、Chao-Lun Liu、Jian-Hua Xie、Qi-Lin Zhou

  DOI：10.1002/anie.201502860

  日期：2015.7.20

  The chiral tridentate spiro P‐N‐S ligands (SpiroSAP) were developed, and their iridium complexes were prepared. Introduction of a 1,3‐dithiane moiety into the ligand resulted in a highly efficient chiral iridium catalyst for asymmetric hydrogenation of β‐alkyl‐β‐ketoesters, producing chiral β‐alkyl‐β‐hydroxyesters with excellent enantioselectivities (95–99.9 % ee) and turnover numbers of up to 355 000

  研发了手性三齿螺旋螺-N‐S配体（SpiroSAP），并制备了其铱配合物。在配体中引入1,3-二硫杂环丁烷部分产生了高效的手性铱催化剂，用于β-烷基-β-酮酸酯的不对称加氢，生成具有出色对映选择性（95-99.9％ee的手性β-烷基-β-羟基酯）），营业额高达355 000。
• 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。
• Formamide compounds as therapeutic agents
  申请人：Glaxo Wellcome Inc.

  公开号：US06191150B1

  公开（公告）日：2001-02-20

  A family of compounds having the general structural formula where W is a reverse hydroxamic acid group, and R1, R2, R3, R4, R5 and R6 are as described in the specification, or a pharmaceutically acceptable salt, solvate, biohydrolyzable ester, biohydrolyzable amide, affinity reagent, or prodrug thereof.

  具有一般结构式的化合物家族，其中W是一个反向羟肟酸基团，而R1、R2、R3、R4、R5和R6如规范中所述，或其药学上可接受的盐、溶剂化合物、生物水解酯、生物水解酰胺、亲和试剂或其前药。
• 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。