3-羟基-4,4-二甲基戊酸甲酯 | 150943-32-1

• 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
• 中文名称: 3-羟基-4,4-二甲基戊酸甲酯
• 英文名称: (+/-)-methyl 3-hydroxy-4,4-dimethylpentanoate
• 英文别名: methyl 3-hydroxyl-4,4-dimethylpentanoate；methyl 3-hydroxy-4,4-dimethylpentanoate；methyl 3-hydroxy-4,4-dimethylvalerate；3-hydroxy-4,4-dimethyl-pentanoic acid methyl ester
• CAS: 150943-32-1
• 化学式: C₈H₁₆O₃
• 分子量: 160.213
• InChiKey: PRKGPKOSRBEOHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  69 °C(Press: 0.08 Torr)
• 密度：
  0.988±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  3-羟基-4,4-二甲基戊酸甲酯 在 palladium on activated charcoal 四氯化碳 、 氢气 、 三甲基铝 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 作用下， 以 甲醇 、 正庚烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 生成 (+/-)-4-((1,1-dimethyl)ethyl)-1-tosyloxy-2-azetidinone
  参考文献：
  名称：

  Enantioselective Synthesis of α-Amino Acids from N-Tosyloxy β-Lactams Derived from β-Keto Esters

  摘要：

  A novel synthetic sequence has been developed to convert simple beta-keto esters into enantiomerically enriched alpha-amino acids. The key features of this sequence include the addition of azide to the C3 position of beta-keto ester derived N-tosyloxy-beta-lactams through a concomitant nucleophilic addition/ N-O bond reduction reaction, a mild CsF-induced N1 benzylation of a-azido monocyclic beta-lactams, the preparation of alpha-keto-beta-lactams through a novel four-step sequence from the corresponding 3-azido-1-benzyl-beta-lactams, and TEMPO-mediated ring expansion of these compounds to the corresponding N-carboxy anhydrides (NCAs). In addition, the synthesis, isolation, and characterization of unusual 3-imino and 3-chloramino-beta-lactams is reported.

  DOI：

  10.1021/jo0162437
• 作为产物：
  描述：

  1-(三甲基乙酰基)咪唑 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 3-羟基-4,4-二甲基戊酸甲酯
  参考文献：
  名称：

  Enantioselective Synthesis of α-Amino Acids from N-Tosyloxy β-Lactams Derived from β-Keto Esters

  摘要：

  A novel synthetic sequence has been developed to convert simple beta-keto esters into enantiomerically enriched alpha-amino acids. The key features of this sequence include the addition of azide to the C3 position of beta-keto ester derived N-tosyloxy-beta-lactams through a concomitant nucleophilic addition/ N-O bond reduction reaction, a mild CsF-induced N1 benzylation of a-azido monocyclic beta-lactams, the preparation of alpha-keto-beta-lactams through a novel four-step sequence from the corresponding 3-azido-1-benzyl-beta-lactams, and TEMPO-mediated ring expansion of these compounds to the corresponding N-carboxy anhydrides (NCAs). In addition, the synthesis, isolation, and characterization of unusual 3-imino and 3-chloramino-beta-lactams is reported.

  DOI：

  10.1021/jo0162437

文献信息

• Exploring the Synthetic Applicability of a Cyanobacterium Nitrilase as Catalyst for Nitrile Hydrolysis
  作者：Chandrani Mukherjee、Dunming Zhu、Edward R. Biehl、Ling Hua

  DOI：10.1002/ejoc.200600699

  日期：2006.12

  specificity and synthetic applicability of the nitrilase from cyanobacterium Synechocystis sp. strain PCC 6803 have been examined. This nitrilase catalyzed the hydrolysis of both aromatic and aliphatic nitriles to the corresponding acids in high yields. Furthermore, the stereoselective hydrolysis of phenyl-substituted β-hydroxy nitriles to (S)-enriched β-hydroxy carboxylic acids and selective hydrolysis of α

  蓝藻集胞藻腈水解酶的底物特异性和合成适用性。菌株 PCC 6803 已被检查。这种腈水解酶以高产率催化芳香族和脂肪族腈水解为相应的酸。此外，还实现了苯基取代的 β-羟基腈立体选择性水解为 (S) 富集的 β-羟基羧酸，以及具有五个或更少亚甲基的 α,ω-二腈选择性水解为 ω-氰基羧酸。这表明来自集胞藻属的腈水解酶。PCC 6803 可能是“绿色”腈水解的有用酶催化剂。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Development of an axially chiral sp3P/sp3NH/sp2N-combined linear tridentate ligand—fac-selective formation of Ru(II) complexes and application to ketone hydrogenation
  作者：Tomoya Yamamura、Satoshi Nakane、Yuko Nomura、Shinji Tanaka、Masato Kitamura

  DOI：10.1016/j.tet.2016.02.007

  日期：2016.6

  A newly developed chiral linear tridentate ligand, R-PN(H)N (R=H or Ph), possesses Ph2P and PyCH2NH groups at C(2) and C(2′) positions of the 1,1′-binaphthyl skeleton without or with a C(3)-Ph substituent. The steric effect of C(3)-Ph and the electronic effect of the DMSO co-ligand realize the facial selective generation of fac-RuCl2(Ph-PN(H)N)(dmso) and fac-[Ru(H-PN(H)N)(dmso)3](BF4)2, respectively

  一种新开发的手性线性三齿配体R-PN（H）N（R = H或Ph），在1,1'的C（2）和C（2'）位置具有Ph 2 P和PyCH 2 NH基团-具有或没有C（3）-Ph取代基的-萘基骨架。C（3）-Ph的空间效应和DMSO共配体的电子效应实现了fac -RuCl 2（Ph-PN（H）N）（DMSO）和fac- [Ru（H- PN（H）N）（DMSO）3 ]（BF 4）2。H-Ru advantageoussp 3 N-H反应位点负责给体-受体双功能催化剂（DACat）和围栏/平面手性环境，均通过以下优点构建：i）sp3 P，sp 3 N和sp 2 N的连接原子具有不同的电子性质；ii）DMSO反式至sp 3 N与Ru强烈配位，并被PyC（6）H = O S氢键固定 iii）单个NH功能简化了DACat反应位点。协同作用已成功地实现了对空间需求的酮的不对称氢化。还研究了R-PN（H）N第一行过渡金属配合物的结构特征。
• Reduction of aromatic and aliphatic keto esters using sodium borohydride/MeOH at room temperature: a thorough investigation
  作者：Juryoung Kim、Kathlia A. De Castro、Minkyung Lim、Hakjune Rhee

  DOI：10.1016/j.tet.2010.04.062

  日期：2010.6

  Reduction of keto esters is a valuable alternative to produce diols. Sodium borohydride/MeOH system at room temperature and short reaction time efficiently reduced α, β, γ, and δ-keto esters having α-keto esters as the most reactive. The ester functionality was reduced effectively due to the presence of oxo group that somehow facilitates the formation of ring intermediate. As expected, the chemoselective

  还原酮酯是生产二醇的有价值的替代方法。在室温和短的反应时间下，硼氢化钠/ MeOH系统有效地还原了以α-酮酸酯为最具反应性的α，β，γ和δ-酮酸酯。由于存在以某种方式促进环中间体形成的氧代基团，有效地降低了酯的官能度。如预期的那样，化学选择性实验表明，使用该系统不会降低酯的官能度。这项研究提出了各种酮酯向其相应的二醇的简单，简便且良性的还原过程。
• Hydroxy-Directed Amidation of Carboxylic Acid Esters Using a Tantalum Alkoxide Catalyst
  作者：Hiroaki Tsuji、Hisashi Yamamoto

  DOI：10.1021/jacs.6b09482

  日期：2016.11.2

  the chemoselective synthesis of amides by using a metal-catalyzed hydroxy-directed reaction. A hydroxy group located at the β-position of an ester group promoted the activation of a carbonyl group with a tantalum alkoxide catalyst followed by amidation reactions, leading to a wide variety of β-hydroxyamides with excellent chemeselectivity. The chemoselective amidation strategy can be extended to the

  我们在此描述了一种通过使用金属催化的羟基定向反应化学选择性合成酰胺的新策略。位于酯基 β 位的羟基促进了羰基在烷氧基钽催化剂下的活化，随后进行了酰胺化反应，从而产生了多种具有优异化学选择性的 β-羟基酰胺。化学选择性酰胺化策略可以扩展到二肽衍生物的催化合成，这在现代有机合成中仍然是具有挑战性的研究课题。
• Asymmetric Hydrogenation of<i>tert</i>-Alkyl Ketones: DMSO Effect in Unification of Stereoisomeric Ruthenium Complexes
  作者：Tomoya Yamamura、Hiroshi Nakatsuka、Shinji Tanaka、Masato Kitamura

  DOI：10.1002/anie.201304408

  日期：2013.8.26

  Face off: The ruthenium complexes of a new axially chiral PNN ligand (L) are highly efficient in the presence of dimethylsulfoxide (DMSO) for hydrogenation of both functionalized and unfunctionalized tert‐alkyl ketones. DMSO is thought to narrow down the many possible complex stereoisomers into a single facial L/Ru complex, thus enhancing the reactivity, selectivity, and productivity.

  面临的挑战：新型的轴向手性PNN配体（L）的钌络合物在二甲基亚砜（DMSO）的存在下对官能化和未官能化叔烷基酮的加氢都非常有效。DMSO被认为可以将许多可能的复杂立体异构体缩小为单个面部L / Ru复杂物，从而提高了反应性，选择性和生产率。

表征谱图